Intramolecular, reductive cyclization of beta-ketoisothiocyanates promoted by using samarium diiodide
Min Seok Cho1, In Sang Lee, Sung Ho Kang
1Department of Chemistry, Center for Molecular Design and Synthesis, Korea Advanced Institute of Science and Technology, Daejon, 305-701, Korea.
Abstract:
A novel samarium diiodide (SmI2) promoted intramolecular cyclization of beta-ketoisothiocyanate, derived from alpha,beta-unsaturated esters and ammonium thiocyanate led to alpha-hydroxythiolactams and/or thiolactams in high yields. Treatment of beta-ketoisothiocyanate with two equivalents of SmI2 gave a mixture of alpha-hydroxythiolactam and thiolactam. Four equivalents of SmI2 afforded only thiolactam in high yields. The intramolecular cyclization took place with high to complete stereoselectivity. A mechanism to explain this transformation is proposed.
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