Department of Chemistry, Shenzhen Key Laboratory of Full Spectral Solar Electricity Generation (FSSEG), South University of Science and Technology of China (SUSTC), No. 1088, Xueyuan Road, Shenzhen, China.
Angew Chem Int Ed Engl. 2017 Jul 24;56(31):9048-9052. doi: 10.1002/anie.201703706. Epub 2017 Jun 16.
Highly selective cross-hydroalkenylations of endocyclic 1,3-dienes at the least substituted site with α-olefins were achieved with a set of neutral (NHC)Ni H(OTf) catalysts and cationic Ni catalysts with a novel NHC ligand. Under heteroatom assistance, skipped dienes were obtained in good yields, often from equal amounts of the two substrates and at a catalyst loading of 2-5 mol %. Rare 4,3-product selectivity (i.e., with the H atom at C4 and the alkenyl group at C3 of the diene) was observed, which is different from the selectivity of known dimerizations of α-olefins with both acyclic Co and Fe systems. The influence of the various substituents on the NHC, 1,3-diene, and α-olefin on the chemo-, regio-, and diastereoselectivity was studied. High levels of chirality transfer were observed with chiral cyclohexadiene derivatives.
通过一组中性 (NHC)Ni H(OTf) 催化剂和带有新型 NHC 配体的阳离子 Ni 催化剂，实现了具有高选择性的环内 1,3-二烯在最取代位点与 α-烯烃的交叉氢烯丙基化反应。在杂原子辅助下，以良好的收率得到了 skipped dienes，通常是由等量的两种底物在催化剂负载量为 2-5 mol%的条件下得到。观察到了罕见的 4,3-产物选择性（即，二烯的 C4 位上有 H 原子，C3 位上有烯基），这与已知的 Co 和 Fe 体系中 α-烯烃的环外二聚反应的选择性不同。研究了 NHC、1,3-二烯和 α-烯烃上各种取代基对化学、区域和非对映选择性的影响。带有手性环己二烯衍生物的手性转移水平很高。
