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
Subject
General Chemistry,Catalysis
Cited by
7 articles.
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