Liu Le-Ping, Hammond Gerald B
Department of Chemistry, University of Louisville, Louisville, Kentucky 40292, USA.
Chem Asian J. 2009 Aug 3;4(8):1230-6. doi: 10.1002/asia.200900091.
The reaction of allenoates with cationic gold(I)-generated in situ from a phosphine gold chloride and a silver salt-formed unusual, room temperature stable vinyl gold(I) lactones under very mild conditions. The scope and limitations for the synthesis of this novel organogold complex was investigated. DFT calculations on the highest occupied molecular orbitals (HOMOs) of allenoates and the natural bond orbital (NBO) charge densities provided an explanation for the limitations. A plausible mechanism for its formation was proposed based on in situ (1)H and (31)P NMR spectroscopic analyses. Controlled experiments for the cleavage of the gold-carbon bond by electrophiles indicated that this vinyl gold(I) complex is the likely intermediate in the gold-catalyzed reaction of carbon-carbon multiple bonds.
丙二烯酸酯与由氯化膦金和银盐原位生成的阳离子金（I）反应，在非常温和的条件下形成了不寻常的、室温稳定的乙烯基金（I）内酯。研究了这种新型有机金配合物合成的范围和局限性。对丙二烯酸酯的最高占据分子轨道（HOMO）进行密度泛函理论（DFT）计算以及自然键轨道（NBO）电荷密度分析，为这些局限性提供了解释。基于原位的¹H和³¹P核磁共振光谱分析，提出了一个合理的形成机理。亲电试剂对金 - 碳键断裂的对照实验表明，这种乙烯基金（I）配合物可能是金催化碳 - 碳多重键反应中的中间体。
