Department of Chemistry, University of California , Irvine, California 92697, United States.
J Am Chem Soc. 2017 Feb 8;139(5):1774-1777. doi: 10.1021/jacs.6b12307. Epub 2017 Jan 27.
We communicate a strategy for the hydrofunctionalization of 1,3-dienes via Rh-hydride catalysis. Conjugated dienes are coupled to nucleophiles to demonstrate the feasibility of novel C-C, C-O, C-S, and C-N bond forming processes. In the presence of a chiral JoSPOphos ligand, hydroamination generates chiral allylic amines with high regio- and enantioselectivity. Tuning both the pK and steric properties of an acid-additive is critical for enantiocontrol.
我们提出了一种通过 Rh-氢化物催化实现 1,3-二烯水功能化的策略。共轭二烯与亲核试剂偶联，证明了新型 C-C、C-O、C-S 和 C-N 键形成过程的可行性。在手性 JoSPOphos 配体的存在下，氢胺化反应以高区域和对映选择性生成手性烯丙基胺。对于对映体控制，调节酸添加剂的 pK 和空间性质都至关重要。
