Domino Effects in Organic Chemistry Fudong Wang 2005.7.1
Content •Domino Reaction——Brief Introduction •Domino reaction in Total synthesis •Asymmetric domino reaction •Domino reaction & Organometallics
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Content •Domino Reaction——Brief Introduction •Domino reaction in Total synthesis •Asymmetric domino reaction •Domino reaction & Organometallics
What’s the Domino Effect Take a number of dominoes and build a row by standing them on end with only a small distance in between. If you do it right, you can tip the first domino and cause all others to fall down in succession Clip from “Robots”
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Domino Reaction A domino reaction is a process involving two or more bond-forming transformations (usually C-C bonds) which take place under the same reaction conditions without adding additional reagents and catalysts, and in which the subsequent reactions result as a consequence of the functionality formed in the previous step. －－Lutz F. Tietze Chem. Rev. 1996, 96, 115−136
The First Domino Reaction
Robinson, R. J. Chem. Soc. 1917, 111, 762
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Classification of Domino Reaction •Cationic Domino Reaction •Anionic Domino Reaction •Radical Domino Reaction •Pericyclic Domino Reaction •Transition Metal-Catalyzed Domino Reaction •Enzymatic Domino Reaction •Anionic−Pericyclic and Related Domino Reactions
Cationic Domino Reaction
triterpene sophoradiol
William S. Johnson. J. Org. Chem. 1994, 59, 2324
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Anionic Domino Reaction O
O LiNR2
O
O CO2R'
O
CO2R'
a
path b
O
b
O OR' Li O
O
O
O
Li OR' O
path a
O
CO2R' O
CO2R' O
O
Hisahiro Hagiwara.Org. Lett., Vol. 6, No. 7, 2004
Radical Domino Reaction
Hitchcock, S. A.Tetrahedron Lett. 1992, 33, 4843
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Pericyclic Domino Reaction
Pagodane
H. Prinzbach. J. Am. Chem. Soc. 1987, 109, 4626
Transition Metal-Catalyzed Domino Reaction
n=4
Barry M. Trost. J. Am. Chem. Soc. 1993, 115, 9421
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Enzymatic Domino Reaction
Precorrin-5
Scott, A. I. Synlett 1994, 871
Anionic−Pericyclic and Related Domino Reactions
Tietze, L. F. Angew. Chem., Int. Ed. Engl. 1982, 21, 863
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Content Brief Introduction —— •Domino Reaction ——Brief Reaction—— •Domino reaction in Total synthesis •Asymmetric domino reaction •Domino reaction & Organometallics
Domino reaction in Total synthesis H
H3CO N
H3CO
H R
O n
H
n=0,1 Tetraponerines
Erythrina
O HN
CH2OH OMe
O O
H
H solanapyrone E
OH N HH
N
H MeO2C
hirsutine
H OMe
O Me Me HO Me MeH Stachyflin
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Domino reaction in Total synthesis
Erythrina: n=1, R=Me B-homoerythrina: n=1, R=Me
Lutz F. Tietze. Angew. Chem. Int. Ed. 2004, 43, 5391
Domino reaction in Total synthesis
CH2OH OMe
O O
CHO H
MeO2C
H
H
O
OTBDMS
H
TBDMSO +
H
H
CO2Me
O
solanapyrone E Hisahiro Hagiwara, Org. Lett., 2001, 3, 251 Hisahiro Hagiwara, J. Org. Chem. 2002, 67, 5969
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Domino reaction in Total synthesis
Domino reaction in Total synthesis Tetraponerines T1-T8
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Domino reaction in Total synthesis
Siegfried Blechert, J. Am. Chem. Soc. 2000, 122, 9584
Domino reaction in Total synthesis
N HH
N
H MeO2C
H OMe
hirsutine
Lutz F. Tietze, Angew. Chem. Int. Ed. 1999,38,2045
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Domino reaction in Total synthesis
Domino reaction in Total synthesis
Tadashi Katoh, Org. Lett., 2002, 4, 4483
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Domino reaction in Total synthesis HO Me H
O
O
F3B O
Me Me
HO Me H
Me Me
HO Me H
Me
HO Me
H
O Me
F3B O Me MeH
O Me Me
HO Me MeH
Me
Me
F3B O Me Me
Me Me
Me
HO Me
Me
O Me Me
O Me MeH
Me HO Me MeH
Content Brief Introduction —— •Domino Reaction ——Brief Reaction—— •Domino reaction in Total synthesis •Asymmetric domino reaction •Domino reaction & Organometallics
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Asymmetric domino reaction
Christoph Schneider,Angew. Chem. Int. Ed. 2000,39,2948
Asymmetric domino reaction
Christoph Schneider, Angew. Chem. Int. Ed. 2000,39,2948
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Asymmetric domino reaction
Mario D. Bachi, J. Am. Chem. Soc. 2004, 126, 2708
Asymmetric domino reaction
Lutz F. Tietze, Angew. Chem. Int. Ed. 2005, 44, 257
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Asymmetric domino reaction
Gunter Helmchen, Tetrahedron Letters. 1999, 40, 3867
Asymmetric domino reaction
Ferenc Fulop, Tetrahedron Letters. 2004, 45, 6199
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Content Brief Introduction —— •Domino Reaction ——Brief Reaction—— •Domino reaction in Total synthesis •Asymmetric domino reaction •Domino reaction & Organometallics
Domino reaction & Organometallics (Pd)
Armin de Meijere. Acc. Chem. Res. 2005, 38, 413
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Domino reaction & Organometallics (Pd)
Armin de Meijere. Tetrahedron Lett.1992, 33, 8039
Domino reaction & Organometallics (Pd)
Armin de Meijere. Tetrahedron Lett.1996, 52, 11545
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Domino reaction & Organometallics (Pd)
Armin de Meijere. Synlett. 1991, 777
Domino reaction & Organometallics (Pd)
Armin de Meijere. Eur. J. Org. Chem. 2005, 582
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Domino reaction & Organometallics (Pd)
Armin de Meijere. Eur. J. Org. Chem. 1998, 1521
Armin de Meijere. Chem. -Eur. J., 2001, 7, 4035
Domino reaction & Organometallics (Ni)
Shin-ichi Ikeda. Acc. Chem. Res. 2000, 33, 511
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Domino reaction & Organometallics (Ni)
Shin-ichi Ikeda. J. Org. Chem., 1994 , 59, 6877
Domino reaction & Organometallics (Ni)
R
R
O
OSiMe3 Ni
l SiC Me 3
2
R'
Cl
R''
OSiMe3 R
R'
l SiC Me 3
O
Ni
Cl
or R2Zn
SnR3 four component coupling
R'
Ni
R
R' O
or
R
Ni R'
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Domino reaction & Organometallics (Ni)
Yoshiro Sato. J. Am. Chem. Soc. 1994,116, 5975
Domino reaction & Organometallics (Ni)
John Montgomery. J. Am. Chem. Soc. 1996,118, 2099
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Domino reaction & Organometallics (Cu)
Stephen L. Buchwald. J. Am. Chem. Soc. 2003,125, 2890
Domino reaction & Organometallics (Cu)
Stephen L. Buchwald. J. Am. Chem. Soc. 2003,125, 4978
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Domino reaction & Organometallics (Ru)
Laurence Grimaud. Org. Lett., 2003, 5, 2007
Domino reaction & Organometallics (Rh) OPh O
L= Ph2P
Rh L
Ph
PPh2 Ph
Rh OPh O
O OPh
OPh Rh
L= Ph2P
OPh 88%
OPh
PPh2 Rh
O
O 81%
O L= Ph2P
PPh2
OPh Rh CO
OPh 96%
Masahiro Murakami, J. Am. Chem. Soc. 1998, 120, 9949
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Conclusion
Allow the minimization of waste (solvents, reagents, adsorbents, energy) The amount of labor would go down
Acknowledgement •Prof. Gan •Prof. Yu and Prof. Shi •All the members in our Group •XiangZheng
Thank you for your attention !
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Mercedes Amat, J. Org. Chem. 2002, 67, 5343
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