The Mechanism of Double Olefination Using Titanium-Substituted Ylides.
The adduct 3, derived from TiCl(3)(OiPr) and (Me(2)N)(3)P=CH(2), engages in a complicated set of interactions with NaN(SiMe(3))(2) and aldehydes, resulting in the requirement to use excess amounts of both reagents for the one-pot synthesis of allenes. When TiCl(2)(OiPr)(2) is used instead, ligand substitution reactions with NaN(SiMe(3))(2) are diminished and so stepwise transformations can be accomplished without excess amounts of each reagent. The selective production of vinylphosphonium salts and byproduct titanium oxides from Ti-substituted ylides and aldehydes is proposed to arise from the presence of a chloride leaving group on the metal. Isolated vinylphosphonium compounds may be deprotonated with phenyllithium to give thermally sensitive allenic phosphoranes, which have been characterized by low temperature multinuclear NMR. The reaction of allenic phosphoranes with aldehydes affords oxaphosphetane and betaine intermediates which appear to interconvert upon warming to produce allene and phosphine oxide. Dimethylamino-substituted phosphorus components are required for high yields in both steps of the allene-forming process, presumably to boost the reactivity of the hindered Ti-substituted ylide reagents and to stabilize the allenic phosphorane unit so that it may be trapped by aldehyde. The placement of chiral groups on the phosphorus methylide or aldehyde components results in low levels of enantiomeric and diastereomeric induction, respectively, during allene formation. In two cases, the diastereomeric ratios of initially-formed oxaphosphetanes have been found to differ from the diastereomeric composition of their product allenes, offering examples of the phenomenon known as "stereochemical drift". However, oxaphosphetane/betaine formation from allenic phosphorane and aldehyde has been found to be irreversible, suggesting that an intramolecular betaine olefin isomerization is responsible for the loss of stereochemical integrity during the Wittig step.
Reynolds
Kelly A.
KA
Department of Chemistry, University of Virginia, Charlottesville, Virginia 22901.
Finn
M. G.
MG