A Novel Preparation of Allylic Tins from α,α-Disubstituted Homoallylic Alcohols and Its Application
| Project/Area Number |
12640573
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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 |
物質変換
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| Research Institution | Sophia University |
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Principal Investigator |
MASUYAMA Yoshiro Sophia University, Faculty of Science and Technology, Lecturer, 理工学部, 講師 (30138375)
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| Project Period (FY) |
2000 – 2001
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| Project Status |
Completed (Fiscal Year 2001)
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| Budget Amount *help |
¥3,100,000 (Direct Cost: ¥3,100,000)
Fiscal Year 2001: ¥1,000,000 (Direct Cost: ¥1,000,000)
Fiscal Year 2000: ¥2,100,000 (Direct Cost: ¥2,100,000)
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| Keywords | Carbonyl-allylation / Allylic trichlorotins / Homoallylic alcohols / Tin(II) chloride / N-Chlorosuccinimide / Imine-allylation / Retro-allylation / Regioselectivity / N-トシルイミニウム |
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| Research Abstract |
The retro-(carbonyl-allylation) of α, α-diisopropylhomoallylic alcohols with tin(1I) chloride and N-chlorosuccinimide (NCS) in dichioromethane at -40℃ affords allylic trichiorotins that are utilized for carbonyl-allylation and imine-allylation.
1) Carbonyl-allylation
2-Propenyltrichlorotin, derived from α, α-diisopropylhomoallyl alcohol, causes nucleophilic addition to various aldehydes to produce 1-substituted 3-buten-1-ols in high yields. The nucleophilic addition of 2-butenyltrichlorotin, derived from α, α-diisopropyl-β-methylhomoallyl alcohol, to aldehydes, bearing no coordinating groups or bearing non-coordinating electron-withdrawing groups, exhibits cc-regioselectivity, in contrast to that of usual 2-butenylmetal reagents.
2) Imine-allylation
The 2-propenyltrichlorotin causes nucleophilic addition to N-tosyliminiums, derived from aldehydes and tosylamide with tin(II) chloride and NCS, to produce 1-substituted N-tosyl-3-butenylamines in good yields. The 2-butenyltrichlorotin cannot be applied to the nucleophilic addition to N-tosyliminiums. N-Tosylimines, which can form six-membered cyclic transition state with allylic trichiorotins, instead of using N-tosyliminiums react with not only 2-propenyltrichiorotin but also 2-butenyltrichiorotin to afford the corresponding homoallylic amines in good yields.
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Report
(3 results)
Research Products
(3 results)
