4.8 Article

Efficient Synthesis of Orphaned Cyclopropanes Using Sulfones as Carbene Equivalents

期刊

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
卷 144, 期 32, 页码 14471-14476

出版社

AMER CHEMICAL SOC
DOI: 10.1021/jacs.2c07063

关键词

-

资金

  1. UNC Department of Chemistry
  2. National Science Foundation [CHE-0922858, CHE-1828183, CHE-1726291]

向作者/读者索取更多资源

In this study, a new platform for transferring 1,1-dialkylcarbene units to olefins using carbometalation reactions was introduced. By reacting dialkyl sulfones with styrenes and arylbutadienes, 1,1-dialkylcyclopropanes were synthesized successfully. The potential of this method was showcased through various examples.
Small molecules containing 1,1-dimethylcyclopropanes are prevalent throughout nature but are difficult to synthesize using state-of-the-art metal-catalyzed carbene transfer methods without competing 1,2-hydride shifts. Herein, we introduce a mechanistically distinct platform to transfer 1,1-dialkylcarbene units to olefins using carbometalation reactions of dialkyl sulfonyl anions. In the presence of NaNH2 or n-BuLi in ethereal solvents, dialkyl sulfones react with styrenes and arylbutadienes between 23 and 70 degrees C to produce the corresponding 1,1-dialkylcyclopropanes. We report 40 examples of this reactivity including 16 different styrenes (up to 89% isolated yield), 9 arylbutadienes (51-88% yield), and 13 different sulfones (46-80% yield). In addition, we report an example of a sequential cyclopropanation reaction using this method. Preliminary mechanistic studies suggest a stepwise anionic process that is initiated by the direct addition of sulfonyl anions to a carbon-carbon double bond.

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