Catalytic Sulfamoylation of Alcohols with Activated Aryl Sulfamates
Peter B Rapp1, Koichi Murai2, Naoko Ichiishi2
1Department of Chemistry , Yale University , P.O. Box 208107, New Haven , Connecticut 06520-8107 , United States.
Abstract:
We report a new catalytic method for alcohol sulfamoylation that deploys electron-deficient aryl sulfamates as activated group transfer reagents. The reaction utilizes the simple organic base N-methylimidazole, proceeds under mild conditions, and provides intrinsic selectivity for 1° over 2° alcohols (up to >40:1 for certain nucleosides). The requisite aryl sulfamate donors are stable crystalline solids that can be readily prepared on a large scale. Mechanistic considerations support the intermediacy of HNSO2 "aza-sulfene" in the transfer reaction.
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