Chang Chieh-Yu, Aponick Aaron
Center for Heterocyclic Compounds, Department of Chemistry, University of Florida, Gainesville, Florida 32611, United States.
J Am Chem Soc. 2024 Jun 26;146(25):16996-17002. doi: 10.1021/jacs.4c05629. Epub 2024 Jun 14.
A highly regio- and enantioselective hydrosulfonylation using commercially available sodium sulfinates is reported, providing the first direct asymmetric rhodium-catalyzed hydrosulfonylation of allenes/alkynes to synthesize chiral allylic sulfones. Ligand screening studies demonstrated the indispensable role of the -symmetric P,N-ligand (,,)-StackPhim for achieving both high regioselecitivity (>20:1) and enantioselectivity (up to 97% ee). Notably, the operationally simple method and mild conditions allow for the rapid preparation of chiral allylic sulfones with a wide scope of functional groups. Moreover, the use of sodium -butyldimethylsilyloxymethanesulfinate enables the collective synthesis of various chiral sulfone derivatives after simple transformations of the protected hydroxymethyl product.
报道了一种使用市售亚磺酸钠进行的高度区域和对映选择性氢磺酰化反应，该反应首次实现了铑催化的丙二烯/炔烃直接不对称氢磺酰化反应，用于合成手性烯丙基砜。配体筛选研究表明，对称的P，N配体（，，）-StackPhim对于实现高区域选择性（>20:1）和对映选择性（高达97%ee）起着不可或缺的作用。值得注意的是，该操作简单的方法和温和的条件能够快速制备具有广泛官能团的手性烯丙基砜。此外，使用丁基二甲基硅氧基甲基亚磺酸钠，在对受保护的羟甲基产物进行简单转化后，能够集体合成各种手性砜衍生物。
