Catalytic enantioselective α-sulfenylation of β-ketocarbonyls by chiral primary amines

Abstract

A simple chiral primary amine catalyst was identified to enable effective catalysis in direct α-sulfenylation of acyclic and cyclic β-ketocarbonyls with good yields and excellent enantioselectivities.

Steric Effect of Protonated Tertiary Amine in Primary–Tertiary Diamine Catalysis: A Double-Layered Sterimol Model

“…Recently, we developed the chiral primary− tertiary diamine catalyzed sulfuration reaction of ketones. 18 Survey of the catalysts showed significant dependence on the size of the N-substituents (see the SI). Regression analysis also showed that the enantiocontrol was mainly determined by the outsphere B1 and innersphere B 1 ′ (Scheme 4, eq 7, and Figure S4B).…”

β‐Keto Amides: A Jack‐of‐All‐Trades Building Block in Organic Chemistry

“…reported the KI‐catalyzed oxidative sulfenylation of 375 to 376 with aryl thiols by using oxygen as the green oxidant (Scheme 75). [170] In 2018, Luo and co‐workers identified a simple chiral amine 379 to catalyze the enantioselective α ‐sulfenylation of β ‐dicarbonyls with N ‐phenylthio phthalimide 378 [171] . The α ‐methyl β ‐keto amide 377 was converted to the α ‐sulfenylation product 380 in 99 % yield and 45 % ee (Scheme 76).…”

Recent Advances in Synthesis of Chiral Thioethers

“…Asymmetric α‐sulfenylation of acyclic and cyclic β‐ketocarbonyls 188 were developed by Mi and co‐workers, providing corresponding products in ideal results (Scheme 62). [64] The Bronsted acid acted as a liaison throughout the reaction, which could promote the isomer conversion of enamine and iminium. The whole reaction process was performed by forming enamine/iminium intermediates.…”