转自：康龙化成

Remote Spin-Center Shift Enables Activation of Distal Benzylic C-O and C-N Bonds

Li-Wen Hui,

[a]

Yee Lin 

Phang

,

[a]

Chen-Yang Ye ,

[a]

Jin-Yu Lai,

[b]

Feng-

Lian

 Zhang,

[a]

Yao Fu,*

[a]

and Yi-Feng Wang*

[a]

[a] State Key Laboratory of Precision and Intelligent Chemistry, Anhui Provincial Key Laboratory of Biomass Chemistry, Department of Chemistry

University of Science and Technology of China 96 Jinzhai Road, Hefei, Anhui 230026, China.; 

[b] Institute of Advanced Technology University of Science and Technology of China 96 Jinzhai Road, Hefei, Anhui 230026, China.

—Angew. Chem. Int. Ed. 2025, 10.1002/anie.202506771.

Recommended by Bingbing Chang_ MC5

KEY WORDS: spin-center shift (SCS), radical chemistry, deoxygenation, deamination (反应类型), C(sp3)-C(sp3) (成键类型), benzylic alcohols, benzylic amines, alkenes(反应物), alkylated products (产物), DMAP-BH3, TBHN, methyl 2-mercaptobenzoate (其他)

ABSTRACT: A spin-center shift (SCS) is a radical process that commonly involves a 1,2-radical shift along with the elimination of an adjacent leaving group by a two-electron ionic movement. The conventional SCS process is largely limited to 1,2-radical translocation, while a remote SCS event involving 1,n-radical translocation over a greater distance to enable distal bond functionalization remains largely underexplored. Herein, Yao Fu et alreport the borylradical-promoted distal deoxygenation and deamination of free benzylic alcohols and simple benzylic amines, respectively, through a remote SCS event. The reaction was initiated by the addition of a 4-dimethylaminopyridine (DMAP)-borylradical to the carbonyl oxygen atom of a benzoate or benzamide. Then, radical translocation took place across the aromatic ring to promote benzylic C-O or C-N bond cleavage. The resulting radical intermediate subsequently coupled with various alkenes to afford a wide range of alkylated products.

Background and this work

Optimization of the reaction conditions

Scope of radical deoxygenative functionalization of free benzylic alcohols (selected examples)

Scope of radical deaminative functionalization of benzylic amines (selected examples)

Proposed Mechanism

Prof. Yi-Feng Wang et al have developed a distinct mode of remote SCS process by employing benzene or furan ring as the effective π-conjugated system for distant radical translocation. Utilizing this unique reaction pathway, they have successfully developed a general radical deoxygenation and deamination of free benzylic alcohols and simple amines. Mechanistic studies supported the formation of benzylic radical through a distant radical shift which travels across the aromatic system before it finally resides at the benzylic position along with the concurrent elimination of the leaving group. They expect that such a remote SCS process would inspire the design of new strategies in synthetic organic chemistry, drug delivery and other advanced fields.

（转自：康龙化成）