康 · 學(xué)術(shù) | Reaction of the Day No. 1670

來源：市場資訊

（來源：康龍化成）

Nickel-Catalyzed One-Pot Deoxygenative Arylation of Benzylic Alcohols with Aryl Electrophiles Using TCT as an Activating Agent

Zhihua Peng,* Xiaoqian Wang, Chuanman Yu, Chuanqi Liu, Zhao Du, Meng Zhou, Wenyu Yang, Yilei Wang, and Zifeng Yan*

Department of Chemistry, College of Chemistry and Chemical Engineering, China University of Petroleum (East China), Qingdao, Shandong 266580, China

— J. Org. Chem., 2026, 91(15), 5316-5333.

Recommended by Shi Li_MOC

KEYWORDS: Ni Catalysis, Deoxygenation, late-stage functionalization (反應(yīng)類型), Benzylic Alcohols, Aryl Electrophiles (原料), Diarylmethanes (產(chǎn)物), C(sp2)-C(sp3) (成鍵類型), Ni(dppf)Cl2/bpp, TCT (2,4,6-trichloro-1,3,5-triazine) (其他)

ABSTRACT: Direct coupling of alcohols remains a challenge in current synthetic chemistry. The authors herein demonstrate a one-pot activation/coupling strategy for C(sp2)-C(sp3) cross-electrophile coupling of alcohols with aryl electrophiles using 2,4,6-trichloro-1,3,5-triazine as an activating agent. The reaction proceeds under mild conditions and tolerates various functionalities, including aldehyde, ketone, ester, lactone, nitrile, pyridine, quinoline, Ar-Bpin, and Ar-SiMe3. Additionally, the electron-rich, electron-poor, and ortho-/meta-/para-substituted aryl electrophiles such as Ar-OTf, Ar-Br, and inert Ar-Cl all coupled well with benzyl alcohols. This one-pot protocol does not require preactivation of alcohols, providing a very robust and powerful alternative to the existing methods for the synthesis of diarylmethanes. The synthetic value of this operationally simple protocol was demonstrated by late-stage functionalization of complex molecules and gram-scale experiments.

Background and this work

Scopes of Benzyl Alcohols

Scopes of Aryl Bromides (selected examples)

Scope of Aryl Chlorides (selected examples)

Scopes of Aryl Triflates

Synthetic Application

Proposed Mechanism

Summary and Comments

Zhihua Peng et al. have demonstrated an efficient and attractive strategy that enables deoxygenative arylation of benzyl alcohols with aryl electrophiles. This one-pot protocol does not require preactivation of alcohols, thus providing a very robust and powerful alternative to the existing methods for the synthesis of diarylmethanes which exist widely in pharmaceuticals and functional organic materials. The developed method exhibits a broad substrate scope and excellent functional group compatibility with aldehydes, ketones, lactones, esters, nitriles, haloarenes, and heteroarenes. The synthetic utility of this method was demonstrated by the modification of biologically active compounds and deoxygenative arylation of naturally allylic alcohols.