Like other lithio derivatives of thioacetals bearing a second anionic site, dilithio derivatives of 3,3-, 5 5 , and 6,6-bis(phenylthio) alcohols decompose at or below ambient temperature to yield products ascribable to carbenoid intermediates. The 5,5-derivatives decompose far faster than the other types, and they yield mainly 2-(phenylthio)cyclopentanols and none of the unsaturated alcohols and glycols, arising from 1,2-hydrogen transfer and carbenoid dimerization, respectively, which are the major products from the other two types of reactants. The five-membered ring formation observed in the 5,5-systems results from insertion of a carbenoid carbon atom into the activated carbinol CH bond of the oxyanion, and a stereochemical study reveals that this process is not concerted. The evidence suggests that this ring closure is a result of displacement of a thiophenoxide ion from the lithiothioacetal by a hydride ion which is transferred from the carbinyl carbon atom in a transition state involving coordination of the lithium atom of the carbenoid with the oxyanion.Recently, we proposed the following principle which has led A. J. Am. Chem. Soc. 1973, 95,4100. Brown, H. C.; Krishnamurthy, S. J. J. Am. Chem. Soc. 1972,94,7159. (12) Consistent with literature precedents, 23 and 21 were produced in a ratio of 2.6:l; for example, see: Dauben, W. G.; Fonkcn, G. J.; Noyce, D. S. J. Am. Chem. Soc. 1956, 78, 2519. (13) Mura, A. J., Jr.; Majetich, P. A.; G r i m , P. A.; Cohen, T. Tetrahedron Lett. 1975, 4431. (14) The major product of treatment of the cis-cyclohexanol mixture 21 with excess HCl and 1.5 quiv of thiophenol for 20 h was the octahydrochromene resulting from intramolecular attack of the hydroxyl group on the cation produced by protonation of the vinyl sulfide group, but, as expected, (see, for example, Scheme HI) further treatment of this material led to the monocyclic thioacetal in good yield. An analogous product was formed from 23 along with a much larger amount of 24 after a 5-h treatment with HCI in neat thiophenol (40 quiv). (15) (a) Crandall, J. K.; Magha, H. S. J. Org. Chem. 1982,47,5368. (b) Crandall, J. K.; Magha, H. S.; Henderson, M. A,; Widner, R. K.; Tharp, G.