Synfacts 2018; 14(11): 1145
DOI: 10.1055/s-0037-1611240
Metal-Catalyzed Asymmetric Synthesis and Stereoselective Reactions
© Georg Thieme Verlag Stuttgart · New York

Rhodium-Catalyzed Hydrothiolation of 1,3-Dienes

Hisashi Yamamoto
Takahiro Sawano
Yang X.-H, Davison RT, Dong VM. * University of California-Irvine, USA
Catalytic Hydrothiolation: Regio- and Enantioselective Coupling of Thiols and Dienes.

J. Am. Chem. Soc. 2018;
140: 10443-10446
Further Information

Publication History

Publication Date:
18 October 2018 (online)



The development of reactions for the construction of C–S bonds is important because molecules essential to life contain this linkage. The addition of thiols to alkenes is a direct and atom-economical method for the formation of C–S bonds. The authors have developed an enantioselective addition of thiols to 1,3-dienes catalyzed by a rhodium–chiral bisphosphine ligand complex to give chiral secondary or tertiary allylic sulfides in good to high enantioselectivities.



The enantioselective hydrothiolation proceeds selectively at the more-substituted double bond. A broad range of functional groups are tolerated in this reaction, and the catalyst loading can be lowered to 0.1 mol%.