康 · 学术 | Reaction of the Day No. 1291

转自：康龙化成

Asymmetric 2,3-Addition of Sulfinylamines with Arylboronic AcidsEnabled by Nickel Catalysis

Longlong Xi,# Xiaowu Fang,# Minyan Wang,* and Zhuangzhi Shi*

State Key Laboratory of CoordinationChemistry, Chemistry and Biomedicine Innovation Center (ChemBIC),School of Chemistry and Chemical Engineering,

Nanjing University, Nanjing 210093, China

—J. Am. Chem. Soc., 2024,146, 17587−17594

Recommended by Feng Wang_SC

ABSTRACT:Sulfinamides havebeen widely used in organic synthesis, with research on their preparationspanning more than a century. Despite advancements in catalytic methodologies,creating sulfur stereocenters within these molecules remains a significant challenge. In this study, Prof.Shi and coworker present an effective and versatile method for synthesizing adiverse range of S-chirogenic sulfinamides through catalytic asymmetric aryl addition to sulfinylamines. Byutilizing a nickel complex as a catalyst, this process exhibits impressive enantioselectivity andcan incorporate various arylboronic acids at the sulfur position. The resulting synthetic sulfinamides arestable and highly adaptable, allowing for their conversion to a variety ofsulfur-containing compounds. This study also incorporates detailed experimentaland computational studies to elucidate the reaction mechanism and factorsinfluencing enantioselectivity.

Nickel-catalyzed asymmetric addition of sulfinylamines with arylboronic acids to access chiral sulfinamides

Selectedsubstratescope

Mechanismstudy

Synthetic applications

Summary and comments

Insummary, Prof. Shi and co-worker have introduced a novel method for thesynthesis of chiral sulfinamides containing S(IV) stereocenters bythe nickel-catalyzed 2,3-addition of sulfinylamines with arylboronic acids. The formed products allow for the preparation of various S-stereogenic derivatives in a stereoselective manner. The elucidation of the reaction mechanism governing the selective aryladdition processes was supported by a combination of experimental andcomputational findings. With increasing interest in chiral S-stereogenic derivatives for applications in pharmaceuticals and agrochemicals, Prof. Shiand co-worker anticipate widespread adoption of the techniques outlined in thisstudy.

（转自：康龙化成）