1995 Fiscal Year Final Research Report Summary
Asymmetric Synthesis based on Carbonyl-Ene Reaction
| Project/Area Number |
06453133
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| Research Category |
Grant-in-Aid for General Scientific Research (B)
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| Allocation Type | Single-year Grants |
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| Research Field |
Synthetic chemistry
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| Research Institution | TOKYO INSTITUTE OF TECHNOLOGY |
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Principal Investigator |
MIKAMI Koichi Tokyo Inst.Tech., Fac.Eng., Prof., 工学部, 助教授 (10157448)
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| Project Period (FY) |
1994 – 1995
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| Keywords | Asymmetric ene reaction / diastereoselection / Diastereofacial selection / Binaphthol dervatives / Chiral titanium complexes / ジアステレオ面選択性 / 不斉合成 |
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| Research Abstract |
The purpose of this work is to develop the new method for asymmetric synthesis based on carbonyl-ene reaction. A summary of the research results is as follow :
(1) Internal Asymmetric Induction
The carbonyl-ene reaction with fluoral is found to afford the erythro-trifluoromethylcsarbinol ion more thasn 90% selectivity.
(2) Relative Asymmetric induction
The carbonyl-ene reaction with b-amino aldehyde is found to exhgiobit the-diastereofacial selectivity in more than 99% selectivity. Furthermore, the reavcti0n with un-symmetricallyt substituted ene component provides only sngle regioisomer (>99% regioselectivity).
(3) Enantiofacial Selective Induction
The asymmetric catalysis of carnbonyl-ene reaction catalyzed by chiral (modified) binaphthol-derived titanium complexes with prochiral carbonyl enophiles such as glyoxylate, fluoral, and conjugate ynals is found to give more than 95% enantiomeric excesses. Furthermore, the asymmetric catalytic carbonyl-ene reaction even with non-prochiral enophile such as formaldehyde afford the high levle of asymmetric induction.
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