铑（II）催化的亚磺酰胺与双受体重氮化合物的对映选择性α-烷基化反应实现了具有多种官能团的磺胺氧化合物的合成。
Rh(II)-Catalyzed Enantioselective -Alkylation of Sulfenamides with Acceptor-Acceptor Diazo Compounds Enables the Synthesis of Sulfoximines Displaying Diverse Functionality.
作者信息
Patel Shivani, Greenwood Nathaniel S, Mercado Brandon Q, Ellman Jonathan A
机构信息
Department of Chemistry, Yale University, New Haven, Connecticut 06520, United States.
出版信息
Org Lett. 2024 Jul 26;26(29):6295-6300. doi: 10.1021/acs.orglett.4c02402. Epub 2024 Jul 14.
Abstract
The Rh(II)-catalyzed enantioselective -alkylation of sulfenamides with α-amide diazoacetates at 1 mol % catalyst loading to obtain sulfilimines in high yields and enantiomeric ratios of up to 99:1 is reported. The enantioenriched sulfilimine products incorporate versatile amide functionality poised for further elaboration to diverse sulfoximines with multiple stereogenic centers, including by highly diastereoselective sulfilimine and sulfoximine α-alkylation with alkylating agents and epoxides and by interconversion of the amide to --butanesulfinyl aldimines, followed by diastereoselective additions.
摘要
据报道，在1 mol%的催化剂负载量下，铑（II）催化亚磺酰胺与α-酰胺重氮乙酸酯的对映选择性α-烷基化反应，可高产率地得到亚磺酰亚胺，对映体比例高达99:1。对映体富集的亚磺酰亚胺产物含有多功能酰胺官能团，可进一步转化为具有多个立体中心的各种亚砜亚胺，包括通过与烷基化剂和环氧化物进行高度非对映选择性的亚磺酰亚胺和亚砜亚胺α-烷基化反应，以及通过将酰胺转化为叔丁基亚磺酰醛亚胺，随后进行非对映选择性加成反应。
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