One-Pot Syntheses of Sterically Shielded Phosphorus Ligands by Selective Stepwise Nucleophilic Substitution at Triphenyl Phosphite
作者:Bernd F. Straub、Jan Keller、Clemens Schlierf、Christoph Nolte、Peter Mayer
DOI:10.1055/s-2005-921758
日期:——
have been successfully employed for the first substitution step. Due to the steric shielding, the phosphorus derivatives are sufficiently stable for conventional aqueous work-up. Due to their phenoxide groups, diphenyl phosphonites and phenyl phosphinites usually possess sufficiently high melting points for the isolation by crystallization.
已经开发了一种用于制备具有至少一个空间要求高的取代基的亚膦酸酯、亚膦酸酯和叔膦的通用无氯膦程序。在这种模块化方法中,在低温下向 P(OPh) 3 中连续添加化学计量量的碳负离子亲核试剂(例如有机锂试剂)会导致酚盐离去基团的选择性逐步取代。联苯-2-基、9-蒽基和 N-芳基吡咯-2-基亲核试剂已成功用于第一个取代步骤。由于空间屏蔽,磷衍生物对于常规的水性后处理足够稳定。由于它们的酚盐基团,二苯基亚膦酸酯和苯基亚膦酸酯通常具有足够高的熔点以用于通过结晶分离。