Iridium-Catalyzed, Intermolecular Hydroetherification of Unactivated Aliphatic Alkenes with Phenols

Abstract

Metal-catalyzed addition of an O−H bond to an alkene is a desirable process because it allows for rapid access to ethers from abundant starting materials without the formation of waste, without rearrangements, and with the possibility to control the stereoselectivity. We report the intermolecular, metal-catalyzed addition of phenols to unactivated α-olefins. Mechanistic studies of this rare catalytic reaction revealed a dynamic mixture of resting states that undergo O−H bond oxidative addition and subsequent olefin insertion to form ether products.

A multitasking functional group leads to structural diversity using designer C–H activation reaction cascades

“…of H 2 was observed. Presumably, a phenoxylation catalysed by silver is followed by a rapid dehydrogenative cyclization [20][21][22][23] . Detailed mechanistic aspects are currently under investigation (Fig.…”

Asymmetric Synthesis of Ethers by Catalytic Alkene Hydro­alkoxy­lation

“…29 In 2013, Hartwig's group reported the intermolecular hydroetherification of non-activated aliphatic alkenes with phenols catalyzed by an iridium complex of (S)-DTBM-SEGPHOS 36 (Scheme 11). 30 The mechanism is believed to proceed via oxidative addition of the phenol O-H bond to the Ir(I)-phosphine complex, insertion of the olefin into the Ir-O bond, and reductive elimination to release ether products 48.…”

Stereoselective Synthesis of (Z)-Allyl Alcohols through Coinage-Metal-Catalyzed Nucleophilic Addition of Benzo[d]isoxazoles with Unactivated Propargyl Alcohols

“…10 Hartwig et al developed the iridium-catalyzed intermolecular hydroetherification of unactivated aliphatic alkenes with phenols, to prepare a wide range of ethers. 11 Recently, Zi reported a gold(I)-catalyzed enantioselective hydroetherification of prochiral phenols with Pstereogenic centers, affording P-chiral cyclic phosphine oxides in good yields with high enantioselectivities. 12 Given the critical importance of the allyl alcohols in synthetic organic chemistry, we envisioned that a catalytic nucleophilic addition of the O-H bond to unactivated propargyl alcohols should serve as a rapid avenue to prepare allylic alcohols without the formation of any chemical waste.…”