Abstract

Phenols and aryl thiols are fundamental building blocks in organic synthesis and final products with interesting biological activities. Over the past decades, substantial progress has been made in transition-metal-catalyzed coupling reactions, which resulted in the emergence of new methods for the synthesis of phenols and aryl thiols. Aryl halides have been extensively studied as substrates for the synthesis of phenols and aryl thiols. In very recent years, C–H activation represents a powerful strategy for the construction of functionalized phenols directly from various arenes. However, the synthesis of aryl thiols through C–H activation has not been reported. In this review, a brief overview is given of the recent advances in synthetic strategies for both phenols and aryl thiols.

Highlights

  • Phenols and aryl thiols serve as both important intermediates in organic synthesis and final products, playing important roles in pharmaceutical molecules, pesticides and polymers in both academia and industry [1,2,3,4]

  • The transition-metal-catalyzed Ullmann-type coupling reaction has emerged as an effective method, allowing the synthesis of phenols and aryl thiols from aryl halides through C–O and C–S bond formation, respectively [5,6,7]

  • Tremendous progress has been made towards the synthesis of phenols and aryl thiols through transition-metalcatalyzed coupling reactions

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Summary

Introduction

Phenols and aryl thiols serve as both important intermediates in organic synthesis and final products, playing important roles in pharmaceutical molecules, pesticides and polymers in both academia and industry [1,2,3,4]. The synthesis of phenols has greatly benefited from C–H activation, but the application in the synthesis of aryl thiols is still yet to be reported. Both phenols and aryl thiols have similar chemical properties, such as acidity and nucleophilicity, and to some extent, the synthetic methods could be developed analogously to each other. In this context, it is valuable to compare their existing synthetic methods for better understanding, so as to inspire organic chemists to invent new methods for the synthesis of Beilstein J. The transition-metal-catalyzed phenol synthesis has several advantages: broad substrate scope, mild reaction conditions, and easy access to starting materials

Transition-metal-catalyzed synthesis of phenols
Palladium-catalyzed hydroxylation of aryl halides
Copper-catalyzed hydroxylation of aryl halides
Palladium-catalyzed C–H hydroxylation of arenes
Pyridine and nitrogen containing functional groups as directing groups
Phenol as directing groups
Ruthenium catalyzed C–H hydroxylation of arenes
Vanadium mediated C–H hydroxylation of arenes
Transition-metal-catalyzed synthesis of aryl thiols
Findings
Conclusion
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