Development of a New Stereospecific Allylation and Its Application for Synthesis

新型立体有择烯丙基化的发展及其合成应用

• 批准号: 12450357
• 负责人: NOKAMI Junzo
• 金额: $ 7.94万
• 依托单位: Okayama University of Science
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (B)
• 财政年份: 2000
• 资助国家: 日本
• 起止时间: 2000 至 2002
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-12450357/
• 关键词: allyl-transfer reaction; homoallylic alcohol; alk-2-enylation; chiral auxiliary; asymmetric synthesis; menthone; [3.3]-sigmatropy; six-membered chair-like transition state; allyl-transferreaction; homoallylic aocohol; α-crotylation; stereospeci

To date, there have been no reported methods for effectively synthesizing homoallylic alcohols via alk-2-enylation of an aldehyde. On the other hand, we recently discovered the first convenient and highly stereoselective but-2-enylation of an aldehyde via an ally-transfer reaction due to [3.3]-sigmatropy rearrangement. Further, we demonstrated the possibility of alk-2-enylation of an aldehyde via an allyl-transfer reaction using optically active menthone as a chiral auxiliary. We also discovered that this improved the yield of the product due to an increase in the length of the alkyl chains.Prop-2-enylation of an aldehyd via an allyl-transfer reaction is a valuable reaction is a valuable reaction, particularly for asymmetric syntheses. This discovery makes it possible to efficiently synthesize optically pure poly-substituted tetrahydropyrane derivatives using an optically active homoallylic alcohol. In turn, it also becomes possible to efficiently synthesize many bioactive compounds and their analogues in optically active forms.

到目前为止，还没有报道通过醛的ALK-2-烯基化有效地合成高烯丙醇的方法。另一方面，由于[3.3]-Sigmatroy重排反应，我们最近发现了第一个方便的、高立体选择性的醛的BUT-2-烯基化反应。此外，我们还证明了利用光学活性薄荷酮作为手性助剂，通过烯丙基转移反应来实现醛的ALK-2-烯基化反应的可能性。我们还发现，由于烷基链长的增加，这提高了产物的产率。通过烯丙基转移反应进行醛的丙二烯基化反应是一个有价值的反应，特别是对于不对称合成。这一发现使得使用光学活性的高烯丙醇有效地合成光学纯的多取代四氢吡喃衍生物成为可能。反过来，它也成为可能有效地合成许多生物活性化合物及其类似物的光学活性形式。