The completely diastereoselective silyl triflate‐mediated methyl orthoformate alkylation of chiral N‐acyl‐4‐isopropyl‐1,3‐thiazolidine‐2‐thiones catalyzed by commercially available nickel(II) complexes is reported. The simple experimental procedure requires 2.5–5 mol% of bis(phosphine)nickel dichloride [(R3P)2NiCl2] complexes, proceeds under very mild conditions, and covers a wide array of acyl groups. Furthermore, it can potentially be expanded to different electrophiles.magnified image

Diastereoselective Methyl Orthoformate Alkylations of Chiral N-Acylthiazolidinethiones Catalyzed by Nickel(II) Complexes. -The reaction proceeds with complete diastereoselectivity. The exocyclic bond in the thiazolidinethione auxiliary is required to achieve a high stereocontrol of the reaction and the endocyclic sulfur atom asures that no undesired decomposition takes place. Preliminary results on the extension of the method to the alkylation reaction with different electrophiles are presented. -(ROMO, J. M.; GALVEZ, E.; NUBIOLA, I.; ROMEA*, P.; URPI, F.; KINDRED, M.; Adv. Synth. Catal. 355 (2013) 14-15, 2781-2786, http://dx.