Collaborative Innovation Center of Chemical Science and Engineering (Tianjin) , Tianjin 300071, China.
J Am Chem Soc. 2016 Mar 9;138(9):2957-60. doi: 10.1021/jacs.6b00024. Epub 2016 Feb 25.
The first nickel-catalyzed intermolecular hydroacylation reaction of alkenes with simple aldehydes has been developed. This reaction offers a new approach to the selective preparation of branched ketones in high yields (up to 99%) and branched selectivities (up to 99:1). Experimental data provide evidence for reversible formation of acyl-nickel-alkyl intermediate, and DFT calculations show that the aldehyde C-H bond transfer to a coordinated alkene without oxidative addition is involved. The origin of the reactivity and regioselectivity of this reaction was also investigated computationally, which are consistent with experimental observations.
发展了首例镍催化的烯烃与简单醛的分子间氢甲酰化反应。该反应为高收率（高达 99%）和高区域选择性（高达 99:1）地选择性制备支链酮提供了新途径。实验数据为酰基-镍-烷基中间物的可逆形成提供了证据，并且 DFT 计算表明涉及配位烯烃的醛 C-H 键转移而无需氧化加成。该反应的反应性和区域选择性的起源也通过计算进行了研究，与实验观察结果一致。
