The formation of open-chain thioesters in the reaction of 2-lithio-2-methyl- and 2-lithio-2-phenyl-1,3-dithiane with chlorodiphenylphosphane followed by oxidation

The unexpected formation of open-chain thioesters (3) and (6) from the reaction of 2-lithio-r-2-t-4-t-6-trimethyl (1-Li) and 2-lithio-r-2-phenyl-t-4-t-6-dimethyl-1,3-dithiane (4-Li), respectively, with chlorodiphenylphosphane followed by oxidation was observed instead of the anticipated gem-derivatives. The X-ray diffraction analysis of (6) and the trapped intermediate (10) confirmed the structure and the proposed mechanism of formation of the open-chain products.