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Asymmetric synthesis by alkylation of alpha, beta-unsaturated aldehyde hydrazones

Research Project

Project/Area Number 05650887
Research Category

Grant-in-Aid for General Scientific Research (C)

Allocation TypeSingle-year Grants
Research Field Synthetic chemistry
Research InstitutionDoshisha University, Faculty of Engineering

Principal Investigator

YAMASHITA Masakazu  Doshisha Univ., Fac. Eegineering, Professor, 工学部, 教授 (20113102)

Project Period (FY) 1993 – 1994
Project Status Completed (Fiscal Year 1994)
Budget Amount *help
¥1,900,000 (Direct Cost: ¥1,900,000)
Fiscal Year 1994: ¥700,000 (Direct Cost: ¥700,000)
Fiscal Year 1993: ¥1,200,000 (Direct Cost: ¥1,200,000)
KeywordsAsymmetric carbon / Hydrazones / Asymmetric synthesis / Alkylation / Aldehydes / Nitriles / 不斉アルキル化反応 / alpha-ビニルアルデヒド / 転位反応 / alpha,beta-不飽和アルデヒドヒドラゾン / 不斉第4級炭素原子
Research Abstract

Enantio-and regioselective alkylation of alpha, beta-unsaturated aldehyed hydrazones or imines to alpha-alkyl-beta, gamma-unsaturated carbonyl compounds are described.
2-Alkyl-2-methyl-3-butenal which has quaternary carbon atom at alpha-position was synthesized from 2-methyl-2-butenal cyclohexylimine by successive deprotonation by base, alkylation, and the following hydrolysis. This shows that alkylation occurred at alpha-position selectively and the alpha, beta-unsaturated double bond migrated to beta, gamma.
Similar results were obtained using hydrazone derivatives such as dimethylhydrazones instead of cyclohexylimines. 2-Alkyl-2-methyl-3-butenal was obtained from these dimethylhydrazones by hydrolysis with copper (II) choride. When magnesium mono-peroxyphthalate was used, 2-methyl-2-butenonitrile which has quaternary carbon atom at alpha-position were produced from these dimethylhydrazones in good yields.
When chiral hydrazones such as 2-methyl-2-butenal SAMP ( (S) -1-amino-2- (methoxymethyl) pyrrolidine) hydrazone were used, chiral nitriles were produced in good enantioselectivity. The absolute configuration of (-) -2-benzyl-2-methyl-3-butenonitrile was elucidated as (R) -series by chemical correlation with (S) - (+) -methyl 2-cyano-2-methyl-3-phenylpropionate, whose absolute configuration is already established.
Moreover, chiral aldehydes which have asymmetric quaternary carbon atom at alpha-position were produced in moderate enantioselectivity when chiral imines such as 2-methly-2-butenal (S,S) -ADPD ( (4S,5S) - (+) -5-amino-2,2-dimethyl-4-phenyl-1,3-dioxane) imine were used.

Report

(3 results)
  • 1994 Annual Research Report   Final Research Report Summary
  • 1993 Annual Research Report

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Published: 1993-04-01   Modified: 2016-04-21  

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