Chiral BINOL-derived phosphoric acids: privileged Brønsted acid organocatalysts for C–C bond formation reactions

Abstract

BINOL-derived phosphoric acids have emerged during the last five years as powerful chiral Brønsted acid catalysts in many enantioselective processes. The most successful transformations carried out with chiral BINOL phosphates include C-C bond formation reactions. The recent advances have been reviewed in this article with a focus being placed on hydrocyanations, aldol-type, Mannich, Friedel-Crafts, aza-ene-type, Diels-Alder, as well as cascade and multi-component reactions.

A Practical, One‐Pot Multicomponent Synthesis of α‐Amidosulfides and Their Application as Latent N‐Acylimines in the Friedel–Crafts Reaction

“…[21a, [23][24][25] After a survey of reaction parameters, solvents, and temperatures, the optimized conditions consist of performing the alkylation of 10 in CH 2 Cl 2 in the presence of phosphoric acid 12 (20 mol-%). As shown in Table 3, α-amidosulfides 4a-l and 4o, whether linear or α-branched, effectively participate in this reaction, leading to 2-indolylmethanamines 11 in good yields.…”

2.07 The Aldol Reaction: Organocatalysis Approach

“…In general, the activation of the substrate is enabled through hydrogen bonding or formation of ion pairs, depending on the acidic strength of the catalyst such as phosphoric acids, [188][189][190][191][192][193][194][195] ammonium salts, thioureas, 196 diols, 197 and squaramides. 198 Among the different chiral Brønsted acids (Figure 15), axial chiral phosphoric acid derivatives have shown astonishing versatility.…”

A Protecting‐Group‐Free Route to Chiral BINOL–Phosphoric Acids

“…Pioneering research by Akiyama [1] and Terada [2] have introduced 3,3Ј-disubstituted BNPHs as chiral Brønsted acid organocatalysts that mediate a spectacularly wide spectrum of carbon-carbon bond-forming reactions. [3] A wide variety of 3,3Ј-disubstituted BNPH derivatives has been designed and synthesized for the catalysis of a range of reactions.…”