Department of Chemistry and Institute of Basic Science, Sungkyunkwan University , Suwon 440-746, Korea.
Org Lett. 2016 Mar 18;18(6):1390-3. doi: 10.1021/acs.orglett.6b00325. Epub 2016 Mar 3.
A Cu-catalyzed highly Z-stereoselective hydroboration of alkynes with 1,8-naphthalenediaminatoborane (HB(dan)) is developed. DPEphos (bis[(2-diphenylphosphino)phenyl]ether)-ligated Cu catalysts produced alkenylboron compounds from terminal alkynes with excellent Z-stereoselectivity. In contrast, using a SIPr-CuCl complex as the precatalyst exclusively produced E-hydroboration products at mild conditions. Both catalytic procedures form alkenylboron products stereocomplementary to each other, constituting stereodivergent hydroboration of alkynes through Cu catalysis. Deuterium labeling and isomerization studies support the Z-selective hydroboration via trans-addition of the boron reagent to terminal alkynes as opposed to precedent noble-metal-catalyzed trans-hydroborations.
发展了一种铜催化的炔烃与 1,8-萘二胺基硼烷（HB(dan)）的高度 Z-立体选择性氢化硼化反应。DPEphos（双[(2-二苯基膦基)苯基]醚）配体连接的 Cu 催化剂可从末端炔烃生成具有优异 Z-立体选择性的烯基硼化合物。相比之下，在温和条件下，使用 SIPr-CuCl 配合物作为前催化剂仅生成 E-氢化硼化产物。这两种催化程序都形成彼此立体互补的烯基硼产物，通过 Cu 催化构成炔烃的立体发散氢化硼化。氘标记和异构化研究支持通过硼试剂反式加成到末端炔烃进行 Z-选择性氢化硼化，而不是先前的贵金属催化的反式氢化硼化。
