Intramolecular cyclization of ω‐haloalkylsubstituted thiophosphorylacetonitriles: Synthesis and stereochemistry of 3‐cyano‐2‐oxo‐1,2‐thiaphosphacyclanes

Abstract

Abstract Intramolecular S‐alkylation in a series of ω‐haloalkyl‐substituted thiophosphorylacetonitriles 5–7 presents an effective synthetic route to the hitherto unknown 3‐cyano‐2‐oxo‐1,2‐thiaphospholanes 14 and thiaphosphinanes 15 . The compounds were obtained as a mixture of cis‐ and trans‐isomers that were resolved to individual stereoisomers in most cases. For some of them, X‐ray diffraction analysis has been performed. It was shown that 31 P NMR spectroscopy can be used to assign the stereochemistry of 3‐cyano‐2‐oxo‐1,2‐thiaphosphacyclanes. © 2002 John Wiley & Sons, Inc. Heteroatom Chem 13:1–21, 2002; DOI 10.1002/hc.1101