2017 Fiscal Year Final Research Report
Exploration of allylic substitution as a method to create chiral C-C bond and its application in organic synthesis
| Project/Area Number |
26410111
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| Research Category |
Grant-in-Aid for Scientific Research (C)
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| Allocation Type | Multi-year Fund |
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| Section | 一般 |
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| Research Field |
Synthetic chemistry
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| Research Institution | Tokyo Institute of Technology |
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Principal Investigator |
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| Project Period (FY) |
2014-04-01 – 2018-03-31
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| Keywords | アリル化反応 / ピコリン酸 / 第四級炭素 / Grignard試薬 / 有機銅試薬 / 有機合成 / ジアリルメタン |
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| Outline of Final Research Achievements |
We recently found allylic substitution at secondary carbon with organocopper reagents derived from Grignard reagents and copper salts. The use of the picolinoxy leaving group provides the high stereo- and regioselectivity in the formation of chiral C-C bond via anti SN2'. In this research, 3,3-disubstituted allylic picolinates were used as substrates to form quaternary carbons on cyclohexane rings and acyclic carbon chains. In practice, cyclobakuchiol A, axenol, and anastrephin, the former type of compounds, have been synthesized through anti SN2' with equatorial attack of the reagents to stable chair conformers of cyclohexane rings. On the other hand, acyclic 3,3-disubstituted allylic picolinates upon allylic substitution with Grignard reagents/Cu(acac)2 (each 2:1 ratio) afforded anti SN2' products, which have been converted to LY426965, mesembrine, verapamil, and sporochnol. Furthermore, allylic substitution of secondary allylic phosphates with Ar2CH anions proceeded efficiently.
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| Free Research Field |
有機合成化学
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