66 / 2023-08-16 11:38:57

CAMDOL: A Powerful Chiral Pool for Universal P-Stereogenic Building

P-asymmetry;,CAMDOL;,Asymmetric synthesis

Phosphorus in Synthetic Chemistry > 3) Syntheses of Chiral organophosphorus compounds

The access to P-chiral motifs has always been considered as a very challenging and high attractive mission in modern organic synthesis. P-Stereogenic building based on the most practical Jugé-Stephan methodology relies heavily on the bifunctional chiral auxiliaries empolyed. Recently, we developed a novel camphor-derived 2,3-diols named CAMDOL from camphorquinone in high yields by a column-free protocol at 50 grams scale. Diverse P(III)- & P(V)-chiral compounds were afforded efficiently in high yields and ee values through this powerful heterobifunctional template. Progress in CAMDOL-enabled synthesis of P-stereogenic compounds can be outlined as following: enantioselective synthesis of key synthons of phosphinous acid boranes and their transformation into structurally diverse phosphinites, phosphines, phosphinates, (secondary) phosphine oxides, phosphi(o)nothioates, and phosphine sulfides; enantioselective synthesis of α-substituted phosphonates via asymmetric P-adjacent α-carbon functionalization including α-alkylation (arylation), α-fluorination, and α-acylation, etc; and enantioselective synthesis of α-hydroxyl and β-nitro phosphonates via intermolecular Pudovik addition (Figure 1).