Stereochemical Studies on Hemiorthothiol and Hemiorthothiolate Tetrahedral Intermediates

Article abstract of DOI:10.1021/ja00281a040

This study deals with hemiorthothiol-RC(OR')2SH-tetrahedral intermediates including (a) two acyclic ones of type <11>, (b) two types of monocyclics <12> and <13>, and (c) four bicyclic systems <14>, <15>, <16>, and <17>.The breakdown of <11> (R = Ph, R' = Et) led to thiono esters 34 and 35; that of <12> (R = Me, Ph) resulted in hydroxy thiono esters 36-39, whereas the cleavage of <13> (R =Me, Et) yielded thionolactones 49-53 and hydroxy thiono esters 55-58.The study of rigid bicyclic intermediates <14>-<17> helped uncover the role of stereoelectronic effects in the breakdown of hemiorthothiol tetrahedral intermediates.Finally, a family of isolable hemiorthothiolate tetrahedral intermediates-RC(OR')2S^-+Na-viz. <91^->-<94^-> (monocyclic) and <20^-> (bicyclic) is reported.