Wu Qimin, Zhang Qi, Yin Shuxin, Lin Aijun, Gao Shang, Yao Hequan
State Key Laboratory of Natural Medicines (SKLNM) and Department of Medicinal Chemistry, School of Pharmacy, China Pharmaceutical University, Nanjing, 210009, P. R. China.
Angew Chem Int Ed Engl. 2023 Jul 24;62(30):e202305518. doi: 10.1002/anie.202305518. Epub 2023 Jun 15.
Hydrofunctionalization of alkynes is one of the most efficient ways to access axially chiral styrenes with open-chained olefins. While great advances have been achieved for 1-alkynylnaphthalen-2-ols and analogues, atroposelective hydrofunctionalization of unactivated internal alkynes lags. Herein we reported a platinum-catalyzed atroposelective hydrosilylation of unactivated internal alkynes for the first time. With monodentate TADDOL-derived phosphonite L1 used as a chiral ligand, various axially chiral styrenes were achieved in excellent enantioselectivities with high E-selectivities. Control experiments showed that the NH-arylamide groups have significant effects on both the yields and enantioselectivities and could act as directing groups. The potential utilities of the products were shown by the transformations of the amide motifs of the products.
炔烃的氢官能团化是通过开链烯烃获得轴向手性苯乙烯的最有效方法之一。虽然在1-炔基萘-2-醇及其类似物方面已经取得了很大进展，但未活化的内炔烃的对映选择性氢官能团化仍较为滞后。在此，我们首次报道了铂催化的未活化内炔烃的对映选择性硅氢化反应。使用单齿TADDOL衍生的亚膦酸酯L1作为手性配体，以高E选择性实现了各种轴向手性苯乙烯的优异对映选择性。对照实验表明，NH-芳基酰胺基团对产率和对映选择性都有显著影响，并且可以作为导向基团。产物酰胺基序的转化展示了产物的潜在用途。
