Transition-Metal-Catalyzed Suzuki–Miyaura-Type Cross-Coupling Reactions of π-Activated Alcohols

Abstract

The Suzuki–Miyaura reaction is one of the most powerful tools for the formation of carbon–carbon bonds in organic synthesis. The utilization of alcohols in this powerful reaction is a challenging task. This short review covers progress in the transition-metal-catalyzed Suzuki­–Miyaura-type cross-coupling reaction of π-activated alcohol, such as aryl, benzylic, allylic, propargylic and allenic alcohols, between 2000 and June 2019.1 Introduction2 Suzuki–Miyaura Cross-Coupling Reactions of Aryl Alcohols2.1 One-Pot Reactions with Pre-activation of the C–O Bond2.1.1 Palladium Catalysis2.1.2 Nickel Catalysis2.2 Direct Activation of the C–O Bond2.2.1 Nickel Catalysis3 Suzuki–Miyaura-Type Cross-Coupling Reactions of Benzylic Alcohols4 Suzuki–Miyaura-Type Cross-Coupling Reactions of Allylic Alcohols4.1 Rhodium Catalysis4.2 Palladium Catalysis4.3 Nickel Catalysis4.4 Stereospecific Reactions4.5 Stereoselective Reactions4.6 Domino Reactions5 Suzuki–Miyaura-Type Cross-Coupling Reactions of Propargylic Alcohols5.1 Palladium Catalysis5.2 Rhodium Catalysis6 Suzuki–Miyaura-Type Cross-Coupling Reactions of Allenic Alcohols6.1 Palladium Catalysis6.2 Rhodium Catalysis7 Conclusions

Electrochemically Enabled, Nickel-Catalyzed Dehydroxylative Cross-Coupling of Alcohols with Aryl Halides

“…The ubiquity of alcohols across most classes of molecules makes them attractive as potential C­(sp 3 ) coupling partners. However, on account of the relatively strong bond dissociation energy of the C–O bond and low leaving ability of the OH – group, alcohols are seldom directly employed as alkylating agents in cross-couplings, − with a notable exception being π-activated allylic and benzylic alcohols. − Although many alcohol derivatives have been wildly studied in reductive cross-coupling reactions, including alkyl acetates, , tosylates, − xanthate esters, mesylates, pivalates, oxalates, − phosphates, methyl ethers, and chloroformates (Figure A, right), such derivatives require preparation step(s) from their alcohol precursors, and the substrate scope is often limited to allylic and benzylic alcohol derivatives. Therefore, it would be synthetically appealing to develop a reaction which can directly harness free alcohols to construct C­(sp 2 )–C­(sp 3 ) bonds, ideally supporting both π-activated alcohols and alkyl alcohols as starting materials.…”

Reductive Deoxygenative Functionalization of Alcohols by First‐Row Transition Metal Catalysis

“…These protocols typically involve the Friedel–Crafts (FC) alkylation reaction catalyzed by Lewis acidic metals, [ 3 ] the hydrogen borrowing (HB) strategy for the alkylation of classic nucleophiles such as activated methylene compounds, [ 4 ] and the cross‐coupling reactions of activated alcohols and organometallic species. [ 5 ] Progress in this field offers invaluable methods for installing aliphatic fragments into nucleophilic architectures.…”

Fe3O4 supported [Cu(ii)(met)(pro-H)2] complex as a novel nanomagnetic catalytic system for room temperature C–O coupling reactions

“…Regarding the use of aryl halide-phenol cross-coupling technique, highly functionalized diaryl ethers may be produced in a more straightforward and time-efficient manner. [17][18][19] Diaryl ethers have a variety of applications, i.e. in producing novel materials with improved functionalities, synthesis, and creating new medications.…”