Transition-metal-catalyzed synthesis of phenols and aryl thiols

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.

Domino Reactions Initiated by Copper‐Catalyzed Aryl‐I Bond Thiolation For the Switchable Synthesis of 2,3‐Dihydrobenzothiazinones and Benzoisothiazolones

“…Amazingly, as the simplest, cheapest and most abundant sulfur source, the elemental sulfur has not yet been applied to design such type of domino reactions regardless its widespread application on many other CÀS bond forming reactions [14] and direct thiolation reactions of aryl halides. [15] In this context, developing Ullmann CÀS coupling-based domino reactions using elemental sulfur as the source of sulfur 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 atom is of high merits because of the incomparable atom economy associated with elemental sulfur.…”

“…In these known reports on domino reactions initiated by the Ullmann C−S coupling, various sulfur sources such as thiophenols, sulfide salts, and isothiocyanates etc have been utilized. Amazingly, as the simplest, cheapest and most abundant sulfur source, the elemental sulfur has not yet been applied to design such type of domino reactions regardless its widespread application on many other C−S bond forming reactions and direct thiolation reactions of aryl halides . In this context, developing Ullmann C−S coupling‐based domino reactions using elemental sulfur as the source of sulfur atom is of high merits because of the incomparable atom economy associated with elemental sulfur.…”

Recent Advances in the Synthesis of Sulfides, Sulfoxides and Sulfones via C-S Bond Construction from Non-Halide Substrates

“…The construction of C-S bond is considered as an efficient strategy for the synthesis of sulfur containing compounds. The traditional Ullmann typed reaction, which has been well established in the past several decades, has provided lots of synthetic protocols for diaryl sulfides and aryl alkyl sulfides through transition-metal catalyzed C-S coupling reaction of aryl halides with aryl thiols or other sulfur precursors [9][10][11]. Methodological advancements in C-H functionalization have led to the development of a variety of useful transformations to prepare sulfur containing compounds directly from (hetero)arenes and alkanes [12,13].…”

Copper(II) Catalyzed C–H Alkoxylation of 2‐Phenyl Pyridines with Aliphatic Diols

“…In the past decades, C–H functionalization represents a powerful strategy in the field of organic synthesis . C–H activation/C–O bond coupling reactions have provided various protocols for constructing esters and phenols . It also allows the direct synthesis of aryl alkyl ethers from simple arenes and aliphatic alcohols.…”