2001 Fiscal Year Final Research Report Summary
Studies on Catalytic Activation of Trichlorosilene with Organic Molecules
| Project/Area Number |
12650855
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| Research Category |
Grant-in-Aid for Scientific Research (C)
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| Allocation Type | Single-year Grants |
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| Section | 一般 |
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| Research Field |
Synthetic chemistry
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| Research Institution | Nagasaki University |
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Principal Investigator |
ONEMURA Osamu Nagasaki University, Faculty of Phormactutical Sciences, Associate Professor, 薬学部, 助教授 (60304961)
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| Co-Investigator(Kenkyū-buntansha) |
MATSUMURA Yoshihiro Nagasaki University, Faculty of Phormactutical Sciences, Professor, 薬学部, 教授 (60026309)
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| Project Period (FY) |
2000 – 2001
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| Keywords | Trichlorosilane / Imine / Selective Reduction / Amine / Hypervalent Silicate / Ketone / Alcohol / Optically Active |
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| Research Abstract |
Trichlorosilane (Cl_3SiH) may be one of the candidates sicne it is cheap and easy to handle and has already been used in a larage scale for the reduction of easily reducible compounds as exemplified by transforming phosphine oxide to phosphine (BINAP) and N-acyliminium ion to N-acylamine (herbicide). However, its use for the reduction of ketones is rather limited because of the low reactivity toward ketones. We found that N-formylated pyrrolidine derivatives are efficient catalysts for the activation of Cl_3SiH to reduce ketones, and also that enantiomerically enriched sec-alcohols can be formed with up to 51 % ee when optically active activator was used. This reagent has 7 characteristics described bellow.
1. This is a first example that a catalytic amount of organic molecules can activate Cl_3SiH to reduce ketones.
2. Using L-proline derivatives as activators afford optically active alcohols from ketones.
3. ^<29>Si-NMR indicates the formation of hypervalent silicate species.
4. This reducing reagent has high regioselectivity, diastereoselectivity, and ability of discrimination of substituents.
5. This reducing reagent is highly imino-selective.
6. Using L-proline derivatives as activators afford optically active amines from imines.
7. Trichlorosilane derivatives mediatealdol reaction between N, O-acetals and ketones.
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