Selective Nickel-Catalyzed Hydrodeacetoxylation of Aryl Acetates

被引：9

作者：

De Smet, Gilles ^{[1
]}

Bai, Xingfeng ^{[1
]}

Mensch, Carl ^{[1
]}

Sergeyev, Sergey ^{[1
]}

Evano, Gwilherm ^{[2
]}

Maes, Bert U. W. ^{[1
]}

机构：

[1] Univ Antwerp, Organ Synth Div, Dept Chem, Groenenborgerlaan 171, B-2020 Antwerp, Belgium

[2] Univ Libre Bruxelles ULB, Lab Chim Organ, Serv Chim & PhysicoChim Organ, Ave FD Roosevelt 50,CP160-06, B-1050 Brussels, Belgium

来源：

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION | 2022年 / 61卷 / 38期

关键词：

Aryl Acetates; C-O Bond Activation; Hydrodeacetoxylation; Nickel Catalysis; Renewable Resources; C-O BONDS; REDUCTIVE CLEAVAGE; CROSS-COUPLINGS; NI; ACTIVATION; EFFICIENT; HYDRODEOXYGENATION; ISOPROPANOL; MECHANISM; PROTOCOL;

D O I：

10.1002/anie.202201751

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Acetate serves as a renewable and easily installed leaving group for selective deoxygenation of phenolics (ArOH). Ni-catalyzed hydrodeacetoxylation of aryl acetates (Ar-OAc) with HBpin in a green carbonate solvent selectively delivers the corresponding deoxygenated arenes (ArH). The method is also applicable to highly challenging guaiacyl and syringyl acetates, leaving -OMe groups intact without arene reduction. Renewable 4-propylguaiacol obtained from pine can also be transformed without significant loss in yield versus oil derived feedstock. The observed chemoselectivity for Ar-OAc versus ArO-Ac bond cleavage was rationalized based on mechanistic experiments and DFT calculations. ArOH side-product formation is attributed to direct competitive Ni-catalyzed reduction of the C=O bond. Hydrodeacyloxylation of a set of aryl alkanoates featured interesting chemoselectivity with a dramatic influence of the length and structure of the alkyl chain on catalysis.

引用

页数：10

共 45 条

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