Sunday, June 29, 2008 - 3:30 PM
Diamond I (Sheraton Burlington Hotel and Conference Center)
11

Synthesis of Primary and Secondary Phosphines from Grignard Reagents

Carl A. Busacca, Boehringer-Ingelheim Pharmaceuticals, Inc., Ridgefield, CT

            We have recently described the use of DIBAL-H for the synthesis of secondary and tertiary phosphines from phosphine oxides.  We have now expanded the application of this inexpensive reducing agent to include reductions of phosphinites, phosphonites, phosphinates, and chlorophosphines.  Process Research has been carried out on the direct synthesis of secondary phosphine boranes starting from Grignard reagents and ethyldichlorophosphite (EtOPCl2).  These critical targets have been prepared in good yield without isolation or purification of any of the air-sensitive intermediates in the four step sequence, handling only the air-stable phosphine borane products.  The intermediate phospinites and phosphonites are reduced directly, in situ, with DIBAL-H.  Scope and limitations of the methodology, as well as detailed experimental procedures supported by digital photographs of the laboratory setups will be presented.