Department of Chemistry, University of North Carolina at Chapel Hill, Chapel Hill, North Carolina 27599-3290, USA.
Org Lett. 2010 Apr 16;12(8):1784-7. doi: 10.1021/ol100410k.
The BF(3).OEt(2)-promoted nucleophilic substitution of alpha-aryl-alpha-ketophosphates to afford alpha,alpha-diaryl ketone products is described. Electron-rich alpha-ketophosphates perform best, with electron-neutral and electron-poor substrates also tolerated. The reaction is tolerant of a range of aromatic, heteroaromatic, and nonaromatic nucleophiles, with yields ranging from 44% to 84%. Enantioenriched starting material yields racemic product, suggesting an S(N)1 pathway via an acylcarbenium ion.
BF(3).OEt(2)促进的α-芳基-α-酮膦酸酯的亲核取代反应,可得到α,α-二芳基酮产物。富电子的α-酮膦酸酯表现最佳,电子中性和电子缺电子的底物也可以耐受。该反应对一系列芳基、杂芳基和非芳基亲核试剂具有耐受性,产率范围为 44%至 84%。对映富集的起始原料得到外消旋产物,表明通过酰基卡宾离子进行 S(N)1 途径。