The Royal Society of Chemistry · To the ArZnI residue was added NiBr. 2 (0.4-1.1 mg, 2-5 mol%), 2-(dimethyl(vinyl)silyl)pyridine (16.3 mg, 0.1 mmol), and aryl halide (0.10 mmol)

SI-1

Ni-Catalyzed Regioselective 1,2-Diarylation of Unactivated Olefins by Stabilizing Heck Intermediates as Pyridylsilyl-Coordinated Transient Metallacycles

Surendra Thapa,‡ Roshan K. Dhungana,‡ Rajani Thapa Magar, Bijay Shrestha, Shekhar KC, and

Ramesh Giri*

Department of Chemistry & Chemical Biology, The University of New Mexico, Albuquerque, NM 87131, USA

Table of Contents

1. General Information .............................................................................................................................. 2

2. Substrate Preparation ............................................................................................................................ 2

3. Experimental Section ............................................................................................................................ 4

3.1. General Procedure for the Preparation of Organozinc Reagents .................................................. 4

3.2. General Procedure for Screening Reaction Conditions ................................................................ 4

3.3. General Procedure for Table 2 and 3 ............................................................................................ 4

3.4. Characterization Data for New Compounds ................................................................................. 5

4. References ........................................................................................................................................... 20

Electronic Supplementary Material (ESI) for Chemical Science.This journal is © The Royal Society of Chemistry 2017

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1. General Information Reactions were set up in a nitrogen-filled glovebox unless stated otherwise. All glassware were properly

dried in an oven before use. Bulk solvents were obtained from EMD and BDH. Anhydrous solvents (DMF,

DMA, DMSO, NMP, THF, toluene, dioxane) were obtained from Sigma-Aldrich and were used directly

without further purification. Deuterated solvents were purchased from Sigma-Aldrich. Aryl halides were

purchased from Acros, Sigma-Aldrich, Oakwood, TCI-America, Matrix and Alfa-Aesar. NiBr2 was

procured from Alfa-Aesar and 2-bromopyridine was obtained from Oxychem. 1H, 13C, and 19F NMR spectra

were recorded on a Bruker instrument (300, 75, and 282, respectively) and internally referenced to the

residual solvent signals of CDCl3 for 1H and 13C NMR at 7.26 and 77.16 ppm, respectively, and C6F6 for 19F NMR at −164.9 ppm. NMR chemical shifts (δ) and the coupling constants (J) for 1H, 13C, and 19F NMR

are reported in parts per million (ppm) and in Hertz, respectively. The following conventions are used for

multiplicities: s, singlet; d, doublet; t, triplet; m, multiplet; and dd, doublet of doublet. High resolution mass

and NMR spectra of new compounds were recorded at the Mass Spectrometry and NMR Facilities,

Department of Chemistry and Chemical Biology, University of New Mexico (UNM). Infrared (IR) spectra

were recorded on Bruker Alpha-P ATR-IR, νmax in cm-1.

2. Substrate Preparation

2-(Dimethyl(vinyl)silyl)pyridine (7): This compound was prepared according to a literature procedure.1

2-(Dimethyl(vinyl)silyl)-4-methylpyridine (8): This compound was prepared according to a literature

procedure.1 1H NMR (300 MHz, CDCl3) 0.39 (s, 6H), 2.30 (s, 3H), 5.80 (dd, J = 5.4, 20.9 Hz, 1H), 6.08

(dd, J = 5.6, 16.5 Hz, 1H), 6.33 (dd, J = 16.3, 21.8 Hz, 1H), 7.00 (d, J = 4.6 Hz, 1H), 7.29 (d, J = 16.5 Hz,

1H), 8.62 (d, J = 4.9 Hz, 1H); 13C NMR (75 MHz, CDCl3) -3.5, 21.1, 123.9, 130.6, 133.4, 137.2, 144.9,

150.1, 166.1.

SI-3

8-(Dimethyl(vinyl)silyl)quinolone (9): This compound was prepared according to a literature procedure.1 1H NMR (300 MHz, CDCl3) 0.59 (s, 6H), 5.86 (dd, J = 7.0, 20.4 Hz, 1H), 6.09 (dd, J = 6.7, 14.6 Hz, 1H),

6.68 (dd, J = 14.6, 20.4 Hz, 1H), 7.37 (dd, J = 4.1, 8.2 Hz, 1H), 7.52 (dd, J = 6.8, 8.0 Hz, 1H), 7.82 (d, J =

9.3 Hz, 1H), 7.91 (d, J = 6.7 Hz, 1H), 8.11 (d, J = 8.2 Hz, 1H), 8.93 (d, J = 4.2 Hz, 1H); 13C NMR (75

MHz, CDCl3) -1.8, 120.8, 126.1, 127.8, 129.3, 131.8, 136.1, 136.3, 139.8, 140.3, 149.2, 152.7.

8-(Dimethyl(vinyl)silyl)quinolone (10): This compound was prepared according to a literature procedure.2

2,2'-(Methyl(vinyl)silanediyl)dipyridine (11): This compound was prepared according to a literature

procedure.3

2-(Dimethyl(vinyl)silyl)-N,N-dimethylaniline (12): This compound was prepared according to a literature

procedure.1 1H NMR (300 MHz, CDCl3) 0.41 (s, 6H), 2.65 (s, 6H), 5.76 (dd, J = 18.0, 6.0 Hz, 1H), 6.03

(dd, J = 15.0, 6.0 Hz, 1H), 6.45 (dd, J = 18.0, 12.0 Hz, 1H), 7.19 (t, J = 7.5 Hz, 1H), 7.31 (d, J = 9.0 Hz,

1H), 7.41 (t, J = 9.0 Hz, 1H), 7.52 (d, J = 9.0 Hz, 1H); 13C NMR (75 MHz, CDCl3) -1.80, 47.0, 121.7,

125.0, 130.6, 131.1, 135.8, 136.9, 140.2, 161.4.

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2-(Dimethyl(vinyl)silyl)-4-methylpyridine (13): This compound was prepared according to a literature

procedure.1 1H NMR (300 MHz, CDCl3) 0.42 (s, 6H), 3.85 (s, 3H), 5.76-5.85 (m, 1H), 6.04-6.11 (m, 1H),

6.39-6.51 (m, 1H), 6.88 (d, J = 6.0 Hz, 1H), 6.97-7.03 (m, 1H), 7.37-7.46 (m, 2H); 13C NMR (75 MHz,

CDCl3) -2.63, 55.2, 109.8, 120.6, 126.4, 131.1, 131.8, 135.6, 138.9, 164.5.

3. Experimental Section

3.1. General Procedure for the Preparation of Organozinc Reagents4

To a Schlenk flask under nitrogen, anhydrous LiCl (1.0 equiv) and Zinc powder (1.5 equiv) was added and

dried under high vacuum at 150°C to 170°C for 2 h. Then the flask was taken to a glovebox, anhydrous

THF was added and stirred at room temperature. Zinc was activated by adding 5 mol% of BrCH2CH2Br

and 3 mol% of TMSCl to the zinc/THF suspension and the mixture was stirred for 5 minutes. To this stirred

solution was added corresponding aryl iodides (neat) dropwise and the reaction mixture was refluxed for

electron-deficient and electron rich aryl iodides. The final concentration of the arylzinc reagent was

determined by titration with molecular iodine in THF.5

3.2. General Procedure for Screening Reaction Conditions

In a glovebox, arylzinc reagent (0.15 mmol) prepared in the lab according to the general procedure was

transferred to a 1-dram borosilicate scintillation vial and the solvent was pumped off under high vacuum.

To the ArZnI residue was added NiBr2 (0.4-1.1 mg, 2-5 mol%), 2-(dimethyl(vinyl)silyl)pyridine (16.3 mg,

0.1 mmol), and aryl halide (0.10 mmol). The mixture was then dissolved in 0.5 ml of NMP. The vial was

tightly capped and placed in a hotplate preheated to 50 °C or at room temperature with vigorous stirring.

After 24 h, the reaction mixture was cooled to room temperature and 50 µL of pyrene (0.01 mmol, 0.2 M

stock solution) as an internal standard was added, diluted with EtOAc (2 mL) and filtered through a short

pad of silica gel in a pipette. The filtrate was then analyzed by GC, GC-MS and 1H NMR.

3.3. General Procedure for Table 2 and 3

In a glovebox, arylzinc reagent (0.75 mmol) prepared in the lab according to the general procedure was

transferred to 15 mL sealed tube and the solvent was removed under vacuum. To the residue of ArZnI was

added NiBr2 (2.1-5.5 mg, 2-5 mol%), 2-(dimethyl(vinyl)silyl)pyridine (81.5 mg, 0.5 mmol), and aryl halide

(0.5 mmol). The mixture was then dissolved in NMP (2.5 mL). The sealed tube was tightly capped, and

SI-5

placed in an oil-bath preheated to 50 °C or at room temperature with vigorous stirring. After 24 h, the

reaction mixture was cooled to room temperature, diluted with EtOAc (10 mL) and washed with H2O (5

mL × 3). The aqueous fraction was extracted back with ethyl acetate (5 mL × 3) and combined with the

first ethyl acetate fraction. The combined ethyl acetate fraction was dried over Na2SO4 and the solvent was

removed in a rotary evaporator. The product was purified by silica gel column chromatography using

diethyl ether/hexanes as eluent.

3.4. Characterization Data for New Compounds

2-((1-(4-Fluorophenyl)-2-(3-(trifluoromethyl)phenyl)ethyl)dimethylsilyl)pyridine (15a): The title

compound 15a was obtained as a colorless oil (138.9 mg, 72% yield, using 2 mol % catalyst) after

purification by silica gel column chromatography by gradient elution using 2-10% ether/hexanes.

1H NMR (300 MHz, CDCl3) 0.21 (s, 3H), 0.39 (s, 3H), 2.84 (app. t, J = 7.9 Hz, 1H), 3.09-3.16 (m, 2H), 6.95-6.98 (m, 2H), 7.01-7.08 (m, 3H), 7.13-7.17 (m, 2H), 7.18-7.23 (m, 1H), 7.30-7.35 (m, 3H), 7.53 (ddd, J = 1.7, 1.7, 1.7 Hz, 1H), 8.80 (d, J = 4.7 Hz, 1H); 13C NMR (75 MHz, CDCl3) -5.7, -4.1, 35.7, 37.1, 122.7, 123.1, 124.9 (q, JCF = 3.75 Hz), 126.3, 128.1 (q, JCF = 31.5 Hz), 128.2, 128.3, 128.8, 129.9, 134.0, 141.7, 146.3, 150.3, 166.1; 19F NMR (282 MHz, CDCl3) -61.0; IR (neat) cm-1 2923, 1322, 1117, 1065; GC-MS for C22H22F3NSi was found to be 385.2.

2-(Dimethyl(1-phenyl-2-(4-(trifluoromethyl)phenyl)ethyl)silyl)-4-methylpyridine (15b): The title

compound 15b was obtained as a colorless oil (101.9 mg, 51% yield, using 2 mol % catalyst) after


1H NMR (300 MHz, CDCl3) 0.12 (s, 3H), 0.39 (s, 3H), 2.28 (s, 3H), 2.85 (t, J = 7.6 Hz, 1H), 3.08-3.15 (m, 2H), 6.98-7.09 (m, 7H), 7.13-7.18 (m, 3H), 7.31 (d, J = 7.7 Hz, 1H), 8.66 (d, J = 4.8 Hz, 1H); 13C NMR (75 MHz, CDCl3) -5.3, -3.6, 21.6, 36.2, 37.4, 124.5, 125.3 (q, JCF = 4.2 Hz), 128.4, 128.5, 128.7, 129.3, 131.5, 142.3, 145.4, 145.7, 150.3, 150.4, 165.7; 19F NMR (282 MHz, CDCl3) -60.8; IR (neat) cm-1 2922, 1324, 1121.

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8-(Dimethyl(1-phenyl-2-(4-(trifluoromethyl)phenyl)ethyl)silyl)quinoline (15c): The title compound 15c

was obtained as a colorless oil (122.0 mg, 56% yield, using 2 mol % catalyst) after purification by silica

gel column chromatography by gradient elution using 2-10% ether/hexanes.

1H NMR (300 MHz, CDCl3) 0.31 (s, 3H), 0.45 (s, 3H), 3.00-3.18 (m, 2H), 3.52 (dd, J = 5.3, 10.3 Hz, 1H), 6.94 (d, J = 7.9 Hz, 2H), 7.04 (dd, J = 7.5, 14.1 Hz, 3H), 7.15 (t, J = 6.1 Hz, 4H), 7.38-7.43 (m, 1H); 7.47 (d, J = 7.4 Hz, 1H), 7.78 ( dd, J = 6.7, 10.5 Hz, 2H), 8.11 (d, J = 8.2 Hz, 1H), 8.96 (d, J = 4.1 Hz, 1H) 13C NMR (75 MHz, CDCl3) -4.6, -2.5, 36.0, 37.2, 120.9, 124.5 (q, JCF = 3.7 Hz), 126.1, 127.3, 127.7, 127.8, 128.0, 128.3, 128.7, 129.6, 136.3, 136.8, 139.4, 143.1, 146.7, 149.1, 152.6; 19F NMR (282 MHz, CDCl3) -60.8; IR (neat) cm-1 2957, 1322, 1118.

2-(Dimethyl(1-phenyl-2-(2-(trifluoromethyl)phenyl)ethyl)silyl)pyridine (16): The title compound 16 was

obtained as a colorless oil (144.6 mg, 75% yield, using 5 mol % catalyst) after purification by silica gel

column chromatography by gradient elution using 2-10% ether/hexanes.

1H NMR (300 MHz, CDCl3) 0.30 (s, 3H), 0.40 (s, 3H), 2.87 (dd, J = 4.5, 10.9 Hz, 1H), 3.25-3.40 (m, 2H), 6.94-7.05 (m, 4H), 7.10-7.21 (m, 5H), 7.36 (app. dd, J = 1.0, 7.5 Hz, 1H), 7.53 (app. dd, J = 6.7, 14.1 Hz, 2H), 8.82 (d, J = 3.7 Hz, 1H); 13C NMR (75 MHz, CDCl3) -5.4, -4.4, 31.6, 36.0, 123.0, 124.9, 125.8 (q, JCF = 7.2 Hz), 126.6, 128.2, 128.5, 128.6, 130.0, 130.7, 131.1, 133.9, 140.4, 141.7, 150.2, 166.0; 19F NMR (282 MHz, CDCl3) -58.0; IR (neat) cm-1 2959, 1309, 1114; HRMS (ESI) Calcd for C22H22F3NSi (M+H)+ 385.1474, found 385.1485.

SI-7

2-((2-(3,5-Bis(trifluoromethyl)phenyl)-1-phenylethyl)dimethylsilyl)pyridine (17): The title compound 17



1H NMR (300 MHz, CDCl3) 0.23 (s, 3H), 0.41 (s, 3H), 2.84 (dd, J = 6.2, 9.7 Hz, 1H), 3.15-3.27 (m, 2H), 6.95-6.95 (m, 2H), 7.05 (app. t, J = 7.3 Hz, 1H), 7.14-7.24 (m, 3H), 7.35-7.40 (m, 3H), 7.55 (ddd, J = 1.5, 1.7, 1.7 Hz, 2H), 8.82 (d, J = 4.8 Hz, 1H); 13C NMR (75 MHz, CDCl3) -5.6, -4.0, 35.9, 37.1, 119.7 (app. q, JCF = 3.75 Hz), 121.7, 123.2, 125.4, 128.2, 128.5, 128.8, 129.9, 131.1 (q, JCF = 32.2 Hz), 134.1, 141.1, 144.6, 150.4, 165.8; 19F NMR (282 MHz, CDCl3) -61.4; IR (neat) cm-1 2959, 1375, 1275, 1125; HRMS (ESI) Calcd for C23H21F6NSi (M+H)+ 453.1347, found 453.1410.

2-((2-(3,4-Dichlorophenyl)-1-phenylethyl)dimethylsilyl)pyridine (18): The title compound 18 was obtained as a colorless oil (94.7 mg, 49% yield, using 5 mol % catalyst) after purification by silica gel column chromatography by gradient elution using 5–20% ether/hexanes.

1H NMR (300 MHz, CDCl3) 0.21 (s, 3H), 0.38 (s, 3H), 2.78 (dd, J = 6.7, 9.0 Hz, 1H), 2.98-3.09 (m, 2H), 6.79 (dd, J = 1.8, 8.2 Hz, 1H), 6.96 (d, J = 8.1 Hz, 2H), 7.02-7.18 (m, 5H), 7.21-7.23 (m, 1H), 7.33 (d, J = 7.5 Hz, 1H), 7.51-7.56 (ddd, J = 1.6, 1.5, 1.4 Hz, 1H), 8.81 (d, J = 4.8 Hz, 1H); 13C NMR (75 MHz, CDCl3) -5.6, -4.0, 35.2, 37.3, 123.1, 125.1, 128.1, 128.2, 128.3, 129.5, 129.8, 129.9, 130.6, 131.9, 134.0, 141.7, 142.5, 150.3, 166.1; IR (neat) cm-1 2956, 1471, 1268; HRMS (ESI) Calcd for C21H21Cl2NSi (M+H)+

385.0820, found 385.0767.

2-((2-(4-Fluorophenyl)-1-phenylethyl)dimethylsilyl)pyridine (19): The title compound 19 was obtained as a colorless oil (117.4 mg, 70% yield, using 5 mol % catalyst) after purification by silica gel column chromatography by gradient elution using 2-15% ether/hexanes.

1H NMR (300 MHz, CDCl3) 0.22 (s, 3H), 0.38 (s, 3H), 2.80 (dd, J = 7.9, 15.7 Hz, 1H), 3.06 (dd, J = 15.1, 23.0 Hz, 2H), 6.75 (t, J = 8.7 Hz, 2H), 6.90-6.97 (m, 4H), 7.00-7.05 (m, 1H), 7.12-7.23 (m, 3H), 7.33 (d, J = 7.5 Hz, 1H), 7.53 (ddd, J = 1.6, 1.6, 1.6 Hz, 1H), 8.81 (d, J = 4.4 Hz, 1H); 13C NMR (75 MHz, CDCl3) -5.6, -4.1, 35.0, 37.6, 114.7 (d, JCF = 21.0 Hz), 123.9 (d, JCF = 138.0 Hz), 128.2, 128.3 (d, JCF = 42.0 Hz), 129.8, 129.9, 129.9, 133.9, 137.7 (d, JCF = 3.0 Hz), 142.1, 150.3, 161.1 (d, JCF = 241.5 Hz), 166.3; 19F NMR

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(282 MHz, CDCl3) -116.6; IR (neat) cm-1 2926, 1507, 1218; HRMS (ESI) Calcd for C21H22FNSi (M+H)+

335.1506, found 335.1499.

1-(4-(2-(Dimethyl(pyridin-2-yl)silyl)-2-phenylethyl)phenyl)ethan-1-one (20): The title compound 20 was


column chromatography by gradient elution using 5–20% ether/hexanes.

1H NMR (300 MHz, CDCl3) 0.23 (s, 3H), 0.39 (s, 3H), 2.48 (s, 3H), 2.85 (app. t, J = 7.9 Hz, 1H), 3.15 (d, J = 7.9 Hz, 2H), 6.95 (d, J = 7.1 Hz, 2H), 6.99-7.15 (m, 5H), 7.19-7.23 (m, 1H), 7.34 (d, J = 7.5 Hz, 1H), 7.53 (ddd, J = 1.6, 1.6, 1.6 Hz, 1H), 7.67 (d, J = 8.2 Hz, 2H), 8.82 (d, J = 4.6 Hz, 1H); 13C NMR (75 MHz, CDCl3) -5.6, -4.2, 26.6, 35.8, 37.1, 123.1, 124.9, 128.2, 128.8, 129.9, 134.0, 134.9, 141.7, 148.1, 150.3, 166.1, 198.0; IR (neat) cm-1 2920, 1678, 1604, 1267; HRMS (ESI) Calcd for C23H25NOSi (M+H)+

359.1705, found 359.1718.

3-(2-(Dimethyl(pyridin-2-yl)silyl)-2-phenylethyl)benzonitrile (21): The title compound 21 was obtained as

a colorless oil (90.8 mg, 53% yield, using 5 mol % catalyst) after purification by silica gel column

chromatography by gradient elution using 5–20% ether/hexanes.

1H NMR (300 MHz, CDCl3) 0.21 (s, 3H), 0.39 (s, 3H), 2.80 (dd, J = 6.1, 9.7 Hz, 1H), 3.04-3.16 (m, 2H), 6.94 (d, J = 7.1 Hz, 2H), 7.04 (app. t, J = 7.3 Hz, 1H), 7.15 (app. t, J = 7.4 Hz, 3H), 7.19-7.24 (m, 3H), 7.29 (app. d, J = 7.2 Hz, 1H), 7.36 (app. d, J = 7.5 Hz, 1H), 7.55 (ddd, J = 1.6, 1.6, 1.6 Hz, 1H), 8.82 (d, J = 4.6 Hz, 1H); 13C NMR (75 MHz, CDCl3) -5.7, -4.1, 35.5, 37.2, 112.0, 119.2, 123.2, 125.1, 128.2, 128.3, 128.7, 129.5, 129.9, 132.1, 133.1, 134.1, 141.3, 143.6, 150.3, 165.9; IR (neat) cm-1 2956, 2227, 1417, 1246; HRMS (ESI) Calcd for C22H22N2Si (M+H)+ 342.1552, found 342.1548.

SI-9

Methyl 4-(2-(dimethyl(pyridin-2-yl)silyl)-2-phenylethyl)benzoate (22): The title compound 22 was obtained

as a white solid (107.0 mg, 57% yield, using 5 mol % catalyst) after purification by silica gel column


1H NMR (300 MHz, CDCl3) 0.23 (s, 3H), 0.38 (s, 3H), 2.84 (dd, J = 7.0, 8.7 Hz, 1H), 3.07-3.18 (m, 2H), 3.82 (s, 3H), 6.93-6.96 (m, 2H), 6.98-7.05 (m, 3H), 7.10-7.14 (m, 2H), 7.18-7.23 (m, 1H), 7.33-7.36 (m, 1H), 7.53 (ddd, J = 1.7, 1.7, 1.7 Hz, 1H), 7.75 (d, J = 8.3 Hz, 2H), 8.82 (d, J = 4.8 Hz, 1H); 13C NMR (75 MHz, CDCl3) -5.6, -4.2, 35.9, 37.2, 51.9, 123.1, 124.9, 127.6, 128.2, 128.2, 128.6, 129.4, 129.9, 134.0, 141.7, 147.8, 150.3, 166.1, 167.2; IR (neat) cm-1 2951, 1716, 1275; HRMS (ESI) Calcd for C23H25NO2Si (M+H)+ 375.1655, found 375.1634.

2-(Dimethyl(1-phenyl-2-(p-tolyl)ethyl)silyl)pyridine (23): The title compound 23 was obtained as a white solid (107.7 mg, 65% yield, using 5 mol % catalyst) after purification by silica gel column chromatography by gradient elution using 5–20% ether/hexanes.

1H NMR (300 MHz, CDCl3) 0.25 (s, 3H), 0.40 (s, 3H), 2.22 (s, 3H), 2.86 (app. t, J = 8.2 Hz, 1H), 3.11 (dd, J = 7.5, 15.6 Hz, 2H), 6.91 (s, 4H), 7.03 (dd, J = 8.0, 13.0 Hz, 3H), 7.13-7.22 (m, 3H), 7.34 (dd, J = 0.9, 7.5 Hz, 1H), 7.52 (ddd, J = 1.7, 1.7, 1.7 Hz, 1H), 8.83 (d, J = 4.2 Hz, 1H); 13C NMR (75 MHz, CDCl3) -5.5, -4.2, 21.0, 35.2, 37.3, 122.8, 124.6, 128.0, 128.3, 128.4, 128.7, 129.8, 133.8, 134.9, 138.9, 142.4, 150.2, 166.4; IR (neat) cm-1 2924, 1183, 1134; HRMS (ESI) Calcd for C22H25NSi (M+H)+ 331.1756, found 331.1785.

2-(Dimethyl(1-phenyl-2-(o-tolyl)ethyl)silyl)pyridine (24): The title compound 24 was obtained as a

colorless oil (91.2 mg, 55% yield, using 5 mol % catalyst) after purification by silica gel column


1H NMR (300 MHz, CDCl3) 0.23 (s, 3H), 0.41 (s, 3H), 2.10 (s, 3H), 2.75 (dd, J = 4.7, 10.1 Hz, 1H), 2.99-3.14 (m, 2H), 6.79-7.05 (m, 7H), 7.11-7.22 (m, 3H), 7.36 (app. d, J = 7.5 Hz, 1H), 7.53 (app. t, J = 7.6 Hz, 1H), 8.80 (d, J = 4.8 Hz, 1H); 13C NMR (75 MHz, CDCl3) -5.5, -4.1, 19.5, 33.1, 36.1, 123.0, 124.8, 125.4, 125.7, 128.1, 128.4, 129.1, 129.9, 130.0, 133.9, 135.9, 140.1, 142.5, 150.2, 166.4; IR (neat) cm-1 3022, 2954, 1449, 1246.

SI-10

2-((2-(2-Isopropylphenyl)-1-phenylethyl)dimethylsilyl)pyridine (25): The title compound 25 was obtained

as a colorless oil (109.7 mg, 61% yield, using 5 mol % catalyst) after purification by silica gel column


1H NMR (300 MHz, CDCl3) 0.21 (s, 3H), 0.44 (s, 3H), 0.95 (d, J = 6.8 Hz, 3H), 1.12 (app. d, J = 6.8 Hz, 3H), 2.64 (dd, J = 3.4, 11.2 Hz, 1H), 2.75-2.89 (m, 1H), 3.03 (dd, J = 11.3, 14.5 Hz, 1H), 3.17 (dd, J = 3.3, 14.5 Hz, 1H), 6.75-6.85 (m, 2H), 6.98-7.06 (m, 4H), 7.14 (dd, J = 9.8, 17.4 Hz, 3H), 7.20-7.26 (m, 1H), 7.5 (d, J = 7.5 Hz, 1H), 7.57 (ddd, J = 1.7, 1.7, 1.7 Hz, 1H), 8.83 (d, J = 4.8 Hz, 1H); 13C NMR (75 MHz, CDCl3) -5.7, -4.1, 23.9, 24.2, 28.4, 32.8, 37.8, 122.9, 124.8, 125.0, 125.1, 126.1, 128.2, 128.5, 129.6, 129.9, 133.9, 138.8, 142.4, 146.6, 150.2, 166.6; IR (neat) cm-1 2929, 1383, 1246; HRMS (ESI) Calcd for C24H29NSi (M+H)+ 359.2069, found 359.2072.

2-((2-(4-((tert-Butyldimethylsilyl)oxy)phenyl)-1-phenylethyl)dimethylsilyl)pyridine (26): The title

compound 26 was obtained as a colorless oil (98.5 mg, 44% yield, using 5 mol % catalyst) after purification

by silica gel column chromatography by gradient elution using 5–20% ether/hexanes.

1H NMR (300 MHz, CDCl3) 0.11 (s, 6H), 0.21 (s, 3H), 0.35 (s, 3H), 0.92 (s, 9H), 2.77 (t, J = 7.8 Hz, 1H), 3.01 (dd, J = 7.8, 22.9 Hz, 2H), 6.55 (d, J = 8.4 Hz, 2H), 6.82 (d, J = 8.4 Hz, 2H), 6.93-7.03 (m, 3H), 7.09-7.21 (m, 3H), 7.31 (d, J = 7.5 Hz, 1H), 7.51 (ddd, J = 1.6, 1.6, 1.7 Hz, 1H), 8.80 (d, J = 4.8 Hz, 1H); 13C NMR (75 MHz, CDCl3) -5.4, -4.3, -4.2, 18.3, 25.8, 35.1, 37.6, 119.6, 122.9, 124.6, 128.0, 128.4, 129.4, 129.9, 133.9, 134.8, 142.5, 150.2, 153.5, 166.5; IR (neat) cm-1 2955, 2928, 1507, 1247; HRMS (ESI) Calcd for C27H37NOSi2 (M+H)+ 447.2414, found 447.2388.

SI-11

2-((2-(3-Methoxyphenyl)-1-phenylethyl)dimethylsilyl)pyridine (27): The title compound 27 was obtained as

a colorless oil (99.0 mg, 57% yield, using 5 mol % catalyst) after purification by silica gel column


1H NMR (300 MHz, CDCl3) 0.23 (s, 3H), 0.38 (s, 3H), 2.84 (app. t, J = 8.0 Hz, 1H), 3.09 (app. d, J = 7.9 Hz, 2H), 3.63 (s, 3H), 6.53 (s, 1H), 6.59 (app. t, J = 9.9 Hz, 2H), 6.98-7.05 (m, 4H), 7.12-7.22 (m, 3H), 7.33 (d, J = 7.5 Hz, 1H), 7.52 (app. t, J = 7.6 Hz, 1H), 8.81 (d, J = 4.6 Hz, 1H); 13C NMR (75 MHz, CDCl3) -5.5, -4.2, 35.8, 37.2, 55.1, 111.2, 114.2, 121.1, 122.9, 124.7, 128.1, 128.3, 128.9, 129.9, 133.9, 142.3, 143.7, 150.2, 159.3, 166.4; IR (neat) cm-1 2954, 1598, 1488, 1246; HRMS (ESI) Calcd for C22H25NOSi (M+H)+ 347.1705, found 347.1684.

2-((2-(2-Methoxyphenyl)-1-phenylethyl)dimethylsilyl)pyridine (28): The title compound 28 was obtained as a colorless oil (95.6 mg, 55% yield, using 5 mol % catalyst) after purification by silica gel column chromatography by gradient elution using 5–20% ether/hexanes.

1H NMR (300 MHz, CDCl3) 0.25 (s, 3H), 0.41 (s, 3H), 2.90 (dd, J = 4.5, 10.7 Hz, 1H), 3.07 (dd, J = 10.8, 14.3 Hz, 1H), 3.18 (dd, J = 4.5, 14.3 Hz, 1H), 3.71 (s, 3H), 6.67 (dd, J = 7.4, 14.7 Hz, 2H), 6.89 (dd, J = 1.4, 7.4 Hz, 1H), 6.99-7.05 (m, 4H), 7.11-7.20 (m, 3H), 7.35-7.38 (m, 1H), 7.51 (ddd, J = 1.7, 1.7, 1.7 Hz, 1H), 8.81 (d, J = 4.8 Hz, 1H); 13C NMR (75 MHz, CDCl3) -5.5, -4.2, 29.9, 35.6, 55.2, 110.0, 120.0, 122.7, 124.5, 126.7, 127.9, 128.3, 129.8, 130.0, 130.3, 133.7, 142.9, 150.1, 157.4, 166.7; IR (neat) cm-1 2955, 1490, 1239; HRMS (ESI) Calcd for C22H25NOSi (M+H)+ 347.1705, found 347.1664.

3-(2-(Dimethyl(4-methylpyridin-2-yl)silyl)-2-phenylethyl)benzonitrile (29): The title compound 29 was obtained as a colorless oil (99.7 mg, 56% yield, using 5 mol % catalyst) after purification by silica gel column chromatography by gradient elution using 5–20% ether/hexanes.

1H NMR (300 MHz, CDCl3) 0.19 (s, 3H), 0.38 (s, 3H), 2.30 (s, 3H), 2.79 (dd, J = 6.3, 9.4 Hz, 1H), 3.03-3.14 (m, 2H), 6.95 (d, J = 7.0 Hz, 2H), 7.01-7.07 (m, 2H), 7.11-7.23 (m, 6H), 7.27-7.30 (m, 1H), 8.66 (d, J = 5.1 Hz, 1H); 13C NMR (75 MHz, CDCl3) -5.7, -4.0, 21.2, 35.5, 37.1, 111.9, 119.2, 124.1, 125.1, 128.1, 128.3, 128.7, 129.4, 131.0, 132.1, 133.1, 141.4, 143.6, 144.9, 150.1, 165.1.

SI-12

2-((2-(4-Fluorophenyl)-1-phenylethyl)dimethylsilyl)-4-methylpyridine (30): The title compound 30 was



1H NMR (300 MHz, CDCl3) 0.19 (s, 3H), 0.37 (s, 3H), 2.28 (s, 3H), 2.78 (t, J = 7.9 Hz, 1H), 3.05 (d, J =

7.9 Hz, 2H), 6.74 (t, J = 8.7 Hz, 2H), 6.89-7.06 (m, 6H), 7.11-7.17 (m, 3H), 8.66 (d, J = 4.8 Hz, 1H); 13C

NMR (75 MHz, CDCl3) -5.6, -4.0, 21.1, 35.1, 37.5, 114.7 (d, JCF = 21.0 Hz), 124.4 (d, JCF = 64.5 Hz),

128.1, 128.3, 129.8, 129.9, 131.0, 137.7 (d, JCF = 3.0 Hz), 142.2, 144.7, 150.0, 161.1 (d, JCF = 241.5 Hz),

165.5; 19F NMR (282 MHz, CDCl3) -116.8.

8-((2-(4-Fluorophenyl)-1-phenylethyl)dimethylsilyl)quinoline (31): The title compound 31 was obtained as a colorless oil (100.3 mg, 52% yield, using 5 mol % catalyst) after purification by silica gel column chromatography by gradient elution using 5–20% ether/hexanes.

1H NMR (300 MHz, CDCl3) 0.31 (s, 3H), 0.45 (s, 3H), 2.94-3.10 (m, 2H), 3.46 (dd, J = 4.9, 10.6 Hz,

1H), 6.64 (t, J = 8.1 Hz, 2H), 6.81 (t, J = 5.9 Hz, 2H), 7.01 (dd, J = 7.6, 12.2 Hz, 3H), 7.13 (t, J = 6.9 Hz,

2H), 7.39-7.49 (m, 2H), 7.78 (dd, J = 6.8, 14.9 Hz, 2H), 8.13 (d, J = 8.6 Hz, 1H), 8.96-8.99 (m, 1H); 13C

NMR (75 MHz, CDCl3) -4.4, -2.6, 35.2, 37.7, 114.4 (d, JCF = 21.0 Hz), 120.9, 124.4, 126.1, 127.8, 128.1

(d, JCF = 34.5 Hz), 129.4, 129.7, 129.8, 136.2, 136.7, 138.2 (d, JCF = 2.2 Hz), 139.6, 143.2, 149.1, 152.6,

160.9 (d, JCF = 241.5 Hz); 19F NMR (282 MHz, CDCl3) -117.3.

SI-13

8-(Dimethyl(1-phenyl-2-(o-tolyl)ethyl)silyl)quinoline (32): The title compound 32 was obtained as a colorless oil (103.1 mg, 54% yield, using 5 mol % catalyst) after purification by silica gel column chromatography by gradient elution using 5–20% ether/hexanes.

1H NMR (300 MHz, CDCl3) 0.33 (s, 3H), 0.50 (s, 3H), 1.93 (s, 3H), 2.99-3.11 (m, 2H), 3.41 (dd, J = 5.3, 9.9 Hz, 1H), 6.77 (s, 2H), 6.84 (dd, J = 7.3, 11.2 Hz, 2H), 6.96-7.13 (m, 5H), 7.38 (dd, J = 4.2, 8.2 Hz, 1H), 7.46 (t, J = 7.4 Hz, 1H), 7.79 (t, J = 5.25 Hz, 2H), 8.12 (d, J = 8.2 Hz, 1H), 8.94 (d, J = 4.3 Hz, 1H); 13C NMR (75 MHz, CDCl3) -4.1, -2.6, 19.3, 33.2, 35.9, 120.8, 124.3, 125.2, 125.4, 126.0, 127.8, 128.4, 129.0, 129.4, 129.8, 135.9, 136.2, 136.8, 139.7, 140.6, 143.6, 149.1, 152.7.

2-((1-(4-Fluorophenyl)-2-(p-tolyl)ethyl)dimethylsilyl)pyridine (33): The title compound 33 was obtained as a colorless oil (96.1 mg, 55% yield, using 5 mol % catalyst) after purification by silica gel column chromatography by gradient elution using 2-15% ether/hexanes.

1H NMR (300 MHz, CDCl3) 0.24 (s, 3H), 0.36 (s, 3H), 2.21 (s, 3H), 2.81 (dd, J = 4.7, 10.9Hz, 1H), 2.95-3.11 (m, 2H), 6.78-6.92 (m, 8H), 7.18-7.33 (m, 1H), 7.32 (d, J = 7.5 Hz, 1H), 7.53 (ddd, J = 1.6, 1.6, 1.6 Hz, 1H), 8.81 (d, J = 4.7 Hz, 1H); 13C NMR (75 MHz, CDCl3) -5.4, -4.4, 21.0, 35.4, 36.6, 114.8 (d, JCF = 21.0 Hz), 123.0, 128.4, 128.8, 129.4 (d, JCF = 7.5 Hz), 129.9, 133.9, 135.1, 137.9, 138.7, 150.3, 160.6 (d, JCF = 240.7 Hz), 166.1; 19F NMR (282 MHz, CDCl3) -117.1; IR (neat) cm-1 2955, 2922, 1505, 1157; GC-MS for C22H24FNSi was found to be 349.2.

SI-14

2-((2-(4-Methoxyphenyl)-1-(m-tolyl)ethyl)dimethylsilyl)pyridine (34): The title compound 34 was obtained



1H NMR (300 MHz, CDCl3) 0.20 (s, 3H), 0.35 (s, 3H), 2.21 (s, 3H), 2.76 (dd, J = 6.1, 9.3 Hz, 1H), 2.99-3.10 (m, 2H), 3.69 (s, 3H), 6.63 (d, J = 8.6 Hz, 2H), 6.75 (s, 1H), 6.81 (dd, J = 7.8, 11.8 Hz, 2H), 6.91 (d, J = 8.5 Hz, 2H), 7.03 (t, J = 7.5 Hz, 1H), 7.16-7.21 (m, 1H), 7.29 (d, J = 7.6 Hz, 1H), 7.51 (ddd, J = 1.6, 1.6, 1.7 Hz, 1H), 8.80 (d, J = 4.8 Hz, 1H); 13C NMR (75 MHz, CDCl3) -5.5, -4.2, 21.6, 34.8, 37.3, 55.2, 113.5, 122.9, 125.2, 125.4, 127.9, 129.2, 129.5, 129.9, 133.8, 134.3, 137.4, 142.3, 150.1, 157.5, 166.5; IR (neat) cm-1 2954, 1509, 1242.

2-((1-(3-Methoxyphenyl)-2-(p-tolyl)ethyl)dimethylsilyl)pyridine (35): The title compound 35 was obtained



1H NMR (300 MHz, CDCl3) 0.23 (s, 3H), 0.37 (s, 3H), 2.20 (s, 3H), 2.81 (dd, J = 6.8, 8.6 Hz, 1H), 3.05 (app. d, J = 7.0 Hz, 2H), 3.67 (s, 3H), 6.50 (s, 1H), 6.57 (app. t, J = 8.9 Hz, 2H), 6.89 (s, 4H), 7.05 (t, J = 7.8 Hz, 1H), 7.19 (app. t, J = 6.4 Hz, 1H), 7.32 (d, J = 7.5 Hz, 1H), 7.51 (app. t, J = 7.5 Hz, 1H), 8.80 (d, J = 4.0 Hz, 1H); 13C NMR (75 MHz, CDCl3) -5.7, -4.1, 35.7, 37.1, 55.1, 110.2, 114.0, 120.9, 122.9, 128.4, 128.8, 128.9, 129.9, 133.8, 134.9, 138.9, 144.2, 150.2, 159.4, 166.5; IR (neat) cm-1 2919, 1596, 1575, 1246; GC-MS for C23H27NOSi was found to be 361.2.

Ha NOE correlation Hc NOE correlation

Hb 4.5% Ha 1.8%

Hc 2.2% Hb 1.8%

OMe 1.8%

SI-15

2-((1-(4-Fluorophenyl)-2-(3-(trifluoromethyl)phenyl)ethyl)dimethylsilyl)pyridine (36): The title compound

36 was obtained as a colorless oil (105.0 mg, 52% yield, using 5 mol % catalyst) after purification by silica


1H NMR (300 MHz, CDCl3) 0.24 (s, 3H), 0.38 (s, 3H), 2.82 (dd, J = 4.6, 11.2 Hz, 1H), 3.03-3.20 (m, 2H), 6.74-6.92 (m, 4H), 7.11-7.29 (m, 5H), 7.32-7.35 (m, 1H), 7.54 (ddd, J = 1.7, 1.7, 1.7 Hz, 1H), 8.81 (d, J = 4.8 Hz, 1H); 13C NMR (75 MHz, CDCl3) -5.5, -4.3, 36.0, 36.4, 115.0 (d, JCF = 20.2 Hz), 122.6 (q, JCF

= 3.75 Hz), 123.2, 125.3 (q, JCF = 3.0 Hz), 126.1, 128.4, 129.3, 129.4, 129.9, 130.3 (q, JCF = 31.5 Hz), 131.9, 134.1, 137.3 (d, JCF = 3.0 Hz), 142.7, 150.3, 160.7 (d, JCF = 241.5 Hz), 166.7; 19F NMR (282 MHz, CDCl3) -61.2, -117.3; IR (neat) cm-1 2931, 1505, 1327, 1119; GC-MS for C22H21F4NSi was found to be 403.1.

1-(4-(2-(Dimethyl(pyridin-2-yl)silyl)-2-(4-methoxyphenyl)ethyl)phenyl)ethan-1-one (37): The title

compound 37 was obtained as a white solid (85.7 mg, 44% yield, using 3 mol % catalyst) after purification

by silica gel column chromatography by gradient elution using 5–20% ether/hexanes.

1H NMR (300 MHz, CDCl3) 0.22 (s, 3H), 0.37 (s, 3H), 2.23 (s, 3H), 2.79 (dd, J = 6.8, 8.9 Hz, 1H), 3.04-3.15 (m, 2H), 3.82 (s, 3H), 6.83 (d, J = 8.0 Hz, 2H), 6.92 (d, J = 7.9 Hz, 2H), 7.03 (d, J = 8.2 Hz, 2H), 7.18-7.22 (m, 1H), 7.36 (d, J = 7.5 Hz, 1H), 7.53 (ddd, J = 1.7, 1.7, 1.7 Hz, 1H), 7.74 (d, J = 8.3 Hz, 2H), 8.81 (d, J = 4.8 Hz, 1H); 13C NMR (75 MHz, CDCl3) -5.2, -3.7, 21.4, 36.4, 37.0, 52.4, 123.4, 127.9, 128.5, 129.1, 129.3, 129.8, 130.3, 134.4, 134.6, 138.8, 148.4, 150.7, 166.7, 167.7; IR (neat) cm-1 2921, 1716, 1274; HRMS (ESI) Calcd for C24H27NO2Si (M+H)+ 389.1811, found 389.1753.

SI-16

3-(2-(Dimethyl(pyridin-2-yl)silyl)-2-(3-methoxyphenyl)ethyl)benzonitrile (38): The title compound 38 was



1H NMR (300 MHz, CDCl3) 0.22 (s, 3H), 0.39 (s, 3H), 2.77 (dd, J = 6.6, 9.1 Hz, 1H), 3.03-3.13 (m, 2H),

3.68 (s, 3H), 6.47 (d, J = 1.7 Hz, 1H), 6.57 (dd, J = 7.9, 16.1 Hz, 2H), 7.07 (t, J = 7.9 Hz, 1H), 7.13-731

(m, 5H), 7.36 (d, J = 7.5 Hz, 1H), 7.56 (ddd, J = 1.7, 1.7, 1.7 Hz, 1H), 8.81 (d, J = 4.8 Hz, 1H); 13C NMR

(75 MHz, CDCl3) -5.6, -4.1, 35.5, 37.2, 55.1, 110.4, 111.9, 114.0, 119.2, 120.6, 123.2, 128.7, 129.2,

129.5, 129.9, 132.1, 133.1, 134.1, 143.0, 143.6, 150.3, 159.6, 165.9; IR (neat) cm-1 2955, 2227, 1576, 1557,

1247; HRMS (ESI) Calcd for C23H24N2OSi (M+H)+ 372.1658, found 372.1651.

2-(2-(Dimethyl(pyridin-2-yl)silyl)-2-(m-tolyl)ethyl)benzonitrile (39): The title compound 39 was obtained



1H NMR (300 MHz, CDCl3) 0.28 (s, 3H), 0.41 (s, 3H), 2.20 (s, 3H), 2.89 (dd, J = 6.9, 9.2 Hz, 1H), 3.27-3.38 (m, 2H), 6.75-6.84 (m, 3H), 7.01 (t, J = 7.4 Hz, 1H), 7.07-7.11 (m, 2H), 7.18-7.28 (m, 2H), 7.38-7.45 (m, 2H), 7.55 (ddd, J = 1.6, 1.6, 1.7 Hz, 1H), 8.80 (d, J = 4.7 Hz, 1H); 13C NMR (75 MHz, CDCl3) -5.5, -4.2, 21.5, 34.1, 36.6, 112.4, 118.5, 123.1, 125.3, 125.8, 126.2, 128.0, 129.1, 129.6, 130.1, 132.3, 132.6, 134.0, 137.6, 140.9, 146.1, 150.2, 165.8; IR (neat) cm-1 2955, 2222, 1601, 1269.


Hb 5.4% Ha 3.0%

Hc 3.6% Hb 2.9% Me1 2.9%

SI-17

Methyl 4-(2-(dimethyl(pyridin-2-yl)silyl)-2-(3-methoxyphenyl)ethyl)benzoate (40): The title compound 40


gel column chromatography by gradient elution using 5–20% ether/hexanes.

1H NMR (300 MHz, CDCl3) 0.24 (s, 3H), 0.39 (s, 3H), 2.82 (app. t, J = 7.9 Hz, 1H), 3.11 (app. dd, J = 15.1, 22.9 Hz, 2H), 3.66 (s, 3H), 3.83 (s, 3H), 6.47 (s, 1H), 6.55 (d, J = 8.2 Hz, 2H), 7.04 (app. t, J = 7.7 Hz, 3H), 7.19-7.23 (m, 1H), 7.35 (d, J = 7.5 Hz, 1H), 7.54 (ddd, J = 1.6, 1.6, 1.6 Hz, 1H), 7.75 (d, J = 8.2 Hz, 2H), 8.82 (d, J = 4.7 Hz, 1H); 13C NMR (75 MHz, CDCl3) -5.5, -4.2, 35.9, 37.3, 51.9, 55.1, 110.3, 114.0, 120.8, 123.1, 127.6, 128.6, 129.0, 129.4, 129.9, 134.0, 143.5, 147.8, 150.3, 159.5, 166.1, 167.3; IR (neat) cm-1 2951, 1716, 1605, 1275; HRMS (ESI) Calcd for C24H27NO3Si (M+H)+ 405.1760, found 405.1726.


Hb 4.4% Ha 2.0%

Hc 2.4% Hb 1.9%

OMe 1.9%

2-(Dimethyl(2-(naphthalen-1-yl)-1-(4-(trifluoromethyl)phenyl)ethyl)silyl)pyridine (41): The title

compound 41 was obtained as a yellow solid (108.9 mg, 50% yield, using 5 mol % catalyst) after


1H NMR (300 MHz, CDCl3) 0.38 (s, 3H), 0.58 (s, 3H), 3.21 (dd, J = 3.6, 11.3 Hz, 1H), 3.55 (dd, J = 11.3, 26.8 Hz, 1H), 3.82 (dd, J = 3.6, 14.8 Hz, 1H), 7.07 (d, J = 6.9 Hz, 1H), 7.21 (app. t, J = 7.5 Hz, 3H), 7.35-7.39 (m, 1H), 7.48-7.54 (m, 5H), 7.66-7.72 (m, 2H), 7.86-7.94 (m, 2H), 8.97 (d, J = 4.8 Hz, 1H); 13C NMR

SI-18

(75 MHz, CDCl3) -5.6, -4.1, 33.0, 36.9, 123.3, 123.8, 125.2 (q, JCF = 7.5 Hz), 125.8, 126.5, 126.7, 126.8, 127.3, 128.4, 128.9, 130.0, 131.8, 134.0, 134.1, 137.1, 147.3, 150.4, 165.7; 19F NMR (282 MHz, CDCl3) -60.5; IR (neat) cm-1 2956, 1324, 1119; HRMS (ESI) Calcd for C26H24F3NSi (M+H)+ 435.1630, found 435.1610.

3-(2-(Dimethyl(pyridin-2-yl)silyl)-2-(m-tolyl)ethyl)benzonitrile (42): The title compound 42 was obtained



1H NMR (300 MHz, CDCl3) 0.21 (s, 3H), 0.38 (s, 3H), 2.22 (s, 3H), 2.75 (dd, J = 7.0, 8.6 Hz, 1H), 3.03-3.14 (m, 2H), 6.71 (s, 1H), 6.75 (d, J = 7.7 Hz, 1H), 6.85 (d, J = 7.5 Hz, 1H), 7.04 (t, J = 7.6 Hz, 1H), 7.13-7.25 (m, 4H), 7.28-7.36 (m, 2H), 7.55 (ddd, J = 1.7, 1.7, 1.7 Hz, 1H), 8.81 (d, J = 4.6 Hz, 1H); 13C NMR (75 MHz, CDCl3) -5.7, -4.1, 21.6, 35.5, 37.0, 111.9, 119.3, 123.1, 125.1, 125.9, 128.2, 128.7, 129.1, 129.5, 129.9, 132.2, 133.2, 134.0, 137.7, 141.2, 143.7, 150.3, 166.1; IR (neat) cm-1 2920, 2227, 1246; HRMS (ESI) Calcd for C23H24N2Si (M+H)+ 356.1709, found 356.1732.


Hb 4.5% Ha 2.5%

Hc 3.4% Hb 2.1%

Me1 2.2%




SI-19

1H NMR (300 MHz, CDCl3) 0.23 (s, 3H), 0.42 (s, 3H), 195 (s, 3H), 2.98-3.08 (m, 2H), 3.12-3.22 (m, 1H), 6.92-6.95 (m, 4H), 7.02-7.22 (m, 6H), 7.29 (d, J = 7.5 Hz, 1H), 7.51 (app. t, J = 8.3 Hz, 1H), 8.81 (d, J = 4.8 Hz, 1H); 13C NMR (75 MHz, CDCl3) -5.1, -4.0, 20.5, 32.3, 37.0, 122.9, 124.5, 125.6, 125.8, 127.1, 128.0, 128.4, 129.8, 130.1, 133.8, 136.0, 141.1, 142.5, 150.2, 166.6; IR (neat) cm-1 3024, 2954, 1246.




1H NMR (300 MHz, CDCl3) 0.22 (s, 3H), 0.42 (s, 3H), 196 (s, 3H), 2.96-3.04 (m, 2H), 3.08-3.18 (m, 1H), 6.84 (d, J = 6.0 Hz, 2H), 6.94-6.97 (m, 2H), 7.02 (d, J = 6.0 Hz, 2H), 7.09-7.10 (m, 2H), 7.21 ( t, J = 6.0 Hz, 1H), 7.30 (d, J = 6.0 Hz, 1H), 7.53 ( t, J = 7.5 Hz, 1H), 8.81 (d, J = 6.0 Hz, 1H); 13C NMR (75 MHz, CDCl3) -5.1, -4.0, 20.5, 32.3, 36.4, 123.0, 124.6, 125.9, 127.1, 128.1, 129.7, 129.8, 130.1, 131.3, 133.9, 136.0, 140.6, 141.0, 150.2, 166.4.

2-(4-Fluorophenyl)-1-phenylethan-1-ol (45)6: The title compound 45 was obtained as a colorless oil (86.5

mg, 80% yield) after purification by silica gel column chromatography by gradient elution using 5–20%

ether/hexanes.

1H NMR (300 MHz, CDCl3) 2.30 (s, 1H), 2.99 (d, J = 6.7 Hz, 2H), 4.83 (t, J = 6.6 Hz, 1H), 6.98 (app. t, J = 8.7 Hz, 2H), 7.09-7.14 (m, 2H), 7.29-7.39 (m, 5H); 13C NMR (75 MHz, CDCl3) 45.0, 75.4, 115.2 (d, JCF = 21.0 Hz), 126.0, 127.7, 128.5, 131.0 (d, JCF = 8.2 Hz), 133.8 (d, JCF = 3.0 Hz), 143.7, 161.8 (d, JCF = 243.0 Hz); 19F NMR (282 MHz, CDCl3) -115.1; IR (neat) cm-1 3378, 2921, 1508, 1219.

1-Phenyl-2-(p-tolyl)ethan-1-ol (46)6: The title compound 46 was obtained as a white solid (87.0 mg, 82%

yield) after purification by silica gel column chromatography by gradient elution using 5–20%

ether/hexanes.

SI-20

1H NMR (300 MHz, CDCl3) 1.93 (s, 1H), 2.33 (s, 3H), 2.90-3.05 (m, 2H), 4.89 (dd, J = 4.8, 8.6 Hz, 1H), 7.08-7.14 (m, 4H), 7.27-7.39 (m, 5H); 13C NMR (75 MHz, CDCl3) 21.1, 45.7, 75.4, 126.0, 127.6, 128.4, 129.2, 129.5, 135.0, 136.1, 144.0; IR (neat) cm-1 3282, 2916, 1454, 1203.

2-((2-(2-(But-3-en-1-yl)phenyl)-1-phenylethyl)dimethylsilyl)pyridine (51): The title compound 51 was



1H NMR (300 MHz, CDCl3) 0.23 (s, 3H), 0.43 (s, 3H), 2.15-2.23 (m, 2H), 2.53 (t, J = 7.8 Hz, 2H), 2.74 (dd, J = 3.8, 11.0 Hz, 1H), 3.02-3.19 (m, 2H), 4.97 (dd, J = 4.8, 9.5 Hz, 2H), 5.70-5.83 (m, 1H), 6.84 (app. dd, J = 7.5, 15.5 Hz, 2H), 6.95-7.06 (m, 5H), 7.12-7.23 (m, 3H), 7.39 (d, J = 7.4 Hz, 1H), 7.55 (t, J = 7.6 Hz, 1H), 8.82 (d, J = 4.7 Hz, 1H); 13C NMR (75 MHz, CDCl3) -5.5, -4.1, 32.0, 32.5, 35.2, 36.8, 114.8, 123.0, 124.8, 125.5, 125.8, 128.1, 128.4, 129.0, 129.4, 129.9, 133.9, 138.4, 139.6, 139.7, 142.4, 150.3, 166.4; IR (neat) cm-1 3061, 2956, 1449, 1246.

4. References

(1) Itami, K.; Mitsudo, K.; Yoshida, J.-i. Angewandte Chemie International Edition 2002, 41, 3481.

(2) Struk, Ł.; Sośnicki, J. G.; Idzik, T. J.; Maciejewska, G. Eur. J. Org. Chem. 2016, 2016, 1292.

(3) Wright, M. E. Tetrahedron Letters 1987, 28, 3233.

(4) Krasovskiy, A.; Malakhov, V.; Gavryushin, A.; Knochel, P. Angewandte Chemie International

Edition 2006, 45, 6040.

(5) Krasovskiy, A.; Knochel, P. Synthesis 2006, 2006, 0890.

(6) Nielsen, D. K.; Doyle, A. G. Angewandte Chemie International Edition 2011, 50, 6056.

-1.0-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.511.011.512.0f1 (ppm)

3.01

3.00

1.00

2.02

2.01

3.00

2.00

1.00

3.00

1.00

1.00

0.21

490.

3882

2.81

192.

8382

2.86

433.

0864

3.11

343.

1327

3.15

906.

9534

6.97

076.

9768

6.98

147.

0107

7.01

497.

0319

7.03

927.

0584

7.06

317.

0827

7.12

587.

1510

7.16

947.

1747

7.18

487.

1893

7.20

107.

2056

7.21

047.

2150

7.22

667.

2311

7.25

997.

2978

7.31

757.

3219

7.33

857.

3423

7.34

617.

5043

7.51

017.

5297

7.53

557.

5551

7.56

09

8.79

488.

8106

-100102030405060708090100110120130140150160170180190200210f1 (ppm)

-5.6

7-4

.11

35.7

337

.08

76.7

4 CD

Cl3

77.1

6 CD

Cl3

77.5

8 CD

Cl3

122.

6812

3.10

124.

9212

4.97

125.

0212

6.28

127.

6912

8.11

128.

2112

8.28

128.

6112

8.85

129.

9013

4.03

141.

7514

6.30

150.

29

166.

07

-190-180-170-160-150-140-130-120-110-100-90-80-70-60-50-40-30-20-100f1 (ppm)

-60.

97

-1.0-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.511.011.512.0f1 (ppm)

-20000

0

20000

40000

60000

80000

100000

120000

140000

160000

180000

200000

220000

240000

260000

280000

300000

320000

340000

3.05

3.00

3.05

1.00

2.02

7.00

3.03

1.03

1.01

0.19

860.

3883

2.28

29

2.82

962.

8551

2.88

113.

0821

3.12

793.

1539

6.97

577.

0003

7.02

357.

0429

7.06

447.

0884

7.13

557.

1604

7.18

597.

2605

7.29

417.

3199

8.65

008.

6661

-100102030405060708090100110120130140150160170180190200210f1 (ppm)

0

5000

10000

15000

20000

25000

30000

35000

40000

45000

50000

55000

60000

65000

70000

75000

-5.3

2-3

.59

21.5

7

36.1

737

.43

77.1

6 CD

Cl3

77.5

8 CD

Cl3

78.0

1 CD

Cl3

124.

5212

5.31

125.

3612

5.42

128.

4312

8.50

128.

6812

9.30

131.

5314

2.27

145.

4014

6.74

150.

3315

0.42

165.

66

-190-180-170-160-150-140-130-120-110-100-90-80-70-60-50-40-30-20-100f1 (ppm)

0

1000

2000

3000

4000

5000

6000

7000

8000

9000

10000

-60.

81

-1.0-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.511.011.512.0f1 (ppm)

0

10000

20000

30000

40000

50000

60000

70000

80000

90000

100000

3.00

3.06

2.05

1.00

2.04

3.02

4.03

1.04

1.01

2.03

1.03

1.03

0.30

980.

4531

3.00

473.

0226

3.05

323.

0706

3.09

823.

1328

3.18

133.

4982

3.51

593.

5326

3.55

06

6.92

506.

9513

7.00

667.

0315

7.05

377.

0781

7.13

387.

1543

7.17

567.

2595

7.37

957.

3934

7.40

707.

4209

7.43

297.

4581

7.48

277.7

471

7.769

67.7

823

7.80

948.

1028

8.13

038.

9551

8.96

88

-100102030405060708090100110120130140150160170180190200210f1 (ppm)

0

2000

4000

6000

8000

10000

12000

14000

16000

18000

20000

22000

24000

26000-4.6

1-2

.49

36.0

437

.19

120.

9312

4.50

124.

5512

4.61

126.

0912

7.26

127.

6912

7.80

128.

0312

8.29

128.

7412

9.57

136.

3313

6.77

139.

3914

3.10

146.

7314

9.12

152.

59

-190-180-170-160-150-140-130-120-110-100-90-80-70-60-50-40-30-20-100f1 (ppm)

-1000

0

1000

2000

3000

4000

5000

6000

7000

8000

9000

10000

11000

12000

13000

14000

15000

16000

17000

18000

19000

20000

-60.

83

-1.0-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.511.011.512.0f1 (ppm)

3.00

3.03

1.00

2.01

4.02

5.00

1.00

2.01

1.00

0.29

900.

4017

2.84

882.

8637

2.88

532.

9002

3.24

943.

3013

3.33

713.

3489

3.38

753.

4008

6.94

116.

9673

6.99

286.

9971

7.02

277.

0461

7.04

987.

1028

7.12

697.

1498

7.15

377.

1802

7.19

637.

2010

7.20

577.

2218

7.25

657.

2596

7.35

007.

3534

7.37

517.

3786

7.49

017.

5123

7.53

717.

5624

8.81

048.

8227

-100102030405060708090100110120130140150160170180190200210f1 (ppm)

-5.4

5-4

.39

31.5

8

36.0

1

76.7

4 CD

Cl3

77.1

6 CD

Cl3

77.5

8 CD

Cl3

123.

0412

4.92

125.

6612

5.79

125.

8712

5.95

126.

6312

8.18

128.

4912

8.63

129.

9713

0.66

131.

1513

3.90

140.

4414

1.73

150.

25

165.

97

-360-340-320-300-280-260-240-220-200-180-160-140-120-100-80-60-40-20020406080100120140160f1 (ppm)

-57.

99

-1.0-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.511.011.512.0f1 (ppm)

3.01

3.00

1.00

2.02

2.00

1.03

3.02

3.00

2.00

1.00

0.23

470.

4139

2.80

992.

8305

2.84

232.

8630

3.15

243.

2012

3.21

753.

2358

3.26

61

6.94

956.

9730

6.97

717.

0282

7.05

277.

0768

7.13

997.

1652

7.19

237.

1965

7.20

887.

2133

7.21

817.

2226

7.23

447.

2387

7.25

987.

3506

7.35

387.

3756

7.37

907.

4023

7.52

007.

5251

7.54

557.

5511

7.57

097.

5765

8.81

138.

8272

-100102030405060708090100110120130140150160170180190200210f1 (ppm)

-5.6

3-3

.99

35.9

337

.10

76.7

4 CD

Cl3

77.1

6 CD

Cl3

77.5

8 CD

Cl3

119.

6911

9.74

119.

7812

1.71

123.

2312

5.36

128.

2212

8.48

128.

7812

9.92

130.

4113

0.85

131.

2813

1.72

134.

1214

1.10

144.

61

150.

42

165.

82

-360-340-320-300-280-260-240-220-200-180-160-140-120-100-80-60-40-20020406080100120140160f1 (ppm)

-61.

36

-1.0-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.511.011.512.0f1 (ppm)

3.00

3.01

1.00

2.01

1.01

2.00

5.05

1.00

1.03

1.02

1.00

0.21

080.

3786

2.75

962.

7819

2.78

962.

8122

2.98

283.

0314

3.04

153.

0628

3.09

00

6.77

296.

7790

6.80

026.

8064

6.94

396.

9709

7.02

127.

0455

7.06

897.

0893

7.11

677.

1334

7.15

897.

1846

7.20

597.

2108

7.21

487.

2313

7.25

997.

3179

7.34

297.

5081

7.51

347.

5335

7.53

847.

5588

7.56

358.

8006

8.81

67

-100102030405060708090100110120130140150160170180190200210f1 (ppm)

-5.5

9-4

.03

35.2

537

.26

76.7

4 CD

Cl3

77.1

6 CD

Cl3

77.5

8 CD

Cl3

123.

0612

5.13

128.

0912

8.25

128.

3412

9.53

129.

8612

9.90

130.

6213

1.89

133.

9714

1.66

142.

53

150.

32

166.

09

-1.0-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.511.011.512.0f1 (ppm)

3.02

3.02

1.00

2.04

2.01

4.01

1.03

3.02

1.00

1.02

1.00

0.21

810.

3775

2.76

622.

7924

2.81

852.

8467

3.00

463.

0551

3.08

123.

1215

6.72

346.

7525

6.78

176.

8984

6.91

706.

9262

6.94

596.

9707

7.00

407.

0285

7.05

267.

1173

7.14

247.

1665

7.18

467.

2011

7.20

587.

2101

7.22

627.

2595

7.31

797.

3429

7.50

177.

5072

7.52

717.

5325

7.55

247.

5578

8.80

678.

8214

-100102030405060708090100110120130140150160170180190200210f1 (ppm)

-5.5

5-4

.15

35.0

537

.57

76.7

4 CD

Cl3

77.1

6 CD

Cl3

77.5

8 CD

Cl3

114.

6011

4.88

123.

0012

4.84

128.

1712

8.29

129.

8212

9.88

129.

9213

3.94

137.7

013

7.74

142.

07

150.

28

159.

5216

2.74

166.

28

-360-340-320-300-280-260-240-220-200-180-160-140-120-100-80-60-40-20020406080100120140160f1 (ppm)

-116

.62

-1.0-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.511.011.512.0f1 (ppm)

3.01

3.01

3.01

1.00

2.00

2.02

5.05

1.03

1.03

1.03

2.00

1.01

0.22

910.

3884

2.47

592.

8230

2.84

922.

8756

3.13

403.

1603

6.93

846.

9622

6.99

367.

0180

7.04

797.

0756

7.10

507.

1302

7.15

427.

1869

7.19

077.

2071

7.21

197.

2161

7.22

857.

2323

7.26

057.

3323

7.35

737.

5074

7.51

287.

5328

7.53

817.

5581

7.56

357.

6590

7.68

648.

8084

8.82

39

-100102030405060708090100110120130140150160170180190200210f1 (ppm)

-5.5

9-4

.17

26.5

7

35.8

337

.10

76.7

4 CD

Cl3

77.1

6 CD

Cl3

77.5

8 CD

Cl3

123.

0712

4.94

128.

2212

8.78

129.

9113

3.99

134.

86

141.

68

148.

1315

0.30

166.

08

197.

96

-1.0-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.511.011.512.0f1 (ppm)

3.01

3.01

1.00

2.00

2.01

1.01

3.00

3.00

1.00

1.01

1.02

1.00

0.21

360.

3862

2.76

982.

7900

2.80

222.

8223

3.04

443.

0931

3.10

933.

1273

3.15

76

6.92

806.

9517

7.01

277.

0372

7.06

127.

1226

7.14

747.

1711

7.18

717.

1988

7.20

377.

2151

7.21

947.

2246

7.22

937.

2447

7.25

967.

2788

7.30

287.

3452

7.37

037.

5265

7.53

197.

5519

7.55

727.

5772

7.58

268.

8104

8.82

58

-20-100102030405060708090100110120130140150160170180190200210220230f1 (ppm)

-5.6

9-4

.09

35.5

337

.18

76.7

4 CD

Cl3

77.1

6 CD

Cl3

77.5

8 CD

Cl3

111.

9611

9.21

123.

1812

5.15

128.

1612

8.35

128.

7412

9.48

129.

8813

2.15

133.

1313

4.06

141.

3214

3.63

150.

35

165.

92

-1.0-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.511.011.512.0f1 (ppm)

3.00

3.02

1.00

2.00

3.02

2.02

3.01

2.02

1.03

1.02

1.00

2.00

1.00

0.22

890.

3842

2.81

172.

8352

2.84

072.

8643

3.07

523.

1239

3.13

013.

1533

3.17

853.

8213

6.92

966.

9530

6.95

756.

9852

6.98

917.

0022

7.00

987.

0258

7.03

297.

0532

7.09

647.

1217

7.14

027.

1453

7.18

267.

1871

7.19

887.

2033

7.20

817.

2127

7.22

447.

2289

7.25

967.

3261

7.33

007.

3337

7.35

117.

3550

7.35

857.

5032

7.50

897.

5286

7.53

437.

5540

7.55

977.7

362

7.763

88.

8101

8.82

61

-100102030405060708090100110120130140150160170180190200210f1 (ppm)

-5.5

6-4

.18

35.8

937

.18

51.9

4

76.7

4 CD

Cl3

77.1

6 CD

Cl3

77.5

8 CD

Cl3

123.

0612

4.91

127.

5712

8.19

128.

2212

8.62

129.

4012

9.89

133.

9714

1.70

147.

8115

0.30

166.

1016

7.25

-1.0-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.511.011.512.0f1 (ppm)

3.00

3.01

3.00

1.00

2.01

4.01

3.01

3.00

1.01

1.01

1.00

0.25

070.

3976

2.21

68

2.83

722.

8644

2.88

893.

0652

3.09

023.

1171

3.15

31

6.91

116.

9943

7.02

107.

0376

7.06

097.

1330

7.15

767.

1804

7.19

157.

1961

7.20

087.

2054

7.21

757.

2215

7.25

987.

3250

7.32

817.

3501

7.35

327.

4940

7.49

967.

5194

7.52

507.

5448

7.55

048.

8233

8.83

72

-100102030405060708090100110120130140150160170180190200210f1 (ppm)

-5.5

2-4

.22

21.0

3

35.2

237

.30

76.7

4 CD

Cl3

77.1

6 CD

Cl3

77.5

8 CD

Cl3

122.

8512

4.64

128.

0512

8.28

128.

4312

8.72

129.

8413

3.81

134.

8713

8.94

142.

40

150.

20

166.

40

-1.0-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.511.011.512.0f1 (ppm)

-5000

0

5000

10000

15000

20000

25000

30000

35000

40000

45000

50000

55000

60000

65000

70000

75000

80000

85000

90000

3.00

3.03

3.00

1.00

2.02

7.03

3.04

1.02

1.02

1.01

0.23

360.

4152

2.09

962.

7276

2.74

352.

7612

2.77

712.

9950

3.04

403.

0765

3.09

023.

1233

3.13

93

6.79

546.

8201

6.85

416.

8788

6.90

656.

9321

6.97

166.

9984

7.02

957.

0518

7.11

527.

1399

7.16

577.

1795

7.19

637.

2008

7.20

417.

2214

7.25

967.

3516

7.35

477.

3767

7.37

977.

5074

7.53

287.

5613

8.79

778.

8136

-100102030405060708090100110120130140150160170180190200210f1 (ppm)

0

500

1000

1500

2000

2500

3000

3500

4000

4500

5000

5500

-5.5

2-4

.15

19.5

0

33.1

036

.08

76.7

4 CD

Cl3

77.1

6 CD

Cl3

77.5

8 CD

Cl3

122.

9812

4.78

125.

4412

5.67

128.

1112

8.41

129.

1012

9.89

130.

0413

3.89

135.

9114

0.15

142.

5515

0.22

166.

44

-1.0-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.511.011.512.0f1 (ppm)

3.01

3.01

3.00

3.00

1.01

1.03

1.03

1.00

2.02

4.03

3.00

1.02

1.01

1.01

1.00

0.20

72

0.44

240.

9419

0.96

461.

1103

1.13

312.

6155

2.62

672.

6528

2.66

402.

7547

2.77

762.

8004

2.82

312.

8468

2.86

862.

8913

2.99

213.

0297

3.04

043.

0778

3.13

893.

1500

3.18

723.

1983

6.75

256.

7780

6.79

286.

7972

6.82

036.

8458

6.98

277.

0058

7.01

087.

0392

7.06

337.

0962

7.12

887.

1542

7.17

797.

2017

7.20

587.

2267

7.23

127.

2432

7.24

757.

2600

7.41

087.

4359

7.54

117.

5467

7.56

657.

5721

7.59

187.

5974

8.82

808.

8441

-100102030405060708090100110120130140150160170180190200210f1 (ppm)

-5.6

8-4

.11

23.9

424

.17

28.4

132

.80

37.7

8

76.7

4 CD

Cl3

77.1

6 CD

Cl3

77.5

8 CD

Cl3

122.

9712

4.82

125.

0112

5.09

126.

0912

8.16

128.

5012

9.61

129.

8613

3.90

138.

7614

2.43

146.

5715

0.24

166.

62

-1.0-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.511.011.512.0f1 (ppm)

6.02

3.01

3.00

9.00

1.00

2.00

2.01

2.00

3.02

3.00

1.00

1.03

1.00

0.10

690.

2124

0.34

86

0.92

30

2.75

052.

7760

2.80

252.

9617

3.01

213.

0383

3.06

34

6.54

296.

5709

6.81

066.

8386

6.93

496.

9588

6.98

007.

0044

7.02

857.

0927

7.11

797.

1420

7.16

457.

1684

7.18

967.

2061

7.21

037.

2597

7.30

097.

3260

7.48

537.

4908

7.51

067.

5161

7.53

597.

5415

8.79

568.

8115

-100102030405060708090100110120130140150160170180190200210f1 (ppm)

-5.3

9-4

.35

-4.2

2

18.2

8

25.8

1

35.1

137

.60

76.7

4 CD

Cl3

77.1

6 CD

Cl3

77.5

8 CD

Cl3

119.

6112

2.91

124.

6512

8.04

128.

3712

9.44

129.

8713

3.87

134.

85

142.

52

150.

2215

3.46

166.

51

-1.0-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.511.011.512.0f1 (ppm)

3.02

3.02

1.00

2.00

3.01

1.00

2.02

4.01

3.03

1.01

1.01

0.98

0.23

080.

3816

2.81

442.

8412

2.86

613.

0793

3.10

55

3.63

47

6.52

806.

5552

6.58

846.

6142

6.97

707.

0025

7.02

197.

0297

7.04

587.

1170

7.14

177.

1689

7.19

767.

2172

7.25

997.

3210

7.34

607.

5000

7.52

537.

5506

8.80

578.

8212

-100102030405060708090100110120130140150160170180190200210f1 (ppm)

-5.5

2-4

.20

35.7

937

.16

55.0

7

76.7

4 CD

Cl3

77.1

6 CD

Cl3

77.5

8 CD

Cl3

111.

2511

4.14

121.

1012

2.95

124.

7412

8.12

128.

3012

8.93

129.

8813

3.89

142.

3514

3.75

150.

22

159.

34

166.

36

-1.0-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.511.011.512.0f1 (ppm)

3.00

3.00

1.00

1.02

1.02

3.00

2.00

1.02

4.00

3.03

1.00

1.01

1.00

0.24

580.

4100

2.87

532.

8902

2.91

102.

9260

3.03

343.

0696

3.08

123.

1170

3.15

133.

1662

3.19

903.

2140

3.70

926.

6333

6.65

806.

6823

6.70

766.

8805

6.88

526.

9051

6.90

996.

9910

7.01

657.

0323

7.04

177.

0480

7.10

557.

1155

7.12

967.

1549

7.15

757.

1697

7.17

447.

1790

7.18

367.

1952

7.19

977.

2605

7.34

727.

3506

7.37

237.

3758

7.47

987.

4856

7.50

527.

5109

7.53

057.

5362

8.79

788.

8137

-100102030405060708090100110120130140150160170180190200210f1 (ppm)

-5.5

0-4

.21

29.8

7

35.5

5

55.1

9

76.7

4 CD

Cl3

77.1

6 CD

Cl3

77.5

8 CD

Cl3

110.

05

120.

0512

2.75

124.

5212

6.75

127.

9012

8.33

129.

8412

9.97

130.

3113

3.70

142.

89

150.

07

157.

43

166.

68

-1.0-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.511.011.512.0f1 (ppm)

-1000

0

1000

2000

3000

4000

5000

6000

7000

8000

9000

10000

11000

12000

13000RD-2-269-2-Proton.3.fidRD-2-269-2-Proton

3.00

3.01

3.01

1.00

2.03

2.00

2.03

6.02

1.02

1.02

0.19

000.

3786

2.30

512.

7657

2.78

662.

7969

2.81

813.

0353

3.08

333.

0959

3.11

623.

1326

3.14

486.

9422

6.96

557.

0162

7.02

057.

0250

7.03

797.

0453

7.05

347.

0586

7.06

427.

0693

7.07

377.

1079

7.12

257.

1328

7.13

777.

1472

7.15

167.

1585

7.16

377.

1717

7.18

187.

1869

7.19

307.

2073

7.21

327.

2352

7.26

077.

2743

7.28

027.

2857

7.29

827.

3040

7.30

948.

6552

8.67

21

-100102030405060708090100110120130140150160170180190200210f1 (ppm)

-500

0

500

1000

1500

2000

2500

3000

3500

4000

4500

5000

RD-2-269-2-Carb.15.fidRD-2-269-2-Carb -5

.77

-4.0

2

21.1

6

35.5

437

.11

76.7

477

.16

77.5

8

111.

87

119.

1912

4.13

125.

0912

8.15

128.

3012

8.68

129.

4113

1.03

132.

1413

3.14

141.

4114

3.62

144.

9415

0.06

165.

11

-1.0-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.511.011.512.0f1 (ppm)

0

1000

2000

3000

4000

5000

6000

7000

8000

9000

RD-2-269-1-1H.8.fidRD-2-269-1-1H

3.03

3.02

3.00

1.00

2.02

2.01

6.02

3.00

1.01

0.18

680.

3660

2.28

28

2.75

942.

7856

2.81

193.

0403

3.06

656.

7113

6.74

046.

7698

6.89

086.

8978

6.90

946.

9192

6.93

046.

9378

6.95

366.

9574

6.96

266.

9727

6.98

026.

9854

7.00

557.

0147

7.01

877.

0220

7.03

047.

0372

7.05

007.

0542

7.05

867.

1151

7.12

197.

1422

7.14

727.

1531

7.17

067.

1739

7.26

038.

6485

8.66

46

-100102030405060708090100110120130140150160170180190200210f1 (ppm)

-1000

-500

0

500

1000

1500

2000

2500

3000

3500

4000

4500

5000

5500

6000

6500

7000

7500

8000

RD-2-269-1-Carbon.13.fidRD-2-269-1-Carbon -5

.64

-4.0

6

21.1

3

35.0

837

.52

76.7

477

.16

77.5

9

114.

5411

4.82

123.

9412

4.80

128.

1412

8.30

129.

8312

9.93

129.

9313

1.04

131.

0413

7.70

137.7

414

2.18

144.

7415

0.02

159.

4916

2.71

165.

48

-190-180-170-160-150-140-130-120-110-100-90-80-70-60-50-40-30-20-100f1 (ppm)

-200

-100

0

100

200

300

400

500

600

700

800

900

1000

1100

1200

1300

1400

1500

1600

1700

1800

1900

2000

2100

2200

2300RD-2-269-1-F.5.fidRD-2-269-1-F

-116

.77

-1.0-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.511.011.512.0f1 (ppm)

-1000

0

1000

2000

3000

4000

5000

6000

7000

8000

9000

10000

11000

ST-8-72-1H.5.fidST-8-72-1H

3.03

3.01

2.03

1.00

2.00

2.01

3.00

2.02

2.01

2.05

1.00

1.00

0.31

070.

4492

2.93

572.

9526

2.98

383.

0014

3.01

723.

0494

3.05

453.

0651

3.10

133.

4327

3.44

933.

4681

3.48

46

6.60

896.

6359

6.66

436.

7920

6.81

166.

8353

6.98

207.

0072

7.02

287.

0466

7.10

717.

1301

7.15

447.

2619

7.38

937.

4023

7.41

647.

4317

7.46

237.

4880

7.744

57.7

671

7.794

37.

8231

8.11

968.

1484

8.96

078.

9668

8.97

388.

9809

8.98

71

-100102030405060708090100110120130140150160170180190200210f1 (ppm)

-1000

0

1000

2000

3000

4000

5000

6000

7000

8000

9000

10000

ST-8-72-13C.1.fidST-8-72-13C -4

.38

-2.5

6

35.2

037

.66

76.7

377

.15

77.5

8

114.

2511

4.53

120.

8912

4.41

126.

0712

7.79

127.

9012

8.36

129.

4012

9.70

129.

8013

6.24

136.

7413

8.18

138.

2113

9.58

143.

2414

9.11

152.

62

159.

2616

2.48

-190-180-170-160-150-140-130-120-110-100-90-80-70-60-50-40-30-20-100f1 (ppm)

-1000

0

1000

2000

3000

4000

5000

6000

7000

8000

9000

10000

11000

12000

13000

14000ST-8-72-19F.4.fidST-8-72-19F

-117

.35

-1.0-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.511.011.512.0f1 (ppm)

0

500

1000

1500

2000

2500

3000

3500

4000

4500

5000ST-8-71-1H.2.fidST-8-71-1H

3.04

3.03

3.04

2.05

1.00

2.02

2.03

5.02

1.05

1.08

2.02

1.00

1.03

0.32

870.

4985

1.92

79

2.98

683.

0192

3.02

543.

0361

3.05

763.

1077

3.38

643.

4042

3.41

953.

4369

6.77

536.

8157

6.84

016.

8532

6.86

756.

9594

6.98

277.

0078

7.03

317.

0772

7.10

167.

1264

7.26

037.

3605

7.37

457.

3879

7.40

207.

4372

7.46

187.

4873

7.768

67.7

861

7.81

288.

1034

8.13

068.

9296

8.94

38

-100102030405060708090100110120130140150160170180190200210f1 (ppm)

-1000

-500

0

500

1000

1500

2000

2500

3000

3500

4000

4500

5000

5500

6000

6500

7000

7500

8000

8500ST-8-71-13C.1.fidST-8-71-13C -4

.14

-2.5

9

19.2

6

33.2

035

.88

120.

8312

4.32

125.

2412

5.37

126.

0512

7.82

128.

4312

9.01

129.

3812

9.79

135.

9213

6.20

136.

8213

9.66

140.

6314

3.56

149.

1015

2.73

-1.0-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.511.011.512.0f1 (ppm)

0

5000

10000

15000

20000

25000

30000

35000

40000

3.02

3.02

3.01

1.00

2.01

8.02

1.02

1.00

1.02

1.00

0.24

120.

3653

2.20

892.

7869

2.80

252.

8235

2.83

912.

9495

2.99

773.

0345

3.04

903.

0646

3.09

723.

1127

6.78

416.

8131

6.84

256.

8762

6.89

306.

9210

7.17

767.

1812

7.19

777.

2025

7.20

677.

2191

7.22

287.

2596

7.30

437.

3293

7.49

847.

5036

7.52

377.

5290

7.54

907.

5543

8.80

108.

8166

-100102030405060708090100110120130140150160170180190200210f1 (ppm)

0

1000

2000

3000

4000

5000

6000

7000

8000

9000

10000

11000

12000

13000

14000

15000

16000

17000

-5.4

1-4

.38

21.0

5

35.4

536

.56

76.7

4 CD

Cl3

77.1

6 CD

Cl3

77.5

8 CD

Cl3

114.

7111

4.99

122.

9812

8.44

128.

8012

9.33

129.

4312

9.88

133.

9213

5.06

137.

9513

8.67

150.

27

158.

9816

2.19

166.

15

-360-340-320-300-280-260-240-220-200-180-160-140-120-100-80-60-40-20020406080100120140160f1 (ppm)

0

100

200

300

400

500

600

700

800

900

1000

1100

1200

1300

1400

1500

1600

1700

1800

1900

2000

2100

-117

.79

-1.0-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.511.011.512.0f1 (ppm)

-10000

0

10000

20000

30000

40000

50000

60000

70000

80000

90000

100000

110000

120000

130000

3.01

3.01

3.01

1.00

2.03

3.01

2.01

0.98

2.00

2.00

1.01

1.02

1.00

1.00

1.00

0.20

110.

3539

2.21

202.

7381

2.75

842.

7691

2.78

972.

9933

3.02

163.

0416

3.05

273.

1012

3.69

09

6.61

346.

6420

6.74

596.

7811

6.80

716.

8205

6.84

646.

8934

6.92

187.

0089

7.03

407.

0592

7.16

527.

1692

7.18

567.

1903

7.19

477.

2108

7.26

047.

2824

7.30

767.

4842

7.48

977.

5097

7.51

517.

5349

7.54

058.

7945

8.81

05

9.59

62

-100102030405060708090100110120130140150160170180190200210f1 (ppm)

0

5000

10000

15000

20000

25000

30000

35000

40000

45000

50000

-5.5

4-4

.19

21.6

1

34.7

737

.29

55.2

2

76.7

4 CD

Cl3

77.1

6 CD

Cl3

77.5

8 CD

Cl3

113.

46

122.

8712

5.23

125.

4512

7.91

129.

2312

9.47

129.

9113

3.85

134.

2813

7.37

142.

2915

0.12

157.

54

166.

54

-1.0-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.511.011.512.0f1 (ppm)

3.02

3.01

3.01

1.00

2.02

3.01

1.00

2.01

4.00

1.03

1.01

1.01

1.02

1.02

0.22

930.

3665

2.20

10

2.78

542.

8082

2.81

402.

8365

3.03

923.

0625

3.66

93

6.50

536.

5479

6.57

756.

6036

6.89

207.

0211

7.04

717.

0733

7.16

677.

1879

7.20

827.

2605

7.30

437.

3294

7.48

787.

5129

7.53

82

8.79

408.

8072

-100102030405060708090100110120130140150160170180190200210f1 (ppm)

-5.4

1-4

.22

21.0

4

35.1

937

.41

55.0

7

76.7

4 CD

Cl3

77.1

6 CD

Cl3

77.5

8 CD

Cl3

110.

2111

3.96

120.

8612

2.87

128.

4412

8.75

128.

9012

9.89

133.

8513

4.92

138.

9414

4.17

150.

20

159.

40

166.

46

-1.0-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.511.011.512.0f1 (ppm)

3.00

3.01

1.00

2.01

4.02

5.00

1.00

1.00

1.00

0.24

580.

3857

2.80

192.

8174

2.83

912.

8548

3.03

023.

0684

3.07

873.

1161

3.14

253.

1580

3.19

083.

2064

6.73

556.

7647

6.79

756.

8044

6.82

696.

8482

6.85

576.

8714

6.87

996.

8897

6.90

046.

9109

6.91

917.

1138

7.13

947.

1538

7.17

927.

1857

7.19

057.

2027

7.20

657.

2115

7.21

637.

2284

7.23

217.

2596

7.27

017.

2944

7.32

327.

3272

7.33

087.

3485

7.35

237.

3558

7.51

207.

5176

7.53

747.

5431

7.56

277.

5684

8.80

608.

8220

-100102030405060708090100110120130140150160170180190200210f1 (ppm)

-5.5

1-4

.26

35.9

636

.42

76.7

4 CD

Cl3

77.1

6 CD

Cl3

77.5

8 CD

Cl3

114.

9211

5.19

122.

5912

2.64

123.

1912

5.30

125.

3412

8.44

129.

3312

9.43

129.

9213

0.11

130.

5313

0.96

131.

9313

4.09

137.

2813

7.32

142.

75

150.

34

159.

1216

2.34

165.

75

-190-180-170-160-150-140-130-120-110-100-90-80-70-60-50-40-30-20-100f1 (ppm)

-117

.34

-61.

24

-1.0-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.511.011.512.0f1 (ppm)

3.00

3.02

3.01

1.00

2.00

3.01

2.02

2.00

2.01

1.02

1.00

1.01

2.00

0.98

0.21

900.

3750

2.22

902.

7727

2.79

532.

8026

2.82

533.

0447

3.09

333.

1015

3.12

373.

1500

3.82

36

6.81

946.

8462

6.91

886.

9451

7.02

447.

0519

7.18

127.

1857

7.19

747.

2020

7.20

677.

2113

7.22

307.

2275

7.26

037.

3491

7.37

417.

5086

7.51

447.

5341

7.53

987.

5594

7.56

517.7

356

7.763

38.

8067

8.82

27

-100102030405060708090100110120130140150160170180190200210f1 (ppm)

-5.1

8-3

.68

21.4

5

36.3

636

.97

52.3

6

77.1

6 CD

Cl3

77.5

8 CD

Cl3

78.0

1 CD

Cl3

123.

4412

7.93

128.

5012

9.06

129.

3512

9.81

130.

3313

4.39

134.

6213

8.81

148.

3815

0.70

166.

7116

7.71

-1.0-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.511.011.512.0f1 (ppm)

-10000

0

10000

20000

30000

40000

50000

60000

70000

80000

90000

100000

110000

3.01

3.01

1.00

2.01

3.01

1.02

2.01

1.02

5.04

1.02

1.01

1.00

0.22

390.

3891

2.75

062.

7726

2.78

092.

8029

3.02

753.

0763

3.08

593.

1072

3.13

413.

6751

6.47

296.

4787

6.54

466.

5710

6.59

836.

6061

7.04

297.

0694

7.09

567.

1320

7.15

737.

1820

7.20

367.

2159

7.22

097.

2296

7.24

197.

2467

7.25

987.

2840

7.28

887.

3080

7.31

297.

3529

7.37

797.

5297

7.53

537.

5552

7.56

087.

5805

7.58

618.

8070

8.82

31

-100102030405060708090100110120130140150160170180190200210f1 (ppm)

-5.6

1-4

.10

35.4

737

.24

55.0

9

76.7

4 CD

Cl3

77.1

6 CD

Cl3

77.5

8 CD

Cl3

110.

4011

1.95

114.

0311

9.20

120.

6512

3.17

128.

7512

9.22

129.

4912

9.90

132.

1113

3.12

134.

0714

3.05

143.

59

150.

31

159.

56

165.

93

-1.0-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.511.011.512.0f1 (ppm)

-10000

0

10000

20000

30000

40000

50000

60000

70000

80000

90000

100000

110000

3.00

3.01

3.03

1.00

2.01

3.02

1.00

2.02

2.03

2.00

1.00

1.01

0.28

300.

4072

2.19

76

2.86

302.

8859

2.89

362.

9164

3.27

163.

2977

3.32

103.

3279

3.37

706.

7458

6.77

226.

8139

6.83

876.

9850

7.00

987.

0346

7.06

707.

0827

7.09

137.

1081

7.11

397.

1856

7.18

987.

2061

7.21

087.

2152

7.23

157.

2599

7.28

077.

2849

7.37

677.

4017

7.42

297.

4455

7.45

037.

5254

7.53

087.

5507

7.55

627.

5758

7.58

158.

7959

8.81

17

-100102030405060708090100110120130140150160170180190200210f1 (ppm)

0

5000

10000

15000

20000

25000

-5.5

5-4

.21

21.5

2

34.0

936

.62

76.7

4 CD

Cl3

77.1

6 CD

Cl3

77.5

8 CD

Cl3

112.

4311

8.49

123.

1012

5.28

125.

8312

6.19

128.

0412

9.14

129.

6313

0.07

132.

2913

2.65

134.

0113

7.61

140.

8814

6.15

150.

24

165.

84

-1.0-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.511.011.512.0f1 (ppm)

3.01

3.02

1.00

2.00

3.02

3.02

1.00

2.01

3.02

1.02

1.00

1.01

2.00

1.00

0.24

040.

3862

2.79

382.

8201

2.84

623.

0612

3.11

173.

1377

3.16

16

3.66

323.

8337

6.47

636.

5451

6.57

257.

0144

7.04

037.

0669

7.19

277.

2091

7.21

387.

2182

7.23

047.

2344

7.26

057.

3388

7.36

397.

5127

7.51

807.

5381

7.54

347.

5634

7.56

887.7

425

7.770

08.

8101

8.82

59

-100102030405060708090100110120130140150160170180190200210f1 (ppm)

-5.4

6-4

.17

35.8

637

.27

51.9

455

.08

76.7

4 CD

Cl3

77.1

6 CD

Cl3

77.5

8 CD

Cl3

110.

3211

4.03

120.

7812

3.06

127.

6212

8.62

129.

0512

9.43

129.

9313

4.00

143.

4714

7.78

150.

27

159.

48

166.

1416

7.27

-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.511.011.512.0f1 (ppm)

3.00

3.01

1.00

1.02

1.02

1.01

3.01

1.01

5.00

2.00

2.01

1.00

0.37

950.

5843

3.18

693.

1991

3.22

453.

2366

3.51

003.

5477

3.55

933.

5968

3.79

383.

8057

3.84

303.

8550

7.05

787.

0809

7.18

457.

2096

7.23

617.

2598

7.34

727.

3518

7.36

397.

3671

7.37

277.

3773

7.38

907.

3935

7.48

157.

5085

7.51

167.

5270

7.53

287.

5371

7.54

077.

5439

7.65

967.

6645

7.67

067.

6901

7.69

607.7

157

7.721

47.

8654

7.87

097.

8828

7.88

827.

8971

7.90

897.

9234

7.94

148.

9693

8.98

53

-100102030405060708090100110120130140150160170180190200210f1 (ppm)

-5.5

7-4

.11

32.9

736

.95

76.7

4 CD

Cl3

77.1

6 CD

Cl3

77.5

8 CD

Cl3

123.

3112

3.84

125.

0912

5.13

125.

2312

5.39

125.

8112

6.48

126.

7212

6.84

127.

2712

8.40

128.

9313

0.01

131.

8213

4.00

134.

1413

7.11

147.

2715

0.39

165.

73

-360-340-320-300-280-260-240-220-200-180-160-140-120-100-80-60-40-20020406080100120140160f1 (ppm)

-60.

54

-1.0-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.511.011.512.0f1 (ppm)

3.02

3.00

3.03

1.00

2.03

1.01

1.02

1.01

1.01

4.02

2.02

1.00

1.00

0.20

510.

3781

2.21

532.

7253

2.74

872.

7541

2.77

763.

0335

3.08

263.

0887

3.11

183.

1372

6.71

316.

7430

6.76

886.

8402

6.86

527.

0180

7.04

327.

0683

7.12

757.

1527

7.17

757.

1956

7.20

007.

2174

7.22

167.

2261

7.24

327.

2468

7.25

977.

2790

7.28

387.

3078

7.33

107.

3561

7.52

247.

5280

7.54

787.

5534

7.57

317.

5788

8.80

758.

8229

-100102030405060708090100110120130140150160170180190200210f1 (ppm)

-5.7

0-4

.08

21.5

7

35.4

836

.97

76.7

4 CD

Cl3

77.1

6 CD

Cl3

77.5

8 CD

Cl3

111.

9311

9.26

123.

1412

5.09

125.

9212

8.18

128.

7412

9.07

129.

4712

9.90

132.

1713

3.16

133.

9913

7.72

141.

2114

3.73

150.

32

166.

07

-1.0-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.511.011.512.0f1 (ppm)

-10000

0

10000

20000

30000

40000

50000

60000

70000

80000

90000

100000

110000

120000

3.00

3.00

3.01

2.03

1.03

4.01

6.02

1.00

1.03

1.00

0.23

380.

4222

1.95

15

2.98

392.

9943

3.01

433.

0325

3.04

773.

0600

3.08

193.

0962

3.12

563.

1579

3.17

393.

1896

3.22

196.

9208

6.94

807.

0179

7.04

127.

0495

7.07

487.

0957

7.10

787.

1309

7.15

627.

1751

7.17

857.

1913

7.19

587.

2004

7.21

677.

2570

7.25

967.

2805

7.28

357.

3055

7.30

867.

4873

7.48

977.

5127

7.51

507.

5380

7.54

048.

8028

8.81

88

-100102030405060708090100110120130140150160170180190200210f1 (ppm)

0

500

1000

1500

2000

2500

3000

3500

4000

4500

5000

5500

6000-5.1

1-4

.07

20.4

9

32.2

6

37.0

3

76.7

4 CD

Cl3

77.1

6 CD

Cl3

77.5

8 CD

Cl3

122.

9412

4.47

125.

5912

5.78

127.

1412

7.99

128.

4112

9.80

130.

1313

3.83

136.

0514

1.06

142.

4915

0.20

166.

62

-1.0-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.511.011.512.0f1 (ppm)

-10000

0

10000

20000

30000

40000

50000

60000

70000

80000

90000

100000

110000

120000

130000

140000

150000

160000

3.08

3.03

2.99

1.97

1.02

1.93

1.97

2.01

2.01

1.04

1.02

1.06

1.00

0.22

0.42

1.96

2.95

2.98

3.00

3.01

3.04

3.05

3.08

3.11

3.13

3.15

3.18

6.83

6.85

6.94

6.95

6.96

6.97

7.01

7.03

7.09

7.10

7.19

7.21

7.23

7.26

7.29

7.31

7.50

7.53

7.55

8.80

8.82

-100102030405060708090100110120130140150160170180190200210f1 (ppm)

0

1000

2000

3000

4000

5000

6000

7000

8000

9000-5.1

9-4

.03

20.5

3

32.2

936

.42

76.7

4 CD

Cl3

77.1

6 CD

Cl3

77.5

8 CD

Cl3

123.

0212

4.65

125.

8612

7.05

128.

0812

9.75

129.

8113

0.28

131.

2713

3.93

136.

0514

0.63

141.

0015

0.25

166.

43

-1.0-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.511.011.512.0f1 (ppm)

-20000

-10000

0

10000

20000

30000

40000

50000

60000

70000

80000

90000

100000

110000

120000

130000

140000

150000

160000

170000

180000

190000

200000

210000

1.01

2.01

1.00

2.00

2.00

5.01

2.30

20

2.98

613.

0083

4.81

214.

8342

4.85

61

6.95

516.

9841

7.01

317.

0955

7.10

237.

1138

7.12

347.

1357

7.14

237.

2597

7.28

677.

3061

7.31

267.

3179

7.32

967.

3456

7.36

467.

3839

7.39

11

-100102030405060708090100110120130140150160170180190200210f1 (ppm)

0

500

1000

1500

2000

2500

3000

3500

4000

4500

5000

5500

6000

6500

45.0

3

75.4

076

.74

CDCl

377

.16

CDCl

377

.58

CDCl

3

115.

0611

5.34

126.

0012

7.75

128.

4813

0.98

131.

0913

3.75

133.

79

143.

72

160.

1516

3.39

-190-180-170-160-150-140-130-120-110-100-90-80-70-60-50-40-30-20-100f1 (ppm)

0

500

1000

1500

2000

2500

3000

3500

4000

4500

5000

5500

6000

6500

7000

-115

.09

-1.0-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.511.011.512.0f1 (ppm)

1.01

3.02

2.01

1.00

4.01

5.00

1.92

63

2.33

112.

8980

2.92

662.

9436

2.97

212.

9924

3.00

823.

0380

3.05

38

4.85

514.

8710

4.88

374.

8995

7.07

777.

0967

7.10

647.

1104

7.13

917.

2596

7.26

967.

2814

7.28

717.

2908

7.29

387.

3017

7.31

057.

3241

7.32

727.

3321

7.34

277.

3507

7.35

327.

3615

7.37

017.

3886

-100102030405060708090100110120130140150160170180190200210f1 (ppm)

0

200

400

600

800

1000

1200

1400

1600

1800

2000

2200

2400

2600

2800

3000

3200

3400

3600

21.1

1

45.7

0

75.3

976

.74

CDCl

377

.16

CDCl

377

.58

CDCl

3

126.

0012

7.57

128.

4112

9.24

129.

4613

5.00

136.

1314

4.00

-1.0-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.511.011.512.0f1 (ppm)

-5000

0

5000

10000

15000

20000

25000

30000

35000

40000

45000

50000

55000

3.00

3.01

2.01

2.00

1.03

2.01

2.01

1.00

2.02

5.03

3.00

1.01

1.01

1.00

0.23

350.

4265

2.15

152.

1762

2.20

852.

2275

2.50

382.

5300

2.55

652.

7216

2.73

442.

7583

2.77

073.

0231

3.07

203.

1089

3.13

203.

1444

3.18

093.

1935

4.93

764.

9536

4.96

945.

0107

5.69

605.

7179

5.73

025.

7401

5.75

195.

7743

5.78

695.

7969

5.80

875.

8304

6.80

516.

8303

6.85

676.

8817

6.95

126.

9760

7.00

247.

0369

7.05

967.

1244

7.14

827.

1744

7.18

937.

2058

7.21

027.

2146

7.23

107.

2602

7.37

807.

4028

7.52

137.

5466

7.57

198.

8127

8.82

83

-100102030405060708090100110120130140150160170180190200210f1 (ppm)

0

500

1000

1500

2000

2500

3000

3500

4000

4500

5000

5500

6000

-5.5

2-4

.11

31.9

832

.53

35.1

936

.83

76.7

4 CD

Cl3

77.1

6 CD

Cl3

77.5

8 CD

Cl3

114.

8112

3.01

124.

8112

5.50

125.

7712

8.14

128.

4412

8.97

129.

4512

9.88

133.

9513

8.40

139.

5713

9.66

142.

4115

0.29

166.

39

Documents

The Royal Society of Chemistry · To the ArZnI residue was added NiBr. 2 (0.4-1.1 mg, 2-5 mol%), 2-(dimethyl(vinyl)silyl)pyridine (16.3 mg, 0.1 mmol), and aryl halide (0.10 mmol)