Application of Hydroxyporphyrins-based Phosphite-type Ligands to Asymmetric Pd-Catalyzed Allylic Substitution Reactions

Abstract

Diamidophosphite and phosphite ligands with (S)-2-(anilinomethyl)pyrrolidine or (S a)

First Tetradentate Diamidophosphite Based on [5,10,15,20-Tetrakis(4-hydroxyphenyl)porphyrinato]zinc: Synthesis, Spectral Features, Coordination, and Application in Asymmetric Pd-Catalyzed Reactions

“…In order to clarify the photophysical properties of the new tetradentate diamidophosphite 2 and the previ-ously reported [44,42] 1 and 5-7 (Figure 3), electronic absorption (EAS) and fluorescence spectra were recorded. EAS of free base porphyrins contain four Q absorption bands corresponding to the split electronic transitions S0-S1 (Table 1).…”

“…[22][23][24][25][26][27][28][29][30][31][32][33][34][35][36][37] We have previously reported the preparation of a series of chiral ligands -phosphorous acid derivatives, which were successfully applied in Pd-catalyzed allyl substitution reactions. [38][39][40][41][42][43] In those cases, porphyrins were used both as achiral additives [38][39][40][41] to increase enantioselectivity, and as starting substrates for phosphorylation. [42][43][44] In a preliminary communication, [44] we reported the synthesis of the first tetradentate diamidophosphite 1 (Figure 1) and its application in asymmetric Pd-catalyzed alkylation of cinnamyl acetate.…”

“…[38][39][40][41][42][43] In those cases, porphyrins were used both as achiral additives [38][39][40][41] to increase enantioselectivity, and as starting substrates for phosphorylation. [42][43][44] In a preliminary communication, [44] we reported the synthesis of the first tetradentate diamidophosphite 1 (Figure 1) and its application in asymmetric Pd-catalyzed alkylation of cinnamyl acetate. This work is devoted to the synthesis of zinc-containing tetradentate diamidophosphite 2, its complexation with [Ru(p-cymene)Cl 2 ] 2 , as well as the study of the photophysical properties of ligands 1 and 2 and their application in a number of asymmetric Pd-catalyzed processes.…”

“…[45] 5,10,15,20-Tetrakis( 4 (7) were synthesized according to literature procedures. [44,42] The [Pd(allyl)Cl] 2 and (E)-1,3-diphenylallyl acetate (8) were obtained as published. [46] [Ru(pcymene)Cl 2 ] 2 , dimethyl malonate, BSA (N,O-bis(trimethylsilyl) acetamide), cinnamyl acetate ( 9) and ethyl 2-oxocyclohexane-1-carboxylate (10) were purchased from Aldrich and Acros Organics and used without further purification.…”