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Synthesis of Biologically Active Natural Products on the Basis of Silafunctional Compounds

基于硅功能化合物的生物活性天然产物的合成

基本信息

批准号：
61470093
负责人：
ITO Yoshihiko
金额：
$ 3.58万
依托单位：
Kyoto University
依托单位国家：
日本
项目类别：
Grant-in-Aid for General Scientific Research (B)
财政年份：
1986
资助国家：
日本
起止时间：
1986 至 1988
项目状态：
已结题

项目摘要

Synthetic methods for stereoselective preparations of polyols have been developed on the basis of silafunctional compounds, of which silicon-carbon bonds can be oxidatively cleaved and hydroxylated. The following results have been obtained.1. Selective alpha-alkylation of (dialkylamino)allylsilanes was achieved by in-situ generation of potassium (dialkylamino)allylsilanes. Total synthesis of ( )-brevicomin was carried out viaseveral steps including the selective alpha-alkylation of (dialkylamino)allylsilane. 2. Selective deoxygenation of (isopropoxy) alpha,beta-epoxy) silanes was found in the reaction with isopropylmagnesium chloride in the presence of CuCN. 3. Stereoselective alpha-hydroxyallylation of aldehydes was achieved by in-situ generation of zinc (dialkylamino)allylsilanes. 4. Selective gamma-allylation of aldehydes was achieved by copper(I) reagents which are in-situ generated by a reaction of CuCN with lithium (dialkylamino)allylsilanes. Usefulness of the gamma-regioselective allylation of aldehydes with (dialkylamino)allylsilanes was demonstrated by synthesis of 2-deoxy-C-nucleoside skeletons.

在硅功能化合物的基础上，发展了立体选择性制备多元醇的合成方法，其中硅碳键可以被氧化裂解和羟化。取得了以下成果：1.通过原位生成二烷氨基烯丙基硅烷钾，实现了二烷氨基烯丙基硅烷的选择性α-烷基化反应。()-Brivicomin的全合成是通过几个步骤进行的，包括(二烷氨基)烯丙基硅烷的选择性α-烷基化。2.在CuCN存在下，(异丙氧基)α，β-环氧基硅烷与异丙基氯化镁发生选择性脱氧反应。3.通过原位生成二烷胺基烯丙基硅烷锌实现了醛的立体选择性α-羟基烯丙基化反应。4.通过CuCN与二烷氨基烯丙基硅烷锂反应原位生成的铜(I)试剂，实现了醛的选择性伽马-烯丙基化反应。通过合成2-脱氧-C-核苷骨架，证明了醛与(二烷氨基)烯丙基硅烷的伽马区域选择性烯丙化反应的有效性。