Rhodium-Catalyzed Double [2 + 2 + 2] Cycloaddition of 1,4-Bis(diphenylphosphinoyl)buta-1,3-diyne with Tethered Diynes: A Modular, Highly Versatile Single-Pot Synthesis of NU-BIPHEP Biaryl Diphosphines

• DOI: 10.1021/ol702390p
• Publication Date: 2007-10-16T15:53:13Z
• Authors: Simon Doherty; Julian G. Knight; Catherine H. Smyth; Ross W. Harrington; William Clegg
• Keywords: Diphosphines; Modular construction

Rhodium-catalyzed double [2 + 2 2] cycloaddition of 1,4-bis(diphenylphosphinoyl)buta-1,3-diyne with tethered diynes provides a straightforward, single-pot procedure for the synthesis new class tropos biaryl diphosphine, NU-BIPHEP. This methodology represents significant improvement on existing multistep procedures. Enantiopure Lewis acid platinum complexes these diphosphines are highly efficient catalysts carbonyl-ene and Diels-Alder reactions, ruthenium diphosphine-diamine catalyze asymmetric reduction ketones to give ee's that rival those obtained their BINAP counterpart.