Sulfonamide Directivity Enables Ni-Catalyzed 1,2-Diarylation of Diverse Alkenyl Amines

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.本研究报道了镍催化下烯基磺酰胺（alkenyl sulfonamides）与芳基碘化物（aryl iodides）、芳基硼酸酯（aryl boronic esters）的1,2-二芳基化反应。所开发的方法可兼容具有不同电子特性与取代模式的偶联底物，二取代、三取代烯烃以及远离导向基团（directing group）的烯烃底物均能适用于该反应。控制实验（control experiments）结果表明，该反应的导向基团采取N-Ni配位模式，这与此前报道的由羰基配位（carbonyl coordination）介导的酰胺导向1,2-二芳基化反应截然不同。该方法的合成应用价值源于磺酰胺兼具导向基团与掩蔽型胺亲核试剂（masked amine nucleophile）的双重功能，这一点可通过多样的产物衍生化实验得到印证：通过N-官能化（N-functionalization）与磺酰基脱保护（deprotection）两步反应序列，即可合成复杂胺类化合物。