Allenyl bisphosphine oxides having variable chirality were prepared in high dr, which was controlled by chiral carbon and phorphorus.

A wide range of R_P or S_P-(l)-menthyl-containing SPOs were prepared via the reaction of 1,1′-bi(2-naphthol) derived phosphonite with a metallic reagent with excellent yield and dr.

Phosphine ligands with up to six chiral sites were prepared, starting from 2-phenylphenol, via O-and P-alkylation, cyclization, and coupling. The chirality was transferred from (L)-menthyl to phosphorus, α-carbon, and axis, to achieve excellent diastereoselectivities. During an intramolecular S N Ar reaction with alkoxyl as the leaving groups, the C−O bond was converted to a C−C bond. Both phosphine boranes and oxides could be used for the conversions, affording a series of cyclic phosphines.

The additions of RP‐1 or SP‐1 to alkynyl esters stereo selectively afforded bis‐phosphinylated derivatives having up to four C‐ and P‐chirogenic centers. The stereochemistry was controlled by kinetic and thermodynamic processes at lower and higher temperature, respectively. At 100 °C, the bis‐adducts were obtained in up to 99% yield and >99 : 1 d.r.

Biphenyl derived secondary phosphine oxides having 2’-hydroxyl were prepared. The compound were converted to hydroxymethyl phosphine oxides when reacted with formaldehyde. After chlorination and cyclization, a series of P,O-heterocycles were...