Advances in the Asymmetric Synthesis of BINOL Derivatives

Silva, Everton Machado da; Vidal, Hérika Danielle Almeida; Januario, Marcelo A.P.; Corrêa, Arlene G.

doi:10.3390/molecules28010012

Cited by 19 publications

(14 citation statements)

References 100 publications

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“…Functionalized biaryls with axial chirality such as 1,1'binaphthyl-2,2'-diol (BINOL) and its derivatives are versatile chiral ligands/catalysts widely used in asymmetric synthesis and natural product synthesis, as demonstrated in the landmark compounds such as BINAP, [47,48] phosphoric acids. [49][50][51][52] Synthesis of axially chiral biaryldiols conventionally relied on the approaches of metal-catalyzed asymmetric oxidative cross-coupling reactions and kinetic resolution, [19,[53][54][55] which often focused on the symmetric biaryldiols derivatives. Recent studies have been switched to the preparation of the nonsymmetric counterparts, for which the Friedel-Crafts arylation of quinone and its derivatives represents a versatile approach.…”

Section: Atroposelective Biaryl Formationmentioning

confidence: 99%

Catalytic Synthesis of Atropoisomers via Non‐Canonical Friedel‐Crafts Reactions

Ye,

Yu,

Deng

et al. 2024

Adv Synth Catal

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The Friedel‐Crafts reaction stands as a powerful synthetic tool for C‐H functionalization of aromatic feedstocks, which is conventionally realized through electrophilic alkylation and acylation. The burgeoning interests in axially chiral compounds across diverse fields have spurred extensive exploration of this classic transformation for catalytic atroposelective synthesis. Consequently, the past decade has witnessed the rapid expansion of various non‐canonical Friedel‐Crafts reactions, including electrophilic arylation, alkenylation, halogenation, sulfenylation, and amination of aryl C‐H bonds, thereby delving into new chemical spaces. A range of catalytic atroposelective synthetic methods have been devised for these significant arene C‐H functionalization. This review provides a comprehensive overview of the cutting‐edge catalytic synthesis of atropoisomers through non‐canonical Friedel‐Crafts reactions, categorized into three parts based on the type of bond formation on the aromatics: C(sp2)‐C(sp3) bond formations, C(sp2)‐C(sp2) bond formations and C(sp2)‐heteroatom bond formations. The richness of electrophiles and the modulation of atroposelectivity by diverse chiral organocatalysts, particularly chiral Brønsted acids, are elucidated. We anticipate that the repertoire of asymmetric Friedel‐Crafts reaction will continue to flourish and to be demonstrated in not only scientific researches but also industrial organic synthesis.

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Section: Atroposelective Biaryl Formationmentioning

confidence: 99%

Catalytic Synthesis of Atropoisomers via Non‐Canonical Friedel‐Crafts Reactions

Ye,

Yu,

Deng

et al. 2024

Adv Synth Catal

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“…It represents a unique class of atropisomeric compounds characterized by two naphthol rings connected by a 1,1′-bond with restricted rotation which imparts stable chiral configuration. Many methods have been developed to either resolve the racemic mixture of BINOL into its two enantiomers, − ( R )- and ( S )-BINOL, or directly prepare one of the enantiomers via asymmetric synthesis, − leading to the optically active BINOL.…”

Section: Introductionmentioning

confidence: 99%

Regioselective Substitution of BINOL

2024

Chem. Rev.

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1,1′-Bi-2-naphthol (BINOL) has been extensively used as the chirality source in the fields of molecular recognition, asymmetric synthesis, and materials science. The direct electrophilic substitution at the aromatic rings of the optically active BINOL has been developed as one of the most convenient strategies to structurally modify BINOL for diverse applications. High regioselectivity has been achieved for the reaction of BINOL with electrophiles. Depending upon the reaction conditions and substitution patterns, various functional groups can be introduced to the specific positions, such as the 6-, 5-, 4-, and 3-positions, of BINOL. Ortho-lithiation at the 3-position directed by the functional groups at the 2-position of BINOL have been extensively used to prepare the 3- and 3,3′-substituted BINOLs. The use of transition metal-catalyzed C–H activation has also been explored to functionalize BINOL at the 3-, 4-, 5-, 6-, and 7-positions. These regioselective substitutions of BINOL have allowed the construction of tremendous amount of BINOL derivatives with fascinating structures and properties as reviewed in this article. Examples for the applications of the optically active BINOLs with varying substitutions in asymmetric catalysis, molecular recognition, chiral sensing and materials are also provided.

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“…As a result, plenty of strategies have been devised to synthesize chiral 3,3′-diaryl BINOL derivatives. There are two elegant synthetic protocols that have been utilized to accomplish the synthesis of 3,3′-diaryl BINOLs: (i) oxidative coupling of 3-aryl-2-naphthols and (ii) cross-coupling reactions with binaphthol derivatives (Figure ). The frequently utilized method involves the coupling of either 3,3′-dihalo BINOL with available aryl boronic acids (Figure A) or BINOL-3,3′-diboronic acid with aryl halides (Figure B) using Suzuki-Miyaura cross-coupling reactions for the synthesis of 3,3′-diaryl BINOLs .…”

Section: Introductionmentioning

confidence: 99%

Decarboxylative Iodination and Suzuki-Miyaura Coupling Reactions to Access Chiral 3,3′-Diaryl-1,1′-bi-2-naphthols

Karthick,

Gupta,

Ramanathan

2023

J. Org. Chem.

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An efficient synthesis of the enantiomerically pure 3,3′-bis-arylated BINOLs is accomplished through decarboxylative iodination of the dimethyl ether derivative of BINOL-3,3′-dicarboxylic acid followed by Suzuki-Miyaura coupling using a one-pot protocol. The decarboxylative iodination is effected with the dimethyl ether derivative of BINOL-3,3′-dicarboxylic acid using iodine as a terminal oxidant and the cheaply available K 3 PO 4 as a base under neat conditions. This protocol facilitated the introduction of the aryl group at the 3,3′-position on the binaphthyl system using aryl boronic acid through a palladium-catalyzed Suzuki-Miyaura coupling reaction.

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Advances in the Asymmetric Synthesis of BINOL Derivatives

Cited by 19 publications

References 100 publications

Catalytic Synthesis of Atropoisomers via Non‐Canonical Friedel‐Crafts Reactions

Catalytic Synthesis of Atropoisomers via Non‐Canonical Friedel‐Crafts Reactions

Regioselective Substitution of BINOL

Decarboxylative Iodination and Suzuki-Miyaura Coupling Reactions to Access Chiral 3,3′-Diaryl-1,1′-bi-2-naphthols

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