1988 Fiscal Year Final Research Report Summary
Studies on the Practical Synthesis of a New Type of Chiral Bisphosphines
| Project/Area Number |
62850150
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| Research Category |
Grant-in-Aid for Developmental Scientific Research
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| Allocation Type | Single-year Grants |
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| Research Field |
Synthetic chemistry
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| Research Institution | Kyushu Institute of Technology |
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Principal Investigator |
MINAMI Toru Kyushu Institute of Technology Professor, 工学部, 教授 (10029134)
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| Co-Investigator(Kenkyū-buntansha) |
榊原 敏之 日本精化, 研究所, 研究所長
YAMAGUCHI Masahiko Kyushu Institute of Technology Associate Professor, 工学部, 助教授 (30158117)
SAKAKIBARA Toshiyuki Nippon Fine Chemical Manager Research Laboratories
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| Project Period (FY) |
1987 – 1988
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| Keywords | Chiral Ligands / Phosphinocarboxylic Acids / Catalytic Asymmetric Reaction / 不斉ヒドロシリル化 / ホスフィノカルボン酸 / 不斉アルキル化 |
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| Research Abstract |
In this project, practical synthesis of chiral bis-phosphine ligands for asymmetric synthesis and development of a new type of chiral ligands were studied.
(1) For putting chiral trans-bis-1,2-(diphenylphosphino)cyclobutane(DPCB), which we have recently developed, into practical use, we examined the reaction conditions such as base, solvent and temperature. The use of t-BuLi instead of n-BuLi as base improved the yield and purity of DPCB oxide. Asymmetric hydrosilylation of ketones using Rh(I)・ (+)- or (-)- DPCB complex was studied.
(2) A new type of chiral phosphine ligands, 2-(diphenylphosphino)cycloalkylcarboxylic acids (abbreviated DPCAC) was synthesized. Each of chiral (+)- and (-)-DPCAC was successfully isolated by treatment of the racemic mixtrue of DPCAC with (+)- or (-)- phenylethylamine. Optically active DPCAC were effective as ligands for the palladiumcatalyzed asymmetric allylic alkylation of allyl acetates such as 1,3-diphenylprop-2-eny1 acetate and cyclohex-2-eny1 acetate with malonic acid esters and ethy1 diethylphosphono-acetate as soft carbon nucleophiles to give the alkylation products in good optical yields.
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