James R. Matz

Reductive Lithiation of Some Thioketals Using Lithium 1-(Dimethylamino)naphthalenide

Abstract Recent work from this laboratory has demonstrated that readily prepared lithium naphthalenide (2) at -70° is capable of the rapid reductive lithiation of cyclopropanone dithioketals (1) to sulfur-stabilized cyclopropyllithiums (4),1 ketene phenylthio-acetals (8) to sulfur-stabilized vinyllithiums (9) which are acyl anion equivalents,2 and a 1,1,3-tris(phenylthio)alkene (11) to the lithio derivative (12) of an α,β-unsaturated thioacetal.3,4

A synthesis of 2-vinylcylobutanones using 1-methoxycyclopropyllithium reagents

Abstract A facile synthesis of 2-vinylcyclobutanones consists of reductive lithiation of 1-phenylthio-1-methoxycyclopropanes) addition of enals or enones to the resulting α-lithioethers, and acid catalyzed rearrangement of the allylic alcohols thus produced.

Cyclopentenone and cyclohexenone annulations via acid-catalyzed 1,2- and 1,3-acyl migration of 2-vinylcyclobutanones. Rearrangement route to spiro- and angularly substituted fused-cyclopentenones.

Abstract In the presence of acid, 2-alkyl-2-vinylcyclobutanones rearrange mainly by a 1,2-acyl migration to give cyclopentenones while 2-vinylcyclobutanones lacking 2-alkyl substituents undergo a 1,3-acyl migration to produce cyclohexenones; the former rearrangement can be used to produce angularly substituted fused bicyclic systems.