Recent advances in oxidative phenol coupling for the total synthesis of natural products

Carson, Matthew C.; Kozlowski, Marisa C.

doi:10.1039/d3np00009e

Cited by 26 publications

(9 citation statements)

References 174 publications

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“…More importantly, the crystal structures of DmlH and the DmlH– 7 complex unveil the first comprehensive observation of the binding mode of macrocyclic peptides recognized by CYPs that catalyze phenol coupling reactions. The substrate conformation captured in this study is the first structural clue for reasonably explaining the regioselectivity of the CYP-catalyzed phenol coupling process, which is a great challenge in oxidative phenol coupling for the total synthesis of natural products . The computational studies reveal a water-mediated diradical mechanism for the C–O phenol coupling, which might be generally applied in CYP-catalyzed phenol coupling reactions.…”

Section: Discussionmentioning

confidence: 88%

Discovery and Biosynthesis of Cihanmycins Reveal Cytochrome P450-Catalyzed Intramolecular C–O Phenol Coupling Reactions

Fang,

Zhang,

Wang

et al. 2024

J. Am. Chem. Soc.

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Cinnamoyl-containing nonribosomal peptides (CCNPs) constitute a unique family of natural products. The enzyme mechanism for the biaryl phenol coupling reaction of the bicyclic CCNPs remains unclear. Herein, we report the discovery of two new arabinofuranosylated bicyclic CCNPs cihanmycins (CHMs) A (1) and B (2) from Amycolatopsis cihanbeyliensis DSM 45679 and the identification of the CHM biosynthetic gene cluster (cih BGC) by heterologous expression in Streptomyces lividans SBT18 to afford CHMs C (3) and D (4). The structure of 1 was confirmed by X-ray diffraction analysis. Three cytochrome P450 enzyme (CYP)-encoding genes cih26, cih32, and cih33 were individually inactivated in the heterologous host to produce CHMs E (5), F (6), and G (7), respectively. The structures of 5 and 6 indicated that Cih26 was responsible for the hydroxylation and epoxidation of the cinnamoyl moiety, and Cih32 should catalyze the β-hydroxylation of three amino acid residues. Cih33 and its homologues DmlH and EpcH were biochemically verified to convert CHM G (7) with a monocyclic structure to a bicyclic skeleton of CHM C (3) through an intramolecular C−O phenol coupling reaction. The substrate 7-bound crystal structure of DmlH not only established the structure of 7, which was difficult for NMR analysis for displaying anomalous splitting signals, but also provided the binding mode of macrocyclic peptides recognized by these intramolecular C−O coupling CYPs. In addition, computational studies revealed a water-mediated diradical mechanism for the C− O phenol coupling reaction. These findings have shed important mechanistic insights into the CYP-catalyzed phenol coupling reactions.

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Section: Discussionmentioning

confidence: 88%

Discovery and Biosynthesis of Cihanmycins Reveal Cytochrome P450-Catalyzed Intramolecular C–O Phenol Coupling Reactions

Fang,

Zhang,

Wang

et al. 2024

J. Am. Chem. Soc.

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“…Traditionally, the coupling of two electron-rich (hetero)arenes can be achieved in the presence of a Lewis acid. − Nevertheless, these conventional synthetic methods encounter challenges associated with strict electronic property requirements and relatively modest regio- and chemoselectivity (dimerization versus oligomerization). In comparison, non-chelation-assisted transition-metal-catalyzed oxidative Ar–H/Ar–H coupling reactions are less dependent on the electron-rich characteristics of substrates and display improved selectivity.…”

Section: Synthetic Strategies Toward Bi(hetero)aryls and Fused (Heter...mentioning

confidence: 99%

Discovery of Organic Optoelectronic Materials Powered by Oxidative Ar–H/Ar–H Coupling

Yang,

Wu,

Bin

et al. 2024

J. Am. Chem. Soc.

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Efficient and streamlined synthetic methods that facilitate the rapid build-up of structurally diverse π-conjugated systems are of paramount importance in the quest for organic optoelectronic materials. Among these methods, transition-metalcatalyzed oxidative Ar−H/Ar−H coupling reactions between two (hetero)arenes have emerged as a concise and effective approach for generating a wide array of bi(hetero)aryl and fused heteroaryl structures. This innovative approach bypasses challenges associated with substrate pre-activation processes, thereby allowing for the creation of frameworks that were previously beyond reach using conventional Ar−X/Ar−M coupling reactions. These inherent advantages have ushered in new design patterns for organic optoelectronic molecules that deviate from traditional methods. This ground-breaking approach enables the transcendence of the limitations of repetitive material structures, ultimately leading to the discovery of novel high-performance materials. In this Perspective, we provide an overview of recent advances in the development of organic optoelectronic materials through the utilization of transition-metal-catalyzed oxidative Ar−H/Ar−H coupling reactions. We introduce several notable synthetic strategies in this domain, covering both directed and non-directed oxidative Ar−H/Ar−H coupling strategies, dual chelation-assisted strategy and directed ortho-C−H arylation/cyclization strategy. Additionally, we shed light on the role of oxidative Ar−H/Ar−H coupling reactions in the advancement of high-performance organic optoelectronic materials. Finally, we discuss the current limitations of existing protocols and offer insights into the future prospects for this field.

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“…In 2019, our group reported a pioneering study where Cs 3 Bi 2 Br 9 nanoparticles were demonstrated to catalyze the ring-opening alcoholysis reactions of epoxides under visible light. [20] Additionally, we showed that SBA-15 silica-supported Cs 3 Bi 2 Br 9 could effectively interact with toluene, leading to the subsequent activation of C(sp 3 )À H bonds on Bi 3 + acidic sites facilitated by Br anion. [21] Despite these advancements, challenges such as limited accessibility of active sites, light adsorption capability, and rapid charge recombination still need to be addressed to enhance their photocatalytic activity.…”

Section: Introductionmentioning

confidence: 99%

“…Nature abounds with instances where electron-rich aromatic moieties, especially phenols and their derivatives, serve as key precursors for various biphenyl products. [1][2][3] Plant extracts containing phenolic compounds have demonstrated various biological functions including antibacterial, antifungal, and antimicrobial activities. [4] The transformative process, involving the selective oxidative coupling of phenols and the formation of carbon-carbon (CÀ C) and carbon-oxygen (CÀ O) bonds, represents a pivotal step in the synthetic pathways of natural products.…”

Section: Introductionmentioning

confidence: 99%

Solar‐Light‐Driven Photocatalytic Oxidative Coupling of Phenol Derivatives over Bismuth‐Based Porous Metal Halide Perovskites

Lee,

Kumar,

Tüysüz

2024

Angewandte Chemie

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The selective oxidative coupling of phenol derivatives, involving carbon‐carbon (C‐C) and carbon‐oxygen (C‐O) bond formation, has emerged as a critical approach in the synthesis of natural products. However, achieving precise control over the selectivity in coupling reactions of unsubstituted phenols utilizing solar light as the driving force remains a big challenge. In this study, we report a series of porous Cs3Bi2X9 (X = Cl, Br, I) photocatalysts with tailored bandgaps and compositions engineered for efficient solar‐light‐driven oxidative phenol coupling. Notably, p‐Cs3Bi2Br9 exhibited about 73 % selectivity for C‐C coupling, displaying a high formation rate of 47.3 μmol gcat.−1 h‑1 under solar radiation. Furthermore, this approach enables control of the site‐selectivity for phenol derivatives on Cs3Bi2X9, enhancing C‐C coupling. The distinctive porous structure and appropriate band‐edge positions of Cs3Bi2Br9 facilitated efficient charge separation, and surface interaction/activation of phenolic hydroxyl groups, resulting in the kinetically preferred formation of C‐C over C‐O bond. Mechanistic insights into the reaction pathway, supported by comprehensive control experiments, unveiled the crucial role of interfacial charge transfers and Lewis acid Bi sites in stabilizing phenolic intermediates, thereby directing the regioselectivity of diradical couplings and resulting in the formation of unsymmetrical biphenols.

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Recent advances in oxidative phenol coupling for the total synthesis of natural products

Abstract: This review highlights modern uses of oxidative phenol coupling in the total synthesis of natural products, spanning catalytic, electrochemical, stoichiometric and enzymatic approaches.

Cited by 26 publications

References 174 publications

Discovery and Biosynthesis of Cihanmycins Reveal Cytochrome P450-Catalyzed Intramolecular C–O Phenol Coupling Reactions

Discovery and Biosynthesis of Cihanmycins Reveal Cytochrome P450-Catalyzed Intramolecular C–O Phenol Coupling Reactions

Discovery of Organic Optoelectronic Materials Powered by Oxidative Ar–H/Ar–H Coupling

Solar‐Light‐Driven Photocatalytic Oxidative Coupling of Phenol Derivatives over Bismuth‐Based Porous Metal Halide Perovskites

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