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Influence of beta-Substituents in Aldol Reactions of Boron Enolates of beta-Alkoxy Methylketones

  作者 DIAS LUIZ C; DE LUCCA EMILIO C JR; FERREIRA MARCO A B; GARCIA DANILO C; TORMENA CLAUDIO F  
  选自 期刊  Organic Letters;  卷期  2010年12-21;  页码  5056-5059  
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[摘要]Moderate to good levels of substrate-based 1,5-syn-stereocontrol could be achieved in the boron-mediated aldol reactions of beta-tert-butyl methylketones with achiral aldehydes, independent of the nature of the beta-alkoxy protecting group (P = PMB or TBS). The analysis of the relative energies of the transition structures by theoretical calculations using the density functional B3LYP shows relative energies favoring the corresponding OUT-1,5-SYN transition structures, explaining the observed 1,5-syn stereoinduction.

 
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