Kinetic resolution of sulfur-stereogenic sulfoximines by Pd(ii)–MPAA catalyzed C–H arylation and olefination

Abstract

A direct Pd(II)-catalyzed kinetic resolution of heteroaryl-enabled sulfoximines through an ortho-C-H alkenylation/arylation of arenes has been developed for the first time. The coordination of sulfoximine pyridyl-motif and the chiral amino...

Cobalt(III)/Chiral Carboxylic Acid‐Catalyzed Enantioselective Synthesis of Benzothiadiazine‐1‐oxides via C−H Activation

“…In these studies, simple achiral catalysts were employed to provide racemic products; however, benzothiadiazine‐1‐oxides possess a chiral sulfur center, whose stereochemistry can affect their biological activity and physiological properties [9] . Although enantioselective C−H functionalization reactions [10] of sulfoximines via desymmetrization [11a,b,d,e, 12] or kinetic resolution [11c,d,f, 13] have been developed using Rh III catalysts with a chiral Cp x ligand [14] by Li [11a] and Cramer [11b,c] or using the combination of a Ru II catalyst and a chiral carboxylic acid co‐catalyst [15–20] by Shi [11d] and our group, [11e] or using a Pd II /MPAA catalyst by Gandon and Sahoo, [11f] only enantioselective C−C bond formation has been reported, while reports on enantioselective C−N bond formation remain elusive. In addition, the enantioselective C−H functionalization of sulfoximines using Earth‐abundant first‐row transition metal catalysts has not yet been reported.…”

Kinetic and Dynamic Kinetic Resolution by Dual Catalysis

“…Sahoo and co‐workers reported KR of sulfoximines by Pd‐amino acid (MPPA) ligand in 2021 (Table 23). [76] Kinetic resolution was achieved through C‐arylation or alkenylation at the ortho position whose C−H bond was activated by sulfoxime‐pyridine coordination of Pd/MPPA. The authors screened several directing groups and ligands and found N,O ‐protected threonine ligands and 3‐methyl pyridyl directing group to be superior.…”

Synthesis of P- and S-Stereogenic Compounds via Enantioselective C–H Functionalization

“…Almost at the same time, Sahoo and co-workers reported the kinetic resolution of sulfur-stereogenic sulfoximines via Pd(II)/MPAA-catalyzed C-H arylation and olefination (Scheme 7). 23 Boc-L-Thr(Bn)-OH was the optimal ligand for this transformation. A variety of sulfoxides rac-16 were compatible with this protocol, giving access to a variety of highly functionalized sulfoximines in good yields with excellent enantioselectivities.…”