4.8 Article

Rhodium-Catalyzed Diastereo- and Enantioselective Divergent Annulations between Cyclobutanones and 1,5-Enynes: Repaid Construction of Complex C(sp3)-Rich Scaffolds

期刊

出版社

AMER CHEMICAL SOC
DOI: 10.1021/jacs.2c09814

关键词

-

资金

  1. NIGMS [2R01GM109054]
  2. University of Chicago
  3. NSF

向作者/读者索取更多资源

This article describes the development of Rh(I)-catalyzed intramolecular annulations for constructing complex C(sp3)-rich scaffolds. Different catalysts exhibit divergent reactivities and achieve excellent diastereo- and enantioselectivity.
Given the emerging demand to escape from flatland for drug discovery, synthetic methods that can efficiently construct complex three-dimensional structures with multi-stereocenters become increasingly valuable. Here, we describe the development of Rh(I)-catalyzed intramolecular annulations between cyclobutanones and 1,5-enyne groups to construct complex C(sp3)-rich scaffolds. Divergent reactivities are realized with different catalysts, and excellent diastereo-and enantioselectivity have been achieved. The use of (R)-H8-binap as the ligand favors forming the bis-bicyclic scaffolds with multiple quaternary stereocenters, while the (R)-segphos ligand prefers to generate the tetrahydro-azapinone products. Owing to the versatile reactivity of ketone moieties, these C(sp3)-rich scaffolds can be further functionalized. Experimental and computational mechanistic studies support a reaction pathway involving enyne-cyclometallation, 1,2-carbonyl addition, and then beta-carbon elimination; the divergent reactivities are dictated by a product-determining Rh-alkyl migrator insertion step.

作者

我是这篇论文的作者
点击您的名字以认领此论文并将其添加到您的个人资料中。

评论

主要评分

4.8
评分不足

次要评分

新颖性
-
重要性
-
科学严谨性
-
评价这篇论文

推荐

暂无数据
暂无数据