We report the first stereoselective synthesis of (2R,3aR,7aR)‐ and (2S,3aS,7aS)‐octahydroindole‐2‐phosphonic acid 2 (OicP derivatives). The key points are the highly diastereoselective synthesis of cis‐fused bicyclic (3aR,7aR)‐ and (3aS,7aS)‐pyrrolidin‐2‐ones 4 through a dynamic kinetic resolution of racemic γ‐keto acid (±)‐5 with (R)‐ and (S)‐phenylglycinol via Meyers' bicyclic lactams, and the highly diastereoselective addition of trimethyl phosphite to the N‐acyliminium ions 3 obtained from 4.

We report here the first diastereoselective synthesis of (2S,5R)-5methyl-5-(phosphono)-proline, a phosphoproline derivative from L-pyroglutamic acid. The main feature of this methodology is the transformation of L-pyroglutamic acid into chiral cyclic imines as a versatile intermediate followed by diastereoselective nucleophilic addition of trialkyl phosphites or diethyl phosphite in the presence of PhB(OH) 2 , Ph 2 P(O)OH, (PhO) 2 P(O)OH, Ph(H)P-(O)OH and TiCl 4 . N-Cbz Cleavage with simultaneous hydrolysis of phosphonate and carboxylate esters in the quaternary cyclic α-aminophosphonate, gave the target compound.