Novel stereospecific nucleophilic addition reaction to optically active vinyl sulfoxide

光学活性乙烯基亚砜的新型立体特异性亲核加成反应

• 批准号: 02640414
• 负责人: NOKAMI Junzo
• 金额: $ 1.41万
• 依托单位: Okayama University of Science
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for General Scientific Research (C)
• 财政年份: 1990
• 资助国家: 日本
• 起止时间: 1990 至 1991
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-02640414/
• 关键词: Optically Active Sulfoxide; Vinyl Sulfoxide; Stereospecific Nucleophilic addition; Asymmetric Induction; Three Contiguous Chiral Carbon Chain; Lithium Enolate; Quarternary Asymmetric Carbon; 3連続不斉炭素; リチウムエノレ-ト

1. Lithium enolates derived from ethyl or tert-butyl alkanoates with lithium diisopropylamide (LDA) and from ethyl 2-alkenoate with lithium N-benzyltrimethylsilyiamide (LSA) reacted with optically active vinyl sulfoxides to give stereospecific nucleophilic addition products possessing two or three contiguous chii'al carbon chain.2. Useful building block having a quartenary asymmetric carbon which would play an efficient role in organic synthesis was built by employin8 the stereospecific nucleophi I ic addition of acetic esterenolate to beta beta-disubstitu ted optica]Iy active vinyl sulfoxide.3. Brefeldin A was synthesi2ed by using (+)-4-cyanomethylcyclopent-2-en-l-one as a key compound. 4-Hydroxy-2-enoate functionality was built by the reaction of the aidehydeintermediate with (S)-ethyl p-chlorophenyisulfinylacetate.

1.烷酸乙酯或叔丁基烷酸乙酯与二异丙胺锂(LDA)和2-烯酸乙酯与N-苄基三甲基硅酰胺锂(LSA)反应生成的锂烯醇与光学活性的乙烯基亚砜反应得到具有两个或三个连续碳链的立体专一性亲核加成产物。利用乙酸酯酯与β-二取代光学活性乙烯基亚砜的立体专一性亲核加成反应，构建了具有四元不对称碳的有用的构筑块，它将在有机合成中起到有效的作用。以(+)-4-氰甲基环戊酮-2-烯-L-酮为关键化合物合成了灯盏花素A。4-羟基-2-烯酸酯官能团是由醛中间体与(S)-对氯苯基异亚氨基乙酸乙酯反应构建的。

项目成果

Junzo Nokami: "Preparation of asymmetric carbon chain by nucleophilic addition reaction of ester enolates to optically active vinyl sultoxides" Chemistry Letters.

Junzo Nokami：“通过酯烯醇化物与光学活性乙烯基亚硫酸盐的亲核加成反应制备不对称碳链”化学快报。

Junzo Nokami: "Facile synthesis of (+)-Brefeldin A" Tetrahedron Letters. 32. 2409-2412 (1991)

Junzo Nokami：“( )-Brefeldin A 的简易合成”四面体字母。

Junzo Nokami, Toshio Kakihara, Akira Nishimura, and Norio Kunieda: "Preparation of asymmetric carbon chain by nucleophilic addition reaction of ester enolate to optically active vinyl sulfoxide" Chem. Lett.

Junzo Nokami、Toshio Kakihara、Akira Nishimura 和 Norio Kunieda：“通过酯烯醇化物与光学活性乙烯基亚砜的亲核加成反应制备不对称碳链” Chem。