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Trans-cyclooctene
and Its Application
Reporter: Peng Yan
Supervisor: Ping Lu
Fudan University
2019-11-1
Background01
The Reaction of TCO—
IEDDA, Click, Bioorthogonal reaction02
03
CONTENTS
Some new reactions of TCO
04 Summary
M. T. Taylor, M. L. Blackman, O. Dmitrenko, J. M. Fox, J. Am. Chem. Soc., 2011, 133, 9646.
The Reaction of TCO02
1
M. T. Taylor, M. L. Blackman, O. Dmitrenko, J. M. Fox, J. Am. Chem. Soc., 2011, 133, 9646.
The Reaction of TCO02
2
Background01
K. Ziegler, H.Wilms, Ann., 1950, 1, 567.; S. W. Fenton, C. F. Spencer, A. C. Cope, J. Am. Chem. Soc., 1952, 74, 5884.
R. A. Pike, C. F. Spencer, A. C. Cope, J. Am. Chem. Soc., 1953, 75, 3212. 5
New Synthesis Method01
J. Deyrup, M. Betkouski, J. Org. Chem., 1972, 37, 3561.
J. S. Swenton, J. Org. Chem., 1969, 34, 3217. 6
New Synthesis Method01
M. Royzen, G. P. A. Yap, J. M. Fox, J. Am. Chem. Soc., 2008, 130, 3760
Transannular Cyclization Reaction
9
N. J. Agard, J. A. Prescher, C. R. Bertozzi, J. Am. Chem. Soc., 2004, 126, 15046.
The Reaction of TCO02
Bioorthogonal chemistry: Any chemical reaction that can occur inside
of living systems without interfering with native biochemical processes.
11
N. J. Agard, J. A. Prescher, C. R. Bertozzi, J. Am. Chem. Soc., 2004, 126, 15046.
The Reaction of TCO02
By Bertozzi
12
N. J. Agard, J. A. Prescher, C. R. Bertozzi, J. Am. Chem. Soc., 2004, 126, 15046.
The Reaction of TCO02
– 2 3 3, [Cu]
k2 of SPAAC = 5 M-1s-1
SPAAC = Strain-Promoted Azide-Alkyne Cycloaddition
13
M. L. Blackman, M. Royzen, J. M. Fox, J. Am. Chem. Soc., 2008, 130, 13518.
Diels-Alder Reactions of Tetrazines with trans-Cyclooctene
Fast Reactivity at Low Micromolar Concentrations
The Reaction of TCO02
14
M. T. Taylor, M. L. Blackman, O. Dmitrenko, J. M. Fox, J. Am. Chem. Soc., 2011, 133, 9646.
The Reaction of TCO02
ΔGǂ = 8.92 kcal/mol
ΔGǂ = 6.95 kcal/mol
ΔGǂ =8.24 kcal/mol
16
M. T. Taylor, M. L. Blackman, O. Dmitrenko, J. M. Fox, J. Am. Chem. Soc., 2011, 133, 9646.
The Reaction of TCO02
17
M. T. Taylor, M. L. Blackman, O. Dmitrenko, J. M. Fox, J. Am. Chem. Soc., 2011, 133, 9646.
The Reaction of TCO02
18
A. Darko, S. Wallace, O. Dmitrenko, M. M. Machovina, R. A. Mehl, J. W. Chinb, J. M. Fox, Chem. Sci., 2014, 5, 3770
The Reaction of TCO02
ΔGǂ = 16.09 kcal/mol
ΔGǂ = 13.27 kcal/mol
19
A. Darko, S. Wallace, O. Dmitrenko, M. M. Machovina, R. A. Mehl, J. W. Chinb, J. M. Fox, Chem. Sci., 2014, 5, 3770
The Reaction of TCO02
20
A. Darko, S. Wallace, O. Dmitrenko, M. M. Machovina, R. A. Mehl, J. W. Chinb, J. M. Fox, Chem. Sci., 2014, 5, 3770
The Reaction of TCO02
21
A. Darko, S. Wallace, O. Dmitrenko, M. M. Machovina, R. A. Mehl, J. W. Chinb, J. M. Fox, Chem. Sci., 2014, 5, 3770
The Reaction of TCO02
22
T. Yokoi, T. Ueda, H. Tanimoto, T. Morimoto, K. Kakiuchi, Chem. Commun., 2019, 55, 1891
The Reaction of TCO02
23
M. Royzen, M. T. Taylor, A. DeAngelis, J. M. Fox, Chem. Sci., 2011, 2, 2162 – 2165.
Some New Reactions of TCO03
25
M. Royzen, M. T. Taylor, A. DeAngelis, J. M. Fox, Chem. Sci., 2011, 2, 2162 – 2165.
Some New Reactions of TCO03
26
M. Royzen, M. T. Taylor, A. DeAngelis, J. M. Fox, Chem. Sci., 2011, 2, 2162 – 2165.
Some New Reactions of TCO03
27
M. Royzen, M. T. Taylor, A. DeAngelis, J. M. Fox, Chem. Sci., 2011, 2, 2162 – 2165.
Some New Reactions of TCO03
28
M. Royzen, M. T. Taylor, A. DeAngelis, J. M. Fox, Chem. Sci., 2011, 2, 2162 – 2165.
Some New Reactions of TCO03
28
S. Einaru, K. Shitamichi, T. Nagano, A. Matsumoto, K. Asano, S. Matsubara, Angew. Chem. Int. Ed., 2018, 57, 13863 –13867
Some New Reactions of TCO03
29
S. Einaru, K. Shitamichi, T. Nagano, A. Matsumoto, K. Asano, S. Matsubara, Angew. Chem. Int. Ed., 2018, 57, 13863 –13867
Some New Reactions of TCO03
30
S. Einaru, K. Shitamichi, T. Nagano, A. Matsumoto, K. Asano, S. Matsubara, Angew. Chem. Int. Ed., 2018, 57, 13863 –13867 31
S. Einaru, K. Shitamichi, T. Nagano, A. Matsumoto, K. Asano, S. Matsubara, Angew. Chem. Int. Ed., 2018, 57, 13863 –13867
Some New Reactions of TCO03
32
S. Einaru, K. Shitamichi, T. Nagano, A. Matsumoto, K. Asano, S. Matsubara, Angew. Chem. Int. Ed., 2018, 57, 13863 –13867
Some New Reactions of TCO03
33
N. Arichi, K. Yamada, Y. Yamaoka, K. Takasu, J. Am. Chem. Soc., 2015, 137, 9579.
Some New Reactions of TCO03
34
Some New Reactions of TCO03
N. Arichi, K. Yamada, Y. Yamaoka, K. Takasu, J. Am. Chem. Soc., 2015, 137, 9579. 35
Some New Reactions of TCO03
N. Arichi, K. Yamada, Y. Yamaoka, K. Takasu, J. Am. Chem. Soc., 2015, 137, 9579. 36
Some New Reactions of TCO03
N. Arichi, K. Yamada, Y. Yamaoka, K. Takasu, J. Am. Chem. Soc., 2015, 137, 9579. 37
C. Denk,D. Svatunek, J. Stanek, T. Filip, D. Matscheko, C. Kuntner, T. Wanek, H. Mikula, Bioconjugate Chem. 2016, 27, 1707
PET: Positron emission tomography
39
Some New Reactions of TCO03
C. Denk,D. Svatunek, J. Stanek, T. Filip, D. Matscheko, C. Kuntner, T. Wanek, H. Mikula, Bioconjugate Chem. 2016, 27, 170740
C. Denk,D. Svatunek, J. Stanek, T. Filip, D. Matscheko, C. Kuntner, T. Wanek, H. Mikula, Bioconjugate Chem. 2016, 27, 170741
Some New Reactions of TCO03
b = brain, bl = bladder, k = kidney, lu = lung
C. Denk,D. Svatunek, J. Stanek, T. Filip, D. Matscheko, C. Kuntner, T. Wanek, H. Mikula, Bioconjugate Chem. 2016, 27, 170742
Some New Reactions of TCO03
PET Image
Summary04
43
• Planar chirality
• High HOMO energy
• High energy of ring strain
Properties:
Reaction:
• IEDDA reaction
• Click reaction
• Bioorthogonal reaction
• Total synthesis
• The catalyst of transition metal