Xiao, Miao; Yue, Xin; Xu, Ruirui; Tang, Weijun; Xue, Dong; Li, Chaoqun; Lei, Ming; Xiao, Jianliang; Wang, Chao published the artcile< Transition-Metal-Free Hydrogen Autotransfer: Diastereoselective N-Alkylation of Amines with Racemic Alcohols>, Reference of 403-41-8, the main research area is diastereoselective alkylation amines alc chiral amine synthesis; alcohols; alkylation; amines; deuterium; reaction mechanisms.
A practical method for the synthesis of α-chiral amines by alkylation of amines with alcs. in the absence of any transition-metal catalysts has been developed. Under the co-catalysis of a ketone and NaOH, racemic secondary alcs. reacted with Ellman’s chiral tert-butanesulfinamide by a hydrogen autotransfer process to afford chiral amines with high diastereoselectivities (up to >99:1) [e.g., 1-phenylethanol + (R)-(+)-tert-butanesulfinamide → I (70%, > 95:5 d.r.) in presence of acetophenone and NaOH in toluene]. Broad substrate scope and up to a 10 g scale production of chiral amines were demonstrated. The method was applied to the synthesis of chiral deuterium-labeled amines with high deuterium incorporation and optical purity, including examples of chiral deuterated drugs. The configuration of amine products is found to be determined solely by the configuration of the chiral tert-butanesulfinamide regardless of that of alcs., and this is corroborated by DFT calculations Further mechanistic studies showed that the reaction is initiated by the ketone catalyst and involves a transition state similar to that proposed for the Meerwein-Ponndorf-Verley (MPV) reduction, and importantly, it is the interaction of the sodium cation of the base with both the nitrogen and oxygen atoms of the sulfinamide moiety that makes feasible, and determines the diastereoselectivity of, the reaction.
Angewandte Chemie, International Edition published new progress about Alkylation catalysts, stereoselective. 403-41-8 belongs to class alcohols-buliding-blocks, and the molecular formula is C8H9FO, Reference of 403-41-8.
Referemce:
Alcohol – Wikipedia,
Alcohols – Chemistry LibreTexts