NHCOCH 3 C 5 H 11 C 5 H 11 C 5 H 11 O HN O CH 3 O NH O H 3 C R eagent Solvent Tem p. Time Yields Pd(C H 3 CN) 2 Cl 2 CH 3 CN CH 3 CN THF DMF DMF NMP NMP DMSO 80 RT 80 RT 80 RT 80 RT 48 2 48 2 48 2 48 8 18 18 48 48 33 48 18 1 2 DMSO 80 2 17 THF 48 12 RT 2 Pd(C H 3 CN) 2 Cl 2 Solvent Pd(O Ac) 2 Pd(PPh 3 ) 2 Cl 2 PdCl 2 NHCOCH 3 C 5 H 11 C 5 H 11 C 5 H 11 O HN O CH 3 O NH O H 3 C R eagent Yields(%) DMF heatto 80 o C Pd(II) 1 2 16 19 15 N H R R R O HN O R' O NH O R' DMF Pd(C H 3 CN) 2 Cl 2 R 1d R = Ph Yields(%) 2d (35 ) R' CH 3 Ph 1e R = C 5 H 11 1g R = Ph 2e (26 ) 2g (22 ) heatto 80 o C R' O 1b R = C 6 H 13 1c R = C 7 H 15 1fR = C 6 H 13 1 2 2b (38 ) 2c (36 ) 2f (24 ) N H R O Pd(C H 3 CN) 2 Cl 2 N H R O N H O Pd Pd R HN O R Pd NH O R Pd O HN O O NH O R R HN O H 2 O 1 3 4 5 8 2 HN O NH O Pd R R Pd 6 HN O NH O Pd R R Pd 7 H 2 O R Pd R O HN O Synthesis of various substituted nap hthalene via Palladium catalyzed Cycl ization Chia-Ying Lee b , Ming-Jung Wu a * a Faculty of Medicinal and Applied Chemistry, Kaohsiung Medical University, Kaohsiung, Taiwan. b Graduate Institute of Pharmaceutical Sciences, Kaohsiung Medical University, Kaohsiung, Taiwan. Tel: 886-7-3121101 ext 2220; Fax: 886-7-3125339; E-mail: [email protected] Abstract A novel palladium catalyzed cyclization of enediynes to give the naphthalene de rivatives was reported. For instance, treatment of N-acetyl-2-(3(Z)-undecen-1, 5-diynyl)anilines 1 with Pd(CH 3 CN) 2 Cl 2 in DMF at 80 o C for 2h in 48 % yield. NHR' R R R O NHR' O R'HN 1 2 Pd(C H 3 CN) 2 Cl 2 D M F,heat80 o C Table 1 Reaction of 1 with Pd(CH 3 CN) 2 Cl 2 in Various Solvents Table 2 Reaction of 1 with Various Pd(II)-catalysts Table 3 Cyclization of enediynes 1b-g Figure 1 X-ray structure of compound 2d Scheme 1 Proposed Mechanism for the Formation of compound 2

Synthesis of various substituted naphthalene via Palladium catalyzed Cyclization

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Synthesis of various substituted naphthalene via Palladium catalyzed Cyclization Chia-Ying Lee b , Ming-Jung Wu a * a Faculty of Medicinal and Applied Chemistry, Kaohsiung Medical University, Kaohsiung, Taiwan. - PowerPoint PPT Presentation

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Page 1: Synthesis of various substituted naphthalene via Palladium catalyzed Cyclization

NHCOCH3

C5H11

OHN

CH3

ONH

H3C

Reagent Solvent Temp. Time Yields

Pd(CH3CN)2Cl2 CH3CN

CH3CN

THF

DMF

NMP

DMSO

1 2

DMSO 80 2 17

THF 48

Pd(CH3CN)2Cl2

Solvent

Pd(OAc)2

Pd(PPh3)2Cl2

PdCl2

NHCOCH3

C5H11

OHN

CH3

ONH

H3C

Reagent Yields(%)

DMFheat to 80oC

Pd(II)

1 2

OHN

R'O

NHO

DMF

Pd(CH3CN)2Cl2

1d R = Ph

Yields(%)

2d ( 35 )

CH3

Ph 1e R = C5H11

1g R = Ph

2e ( 26 )

2g ( 22 )

heat to 80oCR'

1b R = C6H13

1c R = C7H15

1f R = C6H13

1 2

2b ( 38 )

2c ( 36 )

2f ( 24 )

O Pd(CH3CN)2Cl2

Pd Pd

HNO

RPd

NHO

RPd

OHN

NHO R

OH2O

1 3 4

HNO

NHO

PdR R

HNO

NHO

PdR R

H2O

PdR

OHN

Synthesis of various substituted naphthalene via Palladium catalyzed Cyclization

Chia-Ying Lee b, Ming-Jung Wu a*a Faculty of Medicinal and Applied Chemistry, Kaohsiung Medical University, Kaohsiung, Taiwan.

b Graduate Institute of Pharmaceutical Sciences, Kaohsiung Medical University, Kaohsiung, Taiwan.Tel: 886-7-3121101 ext 2220; Fax: 886-7-3125339; E-mail: [email protected]

AbstractA novel palladium catalyzed cyclization of enediynes to give the naphthalene derivatives was reported. For instance, treatment of N-acetyl-2-(3(Z)-undecen-1,5-diynyl)anilines 1 with Pd(CH3CN)2Cl2 in DMF at 80 oC for 2h in 48 % yield.

NHR'

ONHR'O

R'HN

Pd(CH3CN)2Cl2

DMF, heat 80oC

Table 1 Reaction of 1 with Pd(CH3CN)2Cl2 in Various Solvents

Table 2 Reaction of 1 with Various Pd(II)-catalysts

Table 3 Cyclization of enediynes 1b-g

Figure 1 X-ray structure of compound 2d

Scheme 1 Proposed Mechanism for the Formation of compound 2