Synthesis of functionalized 1,4-cyclohexadienes through intramolecular anionic dearomatization of N-alkyl-N-benzyldiphenylphosphinamides. Insight into the reaction mechanism.

A generalization of the intramolecular nucleophilic dearomatization-electrophilic alkylation reactions of N-alkyl-N-benzyldiphenylphosphinamide anions is presented. The process has been optimized by analyzing the effects of metalation and quench times, additives, the nature of the electrophiles used (MeI, CF(3)SO(3)Me, Me(3)O(+)BF(4)(-), AllylBr, PhCH(2)Br, BrCH(2)CO(2)Me, and RCH=O, where R = Ph, 4-Cl-C(6)H(4), 4-MeO-C(6)H(4), and (i)()Pr), and the alkyl substituent linked to the nitrogen of the phosphinamide. Both HMPA and DMPU act as catalysts.

Dilithiated phosphazenes: scaffolds for the synthesis of olefins through a new class of bicyclic 1,2-oxaphosphetanes.

The first examples of the PN-directed dilithiation of (N-methoxycarbonyl)phosphazenes in the C(alpha) and C(ortho) to the phosphorus, and the use of these dianions in the formation of tri- and tetra-substituted olefins through stereospecific thermolysis of a new type of isolable bicyclic 1,2-oxaphosphetanes are described.

The first synthesis of enantiopure alpha-amino ketimines and amino aziridines.

Chiral 1-aminoalkyl chloromethyl ketimines 2 are synthesized in enantiomerically pure form starting from 1-aminoalkyl chloromethyl ketones 1 and different amines. Reduction of amino ketimines 2 and subsequent spontaneous cyclization affords aminoalkyl aziridines 3 with high diastereoisomeric excess and without detectable racemization.