Diastereoselectivity in the Mukaiyama-Michael Reaction Employing alpha-Acyl beta,gamma-Unsaturated Phosphonates.

Abstract

The unique electronic and structural nature of the alpha-acylphosphonate functional group affords both dimeric and chelated complexes of diethyl crotonyl phosphonate (1; DECP) with stannic chloride (SnCl(4)). The dimeric complex, SnCl(4).(DECP)(2) (5) results from the coordination of two DECP molecules, ligated via the phosphoryl oxygens to the tin atom. The chelated complex, SnCl(4).(DECP) (6), is best represented with both phosphoryl and carbonyl oxygens coordinated to the metal center. Both metal ligated and chelated complexes have unique (13)C (31)P, and (119)Sn NMR spectra. In complex 5, the (13)C NMR resonances attributed to the carbonyl carbons were shifted upfield of free DECP. A monocoordinating Lewis acid, BF(3).OEt(2), produced a similar chemical shift trend in both the (13)C and (31)P NMR spectra of the BF(3).DECP complex. Essentially quantitative yields and moderate diastereomeric excesses favoring anti (or trans) diethyl 6-phenyl-4,5-dimethyl-6-(trimethylsilyloxy)-2-dihydropyranphosphonate (3) and diethyl 5-phenyl-3,4-dimethyl-1,5-dioxopentanephosphonate (4) were obtained from both chelated and dimeric SnCl(4).(DECP)(n) (n = 1, 2) when treated with either diastereomeric (Z)- or (E)-1-phenyl-1-(trimethylsilyloxy)-1-propene 2. Diethyl crotonylphosphonate (1), 3, and 4 were fully characterized.