C3-symmetric trialkyl phosphites as starting compounds of asymmetric synthesis

The difference in reactivity of (−)-mono and dimenthyl vs. diethyl alkylphosphonates in the α-lithiation reaction: Carbanionic synthesis of unknown (−)-dimenthyl 1-iodoalkylphosphonates and their first use in the radical iodine atom transfer addition (I-ATRA) and cyclisation (I-ATRC) reactions

“…(À)-Dimenthyl phosphite as well as its sodium and ethylzinc salts were added by Kolodyazhnyi [6,7] to chiral C@N and C@C compounds as an example of efficient multistereoselectivity. The addition of (À)-trimenthyl phosphite to nitrostyrene led to formation of optically active b-nitroalkylphosphonates [7], while addition to C@N bond gave (À)-dimenthyl a-aminoalkylphosphonates [8]. The condensation with aldehydes [8] afforded (À)-dimenthyl a-hydroxyalkylphosphonates and with phenacylchloride gave (À)-dimenthyl a-ketophophonates [8].…”

Double Asymmetric Induction During Addition of Chiral Phosphites to C=N Bond

“…1,2 We found also that di-and trialkylphosphites 1,2 furnish the aminosphosphonic acids with antipodal configuration. 3 Configurations of new stereogenic centers were determined by chemical methods, NMR and, in some cases X-ray analysis.…”

Enantioselective conjugate addition of dialkyl phosphites to nitroalkenes

“…The early asymmetric approaches relied primarily on substrate controlled diastereoselective additions. 3 Recent auxiliary approaches to the synthesis of β-nitrophosphonates include addition of menthol derived 5 and TADDOL derived 6 phosphites to nitroalkenes. Recent catalytic approaches involved Mannich reaction, …”