Department of Chemistry , University of Texas at Austin , Austin , Texas 78712 , United States.
J Am Chem Soc. 2019 May 1;141(17):6864-6868. doi: 10.1021/jacs.9b03113. Epub 2019 Apr 18.
A regiodivergent catalytic method for direct conversion of aldehydes to branched or linear alkyl ketones is described. Rhodium complexes modified by P BuMe catalyze formate-mediated aldehyde-vinyl bromide reductive coupling-redox isomerization to form branched ketones. Use of the less strongly coordinating ligand, PPh, promotes vinyl- to allylrhodium isomerization en route to linear ketones. This method bypasses the 3-step sequence often used to convert aldehydes to ketones involving the addition of pre-metalated reagents to Weinreb or morpholine amides.
描述了一种区域发散的催化方法，可将醛直接转化为支链或直链烷基酮。由 PBuMe 修饰的铑配合物催化甲酸盐介导的醛-溴代乙烯还原偶联-氧化异构化反应，生成支链酮。使用配位能力较弱的配体 PPh 可促进乙烯基-烯丙基铑异构化，从而生成直链酮。该方法绕过了通常用于将醛转化为酮的 3 步序列，该序列涉及向 Weinreb 酰胺或吗啉酰胺中添加预金属化试剂。
