Nickel‐Catalyzed One‐Pot Suzuki–Miyaura Cross‐Coupling of Phenols and Arylboronic Acids Mediated by N,N‐Ditosylaniline

Abstract

An efficient method for the construction of two distinct Caryl–Caryl bonds through the Ni‐catalyzed Suzuki–Miyaura cross‐coupling of phenols with arylboronic acids has been developed. This reaction proceeds through the in situ tosylation of phenols by using N,N‐ditosylaniline as the sulfonylating reagent, which is highly active, markedly stable, and easily prepared. The scope with respect to the coupling partners – phenols and boronic acids – is broad, and sensitive functional groups are tolerated. Phenols, especially those containing an unprotected amino group, which are generally problematic for coupling under conventional one‐pot conditions, are also viable substrates in this transformation.

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

“…The one-pot in situ activation of C-O bonds of phenols with novel N,N-ditosylaniline to generate the corresponding tosylate for the catalytic cross-coupling reaction with arylboronic acid was reported in 2014 by Yu, Wang and coworkers (Scheme 6B). 12 NiCl 2 (dppp) was employed for the C-O bond cleavage of the aryl tosylate (formed in situ). A broad scope of arylboronic acids and phenols were smoothly transformed to furnish biaryls containing chloride, fluoride, cyanide, ether, ester, formyl, acetyl, or even free amine in fair to excellent yields (30-94%).…”

Nickel-Catalyzed One-Pot Deoxygenation and Reductive Homocoupling of Phenols via C–O Activation Using TCT Reagent

“…21 Recently, Chen et al reported an efficient nickel-catalyzed one-pot Suzuki−Miyaura cross-coupling of phenols and arylboronic acids mediated by N,N-ditosylaniline. 22 The one-pot activation strategy possesses important advantages in comparison to a stepwise method. First, the preactivation step limits the efficiency of a two-step protocol in view of overall yields and step economy.…”

“…To use phenolic compounds in coupling reactions, there are two strategies. In the most widely used method (stepwise), phenols are first converted to the corresponding aryl C–O electrophile and then used for the next reaction. − One-pot activation of phenols is another approach for the generation of an active coupling partner in metal-catalyzed cross-coupling reactions. − Bromo-trispyrrolidino phosphonium­hexafluoro­phosphate is the most widely used reagent for one-pot activation of phenolic compounds . In some cases, phenolic salts were used in the one-pot activation process .…”

“…In some cases, phenolic salts were used in the one-pot activation process . Recently, Chen et al reported an efficient nickel-catalyzed one-pot Suzuki–Miyaura cross-coupling of phenols and arylboronic acids mediated by N , N -ditosylaniline . The one-pot activation strategy possesses important advantages in comparison to a stepwise method.…”

“…On the other hand, conversion of some of the phenolic compounds to aryl C–O electrophiles is difficult and has restrictions . For these reasons, the one-pot phenol activation strategy has received more attention recently. − …”