Sulfonamide Directivity Enables Ni-Catalyzed 1,2-Diarylation of Diverse Alkenyl Amines
Sulfonamide Directivity Enables Ni-Catalyzed 1,2-Diarylation of Diverse Alkenyl Amines
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DOI：
10.1021/acscatal.0c03857
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发表时间：
2020-12-04
期刊：
影响因子：
12.9
通讯作者：
Engle, Keary M.
中科院分区：
文献类型：
--
作者：
Apolinar, Omar;Tran, Van T.;Engle, Keary M.
报道了在镍催化下烯基磺酰胺与芳基碘化物和芳基硼酸酯的 1,2-二芳基化反应。所开发的方法可以容忍具有不同电子特性和取代模式的耦合伙伴。二取代和三取代的烯烃以及远离导向基团的烯烃都被容纳。对照实验与导向基团的 N-Ni 配位模式一致，这与之前关于酰胺导向的 1,2-二芳基化（涉及羰基配位）的报道形成鲜明对比。该方法的合成效用源于磺酰胺作为导向基团和掩蔽胺亲核试剂的双重功能。各种产品的多样化凸显了这一点，其中复杂的胺化合物是通过 N-官能化和磺酰基脱保护的两步顺序合成的。
1,2-Diarylation of alkenyl sulfonamides with aryl iodides and aryl boronic esters under nickel catalysis is reported. The developed method tolerates coupling partners with disparate electronic properties and substitution patterns. Di- and trisubstituted alkenes as well as alkenes distal from the directing group are all accommodated. Control experiments are consistent with a N-Ni coordination mode of the directing group, which stands in contrast to a previous report on amide-directed 1,2-diarylation, which involves carbonyl coordination. The synthetic utility of the method arises from the dual function of the sulfonamide as both a directing group and a masked amine nucleophile. This is highlighted by various product diversifications where complex amine compounds are synthesized in a two-step sequence of N-functionalization and deprotection of the sulfonyl group.