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[摘要]：Acylphosphonates behave as carbonyl components in Passerini reactions with isocyanides and carboxylic acids. Under sapon., the adducts undergo a phospha-Brook rearrangement to form a-amido phosphonates. As acylphosphonates are quant. formed from carboxylic derivs., this new reductive procedure allows acyl chlorides to react as aldehydes in a Passerini-type reaction. E.g., reaction of PhCH2CH2COCl with neat P(OMe)3 for 30 min, followed by treatment with 1 equiv CyNC (Cy = cyclohexyl) and 1 equiv AcOH and PhMe for 24 h at room temp. gave 74% PhCH2CH2C(OAc)[P(O)(OMe)2]CONHCy. Treatment of this Passerini product with 1 equiv LiOH in THF for 2 days at 65?gave 100% PhCH2CH2CH[P(O)(OMe)2]CONHCy. |
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