P,S-Bidentate Phosphoramidites with (R_a)-BINOL Core in Palladium-Catalyzed Asymmetric Allylic Substitution

K. N. Gavrilov^a^,* (https://orcid.org/0000-0003-3158-3790), I. V. Chuchelkin (https://orcid.org/0000-0002-3656-468X), V. M. Trunina^a, I. D. Firsin^a (https://orcid.org/0000-0003-3002-2334), Y. P. Bityak^b, D. A. Fedorov^b, V. S. Zimarev^{a, c}, and N. S. Goulioukina^{a, c, d} (https://orcid.org/0000-0002-3823-3999)

^aRyazan State University named for S. Yesenin, Ryazan, 390000 Russia

^bMoscow Institute of Physics and Technology, Dolgoprudny, 141700 Russia

^cLomonosov Moscow State University, Moscow, 119991 Russia

^dA.N. Frumkin Institute of Physical Chemistry and Electrochemistry, Russian Academy of Sciences, Moscow, 119071 Russia

email: *k.gavrilov@365.rsu.edu.ru

Received 4 October, 2022

Abstract— New P,S-bidentate phosphoramidite ligands, including these having a stereogenic phosphorus atom in the 1,3,2-dioxaphosphepine ring, have been synthesized on the basis of (R_a)-BINOL and its adamantanyl derivatives. With their participation in the Pd-catalyzed asymmetric allylic alkylation of (E)-1,3-diphenylallyl acetate with dimethyl malonate and the amination with pyrrolidine involving these ligands have afforded selectivity up to 84 and 75% ee, respectively.

Keywords: chiral phosphoramidites, P,S-bidentate ligands, asymmetric allylation, palladium catalysis

DOI: 10.1134/S1070363222120088

P,S-Bidentate Phosphoramidites with (Ra)-BINOL Core in Palladium-Catalyzed Asymmetric Allylic Substitution

P,S-Bidentate Phosphoramidites with (R_a)-BINOL Core in Palladium-Catalyzed Asymmetric Allylic Substitution