Accelerated and Enantioselective Synthesis of a Library of P‐Stereogenic Urea Phosphines

Chiral phosphorus ligands play a central role in majority of the asymmetric transformations. However, access to chiral phosphorus ligands is limited due to their challenging synthesis. Reported here is a highly efficient and accelerated catalytic asymmetric synthesis of P‐stereogenic urea containing phosphines leading to a small library of 18 chiral phosphorus compounds. Characteristic two doublets in a 31 P NMR spectrum, spectroscopic and analytical evidences authenticated the formation of [Pd‐{( S , S ) Me‐FerroLANE}( m ‐phenylurea)( I )] complex. Indeed, [Pd‐{( S , S ) Me‐FerroLANE}( m ‐phenylurea)( I )] was found to catalyze the C‐P coupling reaction and quantitative conversion was observed within 18 hours. Under optimized conditions, iodophenyl urea's ( 2a – 2j ) were treated with secondary phosphines ( 1a – 1c ) in presence of [Pd‐{( S , S ) Me‐FerroLANE}( m ‐phenylurea)( I )] to obtain P‐stereogenic urea phosphines 5a – 5r . The identity of these urea derived phosphines was unambiguously ascertained using a combination of spectroscopic and analytical methods. The catalyst tolerated various functional groups and yielded corresponding urea containing phosphines with an enantiomeric excess in the range of 15–62 %.