Efficient preparation of chiral non-racemic sulfur compounds

• Published in: Canadian journal of chemistry Vol. 85; no. 9; pp. 603 - 618
• Main Authors: Minville, Joannie, Girardin, Mélina, Spino, Claude
• Format: Journal Article
• Language: English
• Published: Ottawa, Canada NRC Research Press 01-09-2007; Canadian Science Publishing NRC Research Press
• Subjects: Acids; Carbon; Chemical compounds; Chemical reactions; Chirality; Properties; Sulfur; Sulfur compounds; Canada
• ISSN: 0008-4042; 1480-3291
• DOI: 10.1139/v07-091

p-Menthane-3-carboxaldehyde serves as an efficient chiral auxiliary in the preparation of chiral non-racemic S-alkylthiocarbamates or S-dithiocarbonates via the 3,3-sigmatropic rearrangement of the corresponding alkylthionocarbamates or xanthates. The transfer of chirality during rearrangement is complete, and the final products possess a chiral tertiary or quaternary carbon bearing sulfur. The rearranged products are then transformed into enantiopure cyclic or acyclic sulfur-containing products, depending on the means of clivage of the auxiliary. The synthesis of a potent MMP-13 inhibitor is presented.Key words: 3,3-sigmatropic rearrangement, p-menthane-3-carboxaldehyde, S-alkylthiocarbamate, S-dithiocarbonate, alkylthionocarbamate, xanthate, ring-closing metathesis.