{"title":"A Radical Approach to Chiral β-Hydroxyboronate Esters via Synergistic Co/Cr Catalysis","authors":"Ke Gao, Zhaobin Wang","doi":"10.1021/acscatal.5c01704","DOIUrl":null,"url":null,"abstract":"Chiral β-hydroxyboronate esters are versatile intermediates in organic synthesis, serving as bioisosteres of β-hydroxycarboxylic acids and providing access to diverse functionalized molecules. Despite their broad applicability, efficient and general methods for their asymmetric synthesis remain underdeveloped. Here, we report a chromium-catalyzed radical-polar crossover strategy for the asymmetric addition of α-boronate alkyl chlorides to aldehydes, furnishing β-hydroxyboronate esters with a broad substrate scope and high enantioselectivity. The reaction proceeds via CoPc-mediated radical generation followed by Cr-catalyzed stereoselective addition. The resulting products undergo diverse transformations, including oxidation, cross-coupling, and amination, demonstrating their synthetic utility. Mechanistic studies support a monomeric Cr-catalyzed alkylation pathway, expanding the scope of asymmetric Cr catalysis and providing a complementary approach to ionic strategies for β-hydroxyboronate synthesis.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"29 1","pages":""},"PeriodicalIF":13.1000,"publicationDate":"2025-05-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"ACS Catalysis ","FirstCategoryId":"92","ListUrlMain":"https://doi.org/10.1021/acscatal.5c01704","RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, PHYSICAL","Score":null,"Total":0}
引用次数: 0
Abstract
Chiral β-hydroxyboronate esters are versatile intermediates in organic synthesis, serving as bioisosteres of β-hydroxycarboxylic acids and providing access to diverse functionalized molecules. Despite their broad applicability, efficient and general methods for their asymmetric synthesis remain underdeveloped. Here, we report a chromium-catalyzed radical-polar crossover strategy for the asymmetric addition of α-boronate alkyl chlorides to aldehydes, furnishing β-hydroxyboronate esters with a broad substrate scope and high enantioselectivity. The reaction proceeds via CoPc-mediated radical generation followed by Cr-catalyzed stereoselective addition. The resulting products undergo diverse transformations, including oxidation, cross-coupling, and amination, demonstrating their synthetic utility. Mechanistic studies support a monomeric Cr-catalyzed alkylation pathway, expanding the scope of asymmetric Cr catalysis and providing a complementary approach to ionic strategies for β-hydroxyboronate synthesis.
期刊介绍:
ACS Catalysis is an esteemed journal that publishes original research in the fields of heterogeneous catalysis, molecular catalysis, and biocatalysis. It offers broad coverage across diverse areas such as life sciences, organometallics and synthesis, photochemistry and electrochemistry, drug discovery and synthesis, materials science, environmental protection, polymer discovery and synthesis, and energy and fuels.
The scope of the journal is to showcase innovative work in various aspects of catalysis. This includes new reactions and novel synthetic approaches utilizing known catalysts, the discovery or modification of new catalysts, elucidation of catalytic mechanisms through cutting-edge investigations, practical enhancements of existing processes, as well as conceptual advances in the field. Contributions to ACS Catalysis can encompass both experimental and theoretical research focused on catalytic molecules, macromolecules, and materials that exhibit catalytic turnover.