Department of Chemistry, The University of North Carolina at Chapel Hill , Chapel Hill, North Carolina 27599, United States.
J Am Chem Soc. 2017 Sep 13;139(36):12438-12440. doi: 10.1021/jacs.7b07983. Epub 2017 Aug 29.
Despite advances in organometallic cross-coupling of alkyl electrophiles, there are few stereoselective reactions of chiral, nonracemic substrates. Herein we report a stereospecific carbonylative coupling of alkyl tosylates and dienes producing enantioenriched dienones. This catalytic process proceeds under low pressure and mild conditions using a simple cobalt catalyst and extends to diverse tosylate and diene coupling partners. The transformation constitutes a unique, convergent approach to the asymmetric synthesis of valuable carbonyl compounds from easily accessed starting materials.
尽管在烷基亲电体的有机金属交叉偶联方面取得了进展，但手性非外消旋底物的立体选择性反应却很少。在此，我们报告了一种立体特异性的羰基化偶联反应，其中烷基对甲苯磺酸酯和二烯反应生成手性烯酮。该催化过程在低压和温和条件下使用简单的钴催化剂进行，并扩展到各种对甲苯磺酸酯和二烯偶联物。该转化构成了一种从易得起始原料不对称合成有价值的羰基化合物的独特、收敛的方法。
