Synfacts 2007(5): 0523-0523  
DOI: 10.1055/s-2007-968424
Metal-Mediated Synthesis
© Georg Thieme Verlag Stuttgart · New York

Unsymmetrical Sulfides, Selenides, and Tellurides from Organoboronic Acids

Contributor(s):Paul Knochel, Andrei Gavryushin
N. Taniguchi*
Fukushima Medical University, Japan
Convenient Synthesis of Unsymmetrical Organochalcogenides Using Organoboronic Acids with Dichalcogenides via Cleavage of the S-S, Se-Se, Te-Te Bond by a Copper Catalyst
J. Org. Chem.  2007,  72:  1241-1245  
Further Information

Publication History

Publication Date:
24 April 2007 (online)


Significance

This procedure allows a convenient and general transformation of various organoboronic acids into unsymmetrical sulfides, selenides, or tellurides. The mild reaction conditions ensure an excellent functional group tolerance, thus making this reaction useful for the combinatorial-like synthesis of biologically relevant molecules. The best yields are achieved with aryl chalcogenides and arylboronic acids; nevertheless, the scope of suitable substrates is quite broad. This is one of few useful methods for the preparation of unsymmetrical selenides and tellurides.

Comment

In the suggested reaction mechanism, the R1B(OH)2 is first converted into R1Cu(I), which reacts with (R2S)2 or its analogue to give R1SR2 and R2SCu, which after the oxidation by O2 reacts with another molecule of an organoboron compound. The reaction, therefore, requires the presence of air. Dichalcogenides are much easier to handle than the corresponding thiols or selenols, as they are not air-sensitive.

Review

For a review on the Cu-mediated aryl-heteroatom bond formation, see: S. V. Ley, A. W. Thomas Angew. Chem. Int. Ed. 2003, 42, 5400-5449.