Synthesis of P‐Stereogenic Phosphine Oxides via Nickel‐Catalyzed Asymmetric Cross‐Coupling of Secondary Phosphine Oxides with Alkenyl and Aryl Bromides

Abstract

A general and mild nickel‐catalyzed enantioselective C(sp2)−P cross‐coupling for synthesizing P‐stereogenic phosphine oxides has been developed. The asymmetric alkenylation/arylation of racemic secondary phosphine oxides with alkenyl/aryl bromides generated P‐stereogenic phosphine oxides with high yields and enantioselectivities. Various functional groups were tolerated, and the applications of this method were demonstrated through late‐stage functionalization and product transformations.

Organocatalytic Diastereoselective (4 + 1) Cycloaddition of o-Hydroxyphenyl-Substituted Secondary Phosphine Oxides

“…In this context, we conceive to use o -hydroxyphenyl substituted SPOs as suitable four-atom phosphorus-containing building blocks for developing organocatalytic (4 + 1) cycloadditions of SPOs. As shown in Scheme a, o -hydroxyphenyl substituted SPOs are able to transform into the corresponding P­(III) intermediates A . This class of P­(III) intermediates A has unique structural features as the hydroxyl group adjacent to the phosphorus atom can act as an activation site with organocatalysts by hydrogen-bonding interactions .…”