State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, University of Chinese Academy of Sciences, Chinese Academy of Sciences , 345 Lingling Road, Shanghai 200032, P. R. China.
J Am Chem Soc. 2017 Sep 20;139(37):12891-12894. doi: 10.1021/jacs.7b05427. Epub 2017 Sep 7.
A rhodium-catalyzed intermolecular hydroacylation reaction of vinyl cyclobutanols with non-chelating aldehydes has been developed. This reaction offers a new and atom-economical approach for the selective preparation of 1,5-diketones in high yields. Experimental data suggest a sequential ring-opening, transfer hydrogenation, and hydroacylation mechanism. We propose that aldehyde decarbonylation is avoided by the formation of a novel rhodium enolate species that also accounts for the compatibility of a broad range of aldehydes and its anti-Markovnikov selectivity.
发展了一种铑催化的乙烯基环丁醇与非螯合醛的分子间氢酰化反应。该反应为高收率选择性制备 1,5-二酮提供了一种新的、原子经济性的方法。实验数据表明存在一个连续的开环、转移氢化和氢酰化的反应机理。我们提出通过形成一种新型的铑烯醇盐物种来避免醛的脱羰，这也解释了广泛的醛的兼容性及其反马氏选择性。
