General and Practical Formation of Thiocyanates from Thiols

• Published in: Chemistry : a European journal Vol. 21; no. 6; pp. 2662 - 2668
• Main Authors: Frei, Reto, Courant, Thibaut, Wodrich, Matthew D., Waser, Jerome
• Format: Journal Article
• Language: English
• Published: Weinheim WILEY-VCH Verlag 02.02.2015; WILEY‐VCH Verlag; Wiley; Wiley Subscription Services, Inc
• Subjects: Aliphatic compounds; Biology; Chemistry; Chemistry, Multidisciplinary; chemoselectivity; cyanation; Disulfides; Formations; hypervalent iodine; Iodine; Iodine - chemistry; Isomerism; Materials science; Molecular Conformation; Physical Sciences; R&D; Research & development; Science & Technology; Sulfhydryl Compounds - chemistry; synthetic methods; Thermodynamics; Thiocyanates; Thiocyanates - chemical synthesis; Thiocyanates - chemistry; Thiols; hypervalent iodine; chemoselectivity; thiocyanates; DIRECT CYANATION; ALKYNYLATION; ARYL THIOCYANATES; DENSITY FUNCTIONALS; cyanation; HIGHLY STEREOSPECIFIC METHOD; CYANO; ORGANIC THIOCYANATES; CHEMISTRY; M06 SUITE; synthetic methods; HYPERVALENT IODINE REAGENTS
• ISSN: 0947-6539; 1521-3765
• DOI: 10.1002/chem.201406171

A new method for the cyanation of thiols and disulfides using cyanobenziodoxol(on)e hypervalent iodine reagents is described. Both aliphatic and aromatic thiocyanates can be accessed in good yields in a few minutes at room temperature starting from a broad range of thiols with high chemioselectivity. The complete conversion of disulfides to thiocyanates was also possible. Preliminary computational studies indicated a low energy concerted transition state for the cyanation of the thiolate anion or radical. The developed thiocyanate synthesis has broad potential for various applications in synthetic chemistry, chemical biology and materials science. Easy and general: A new method for the cyanation of thiols using cyanobenziodoxol(on)e hypervalent iodine reagents is described. Both aliphatic and aromatic thiocyanates can be accessed in good yields in a few minutes at room temperature with high chemioselectivity. The developed thiol‐cyanation reaction has broad potential for the formation of thiocyanates with various applications in synthetic chemistry, chemical biology and materials science.