Department of Chemistry, Lehigh University, Bethlehem, Pennsylvania 18015, USA.
J Am Chem Soc. 2010 Dec 15;132(49):17396-8. doi: 10.1021/ja1088925. Epub 2010 Nov 19.
The presence of HMPA is critical for the selective coupling of alkyl halides and ketones by SmI2. Although previous rate studies have shown that HMPA dramatically accelerates the reduction of alkyl halides over ketones, the basis of this rate acceleration is unknown. In this communication, we report experimental and computational evidence that demonstrate that the selectivity observed in the samarium Barbier reaction is in part a result of activation of the alkyl halide bond by HMPA.
HMPA 的存在对于 SmI2 选择性偶联卤代烃和酮至关重要。虽然之前的速率研究表明 HMPA 显著加速了卤代烃相对于酮的还原，但这种速率加速的基础尚不清楚。在本通讯中，我们报告了实验和计算证据，证明在钐 Barbier 反应中观察到的选择性部分是 HMPA 活化卤代烃键的结果。
