A practical and cost-effective synthetic method of P-chiral diarylalkyl, aryldialkyl, and triaryl phosphine oxides by using readily available chiral diphenyl-2-pyrrolidinemethanol as the auxiliary is developed. The long-standing racemization issue during solvolysis has been addressed and well controlled by employing a suitable solvent, a low reaction temperature, and an appropriate reaction time.

A highly selective hydrophosphorylation of terminal alkynes was developed for the preparation ofE-alkenylphosphorus compounds. Mechanistic investigations disclosed the deprotonation–protonation equilibrium of terminal alkynes and P(O)H compounds during this process.

The access to P-stereogenic motifs has always been considered a very challenging and high attractive mission in modern organic synthesis. While several chiral auxiliaries employed by the practical Jugé-Stephan-like methodology have been developed, new type of readily accessible bifunctional ligands toward P-stereogenic building still remain much desirable. Herein, we present a powerful chiral template, camphor-derived 2,3-diols named CAMDOL, which were designed and synthesized from the commercially cheap camphorquinone in high yields at 50 grams scale with a column-free purification. Diverse P(III)-chiral compounds and their borane forms including phosphinous acids, phosphinites, and phosphines, as well as the corresponding P(V)-chiral compounds including phosphinates, phosphine oxides, phosphinothioates, phosphine sulfides, and secondary phosphine oxides were afforded in high yields and ee values through the optimal 2,3-diphenyl CAMDOL platform. An unusual C³-OP bond cleavage following the first P-OC² bond breaking was observed during the ring-opening process when quenching by NH₄Cl solution, which generates a unique but valuable camphor-epoxide scaffold as by-product.

A highly regioselective O/C phosphorylation of α-chloroketones with trialkyl phosphites was developed in the preparation of enol phosphates and β-ketophosphonates.

An organobase-catalyzed 1,1-diborylation of terminal alkynes from propargylic derivatives with B₂oct₂ is first reported, providing 1,1-diborylalkene products with high efficiency. The catalytic pathway is well postulated on the basis of DFT calculations.