Metal‐Free 1,3‐Boronate Rearrangement to Ketones Driven by Visible Light

Author:

Hao Kejia1,Li Defang12,Fu Dongmin3,Zou Peng1,Xie Shasha1,Lan Yu34,Chen Yiyun125ORCID

Affiliation:

1. State Key Laboratory of Chemical Biology Shanghai Institute of Organic Chemistry University of Chinese Academy of Sciences Chinese Academy of Sciences 345 Lingling Road Shanghai 200032 China

2. School of Physical Science and Technology ShanghaiTech University 100 Haike Road Shanghai 201210 China

3. Green Catalysis Center College of Chemistry Zhengzhou University Zhengzhou Henan 450001 China

4. School of Chemistry and Chemical Engineering Chongqing Key Laboratory of Theoretical and Computational Chemistry Chongqing University Chongqing 400030 China

5. School of Chemistry and Material Sciences Hangzhou Institute for Advanced Study University of Chinese Academy of Sciences 1 Sub-lane Xiangshan Hangzhou 310024 China

Abstract

AbstractBoronate rearrangements, such as the Matteson and Petasis reactions, are valuable metal‐free reactions for the transfer of the carbo group on boron to intramolecular electrophilic sites. However, only highly reactive electrophiles are suitable, and ketones are too inactive for those boronate rearrangements due to the high energy barriers. We disclose here the 1,3‐boronate rearrangement to ketones, for which a high energy barrier (44.9 kcal/mol) is prohibitory for thermal reactions in the ground state. The reaction is enabled by the key keto‐enol‐boronate bidentate complex formation in situ, which absorbs visible light to reach the excited state for the chemoselective 1,3‐boronate rearrangement to ketones. Experimental and computational investigations exclude free radical intermediates from organoboronates. The aryl, alkenyl, and alkyl boronic acids react with various 1,3‐diketones driven by visible light irradiation to construct structurally diverse β‐keto tertiary alcohols under metal‐free conditions. The reaction demonstrates substrate diversity with 58 examples, yields up to 98 %, and it is suitable for gram‐scale synthesis.

Funder

National Natural Science Foundation of China

Program of Shanghai Academic Research Leader

Publisher

Wiley

Subject

General Chemistry,Catalysis

同舟云学术

1.学者识别学者识别

2.学术分析学术分析

3.人才评估人才评估

"同舟云学术"是以全球学者为主线,采集、加工和组织学术论文而形成的新型学术文献查询和分析系统,可以对全球学者进行文献检索和人才价值评估。用户可以通过关注某些学科领域的顶尖人物而持续追踪该领域的学科进展和研究前沿。经过近期的数据扩容,当前同舟云学术共收录了国内外主流学术期刊6万余种,收集的期刊论文及会议论文总量共计约1.5亿篇,并以每天添加12000余篇中外论文的速度递增。我们也可以为用户提供个性化、定制化的学者数据。欢迎来电咨询!咨询电话:010-8811{复制后删除}0370

www.globalauthorid.com

TOP

Copyright © 2019-2024 北京同舟云网络信息技术有限公司
京公网安备11010802033243号  京ICP备18003416号-3