4.8 Article

Copper-Catalyzed Enantioselective Radical 1,4-Difunctionalization of 1,3-Enynes

Journal

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
Volume 142, Issue 42, Pages 18014-18021

Publisher

AMER CHEMICAL SOC
DOI: 10.1021/jacs.0c06177

Keywords

-

Funding

  1. National Key R&D Program of China [2017YFA0700103]
  2. NSFC [21672213, 21871258, 21922112]
  3. Strategic Priority Research Program of the Chinese Academy of Sciences [XDB20000000]
  4. Haixi Institute of CAS [CXZX-2017-P01]
  5. Scientific Research Foundation of Fujian Normal University in China [IRTL1703]
  6. Innovative Research Teams Program II of Fujian Normal University in China [IRTL1703]
  7. Shenzhen STIC [JCYJ20170412150343516]
  8. Shenzhen San-Ming Project [SZSM201809085]

Ask authors/readers for more resources

Chiral allenes are important structural motifs frequently found in natural products, pharmaceuticals, and other organic compounds. Asymmetric 1,4-difunctionalization of 1,3-enynes is a promising strategy to construct axial chirality and produce substituted chiral allenes from achiral substrates. However, the previous state of the art in 1,4-difunctionalization of 1,3-enynes focused on the allenyl anion pathway. Because of this, only electrophiles can be introduced into the allene backbones in the second functionalization step, consequently limiting the reaction and allene product types. The development of asymmetric 1,4-difunctionalization of 1,3-enynes via a radical pathway would complement previous methods and support expansion of the toolbox for the synthesis of asymmetric allenes. Herein, we report the first radical enantioselective allene formation via a group transfer pathway in the context of copper-catalyzed radical 1,4-difunctionalization of 1,3-enynes. This method addresses a longstanding unsolved problem in asymmetric radical chemistry, provides an important strategy for stereocontrol with free allenyl radicals, and offers a novel approach to the valuable, but previously inaccessible, chiral allenes. This work should shed light on asymmetric radical reactions and may lead to other enantioselective group transfer reactions.

Authors

I am an author on this paper
Click your name to claim this paper and add it to your profile.

Reviews

Primary Rating

4.8
Not enough ratings

Secondary Ratings

Novelty
-
Significance
-
Scientific rigor
-
Rate this paper

Recommended

No Data Available
No Data Available