Catalytic asymmetric synthesis of α-tertiary aminoketones from sulfoxonium ylides bearing two aryl groups

Abstract

Disclosed herein is an efficient organocatalytic formal N-H insertion reactions of arylamines with α-keto sulfoxonium ylides bearing two aryl groups, delivering a broad range of α-tertiary aminoketones with good to...

Recent advance: Sulfur ylides in organic synthesis

“…In 2023, Guo et al used two aryl groups containing sulfur ylides to generate α‐tertiary aminoketones 284 (Scheme 61) [85a, b]. The reaction proceeded at room temperature for 36 h under the influence of p ‐methoxyphenyl, 0.1 M dichloromethane, and a 10 mol% mixture of a Bronsted acid.…”

“…In this reaction scheme, the generation of CN acts as the rate‐determining step and affects the enantioselective nature of the products as well. This reaction is efficient in producing α‐aminoketones which are essential bioactive molecules used in organic synthesis and medicinal chemistry (Figure 30) [85a, b].…”

Application of sulfonium and sulfoxonium ylides in organocatalyzed asymmetric reaction

“…Although that catalytic asymmetric insertion reaction of metal carbenes into N-H bond with the enantioselective control via metal-chiral metal interaction has been well-established [74,75] , the asymmetric insertion reaction of free carbenes into N-H bond faces a challenge due to strong background reactions and lack of any anchor for a catalyst interaction. Recently, Guo et al made progress in the catalytic enantioselective insertion reaction of free carbenes into N-H bond using an indirect approach [76] . In their developed protocol [Figure 16], with visible light as a promoter, the -diazoesters 60 could be converted to free carbene intermediate 61, which was captured rapidly by DMSO to in situ form sulfoxonium ylide 50.…”

“…Visible-light-induced organocatalytic enantioselective N-H insertion of α-diazoesters with in situ generated sulfoxonium ylides. This figure is used with permission from the Royal Society of Chemistry [76] .…”

Racemic Benzenesulfonohydrazide Enantioconvergent Tertiary C(sp3)−H Amination Catalyzed by Copper and Chiral Phosphoric Acid: Mechanistic Insights and Computational Prediction

“…Biocatalysis and biomimic catalyst design were also developed with limitations such as product inhibition and narrow substrate range. [17][18][19] Asymmetric additions as a powerful synthetic strategy to access quaternary stereocentres have been studied in recent years, [20][21][22] but instable enantioselectivity and difficulties in chiral resolution are still major challenges. Arnold et al [23] recently reported the first highly enantioconvergent tertiary CÀ H amination reaction using enzymatic catalysis.…”