Diastereoselective Electrophilic Trifluoromethylthiolation of Chiral Oxazolidinones: Access to Enantiopure α‐SCF₃ Alcohols

Abstract

Lithium imide enolates featuring Evans' chiral oxazolidinone auxiliary were involved in diastereoselective a-trifluoromethylthiolation with electrophilic SCF 3 donors. Diastereopure products were isolated and converted to enantiopure a-SCF 3 alcohols without racemisation.

Synthesis of Alpha‐trifluoromethylthio Carbonyl Compounds: A Survey of the Methods for the Direct Introduction of the SCF3 Group on to Organic Molecules

“…[56] Studies related to the cleavage of the chirala uxiliary were also performed, and it was found that using LiOH/H 2 O 2 at 0 8C enantiomerically pure a-SCF 3 -substituted alcohols couldb eo btained withoutracemization. [56] Studies related to the cleavage of the chirala uxiliary were also performed, and it was found that using LiOH/H 2 O 2 at 0 8C enantiomerically pure a-SCF 3 -substituted alcohols couldb eo btained withoutracemization.…”

“…[56] ChemCatChem 2018, 10,2717 -2733 www.chemcatchem.org 2018 Wiley-VCH Verlag GmbH &Co. KGaA, Weinheim center were obtained in excellenty ields with good to excellent enantioselectivities,w ithouti nfluence of the substitutions on the aromatic ring. Wynberg ion pair hydrogen bonding model.…”

“…Ad iastereoselective electrophilic trifluoromethylthiolation of chiral oxazolidinones was also recently reported by Cahard, using LiHMDS and in the presence of N-SCF 3 phthalimide 5 (Scheme 37). [56] Studies related to the cleavage of the chirala uxiliary were also performed, and it was found that using LiOH/H 2 O 2 at 0 8C enantiomerically pure a-SCF 3 -substituted alcohols couldb eo btained withoutracemization.…”

“…a) general mechanism activationofquinidine;b)calculated lowest TS for the C-SCF 3 bond formationc alculated at the (SMD)-B3LYP-D3(BJ)/6-311 ++G(2d,p)//(SMD)-M06-2X/6-31G(d) leveloft heory.Bond lengths are in .R eproduced withp ermission from Xue, Chenge tal. [56] ChemCatChem 2018, 10,2717 -2733 www.chemcatchem.org center were obtained in excellenty ields with good to excellent enantioselectivities,w ithouti nfluence of the substitutions on the aromatic ring.…”

Trifluoromethylthiolation of α‐Chloroaldehydes: Access to Quaternary SCF3‐Containing Centers

“…Alternatively, the direct introduction of a SCF 3 group onto amides, N ‐acyl oxazolidinones and ketones was also studied, albeit restricted to a handful of examples. [10h], …”