Rapid and Direct Photocatalytic C(sp3)-H Acylation and Arylation in Flow

被引：76

作者：

Mazzarella, Daniele ^{[1
]}

Pulcinella, Antonio ^{[1
]}

Bovy, Loic ^{[1
]}

Broersma, Remy ^{[2
]}

Noel, Timothy ^{[1
]}

机构：

[1] Univ Amsterdam, Vant Hoff Inst Mol Sci HIMS, Flow Chem Grp, Sci Pk 904, NL-1098 XH Amsterdam, Netherlands

[2] Signify Res, High Tech Campus 7, NL-5656 AE Eindhoven, Netherlands

来源：

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION | 2021年 / 60卷 / 39期

基金：

欧盟地平线“2020”;

关键词：

acylation; arylation; flow chemistry; hydrogen atom transfer; TBADT; HYDROGEN-ATOM TRANSFER; VISIBLE-LIGHT PHOTOREDOX; C-H BONDS; CATALYSIS; STRATEGY; NICKEL; FUNCTIONALIZATIONS; CHLORINATION; ALKYLATION; ACTIVATION;

D O I：

10.1002/anie.202108987

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Herein, we report a photocatalytic procedure that enables the acylation/arylation of unfunctionalized alkyl derivatives in flow. The method exploits the ability of the decatungstate anion to act as a hydrogen atom abstractor and produce nucleophilic carbon-centered radicals that are intercepted by a nickel catalyst to ultimately forge C(sp(3))-C(sp(2)) bonds. Owing to the intensified conditions in flow, the reaction time can be reduced from 12-48 hours to only 5-15 minutes. Finally, kinetic measurements highlight how the intensified conditions do not change the reaction mechanism but reliably speed up the overall process.

引用

页码：21277 / 21282

页数：6

共 59 条

[1] Direct C-C Bond Formation from Alkanes Using Ni-Photoredox Catalysis [J].

Ackerman, Laura K. G. ;

Alvarado, Jesus I. Martinez ;

Doyle, Abigail G. .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2018, 140 (43) :14059-14063

[2] Amide Synthesis by Nickel/Photoredox-Catalyzed Direct Carbamoylation of (Hetero)Aryl Bromides [J].

Alandini, Nurtalya ;

Buzzetti, Luca ;

Favi, Gianfranco ;

Schulte, Tim ;

Candish, Lisa ;

Collins, Karl D. ;

Melchiorre, Paolo .

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2020, 59 (13) :5248-5253

[3]

[Anonymous], 2020, ANGEW CHEM, V132, P5286

[4]

[Anonymous], 2017, ANGEW CHEM, V129, P7297

[5]

[Anonymous], 2018, ANGEW CHEM, V130, P15890

[6] FREE-RADICAL REACTIONS OF IODOBENZENE DICHLORIDE WITH HYDROCARBONS [J].

BANKS, DF ;

HUYSER, ES ;

KLEINBERG, J .

JOURNAL OF ORGANIC CHEMISTRY, 1964, 29 (12) :3692-&

[7] Continuous Flow Enables Metallaphotoredox Catalysis in a Medicinal Chemistry Setting: Accelerated Optimization and Library Execution of a Reductive Coupling between Benzylic Chlorides and Aryl Bromides [J].

Brill, Zachary G. ;

Ritts, Casey B. ;

Mansoor, Umar Faruk ;

Sciammetta, Nunzio .

ORGANIC LETTERS, 2020, 22 (02) :410-416

[8] Applications of Continuous-Flow Photochemistry in Organic Synthesis, Material Science, and Water Treatment [J].

Cambie, Dario ;

Bottecchia, Cecilia ;

Straathof, Natan J. W. ;

Hessel, Volker ;

Noel, Timothy .

CHEMICAL REVIEWS, 2016, 116 (17) :10276-10341

[9] Photoinduced site-selective alkenylation of alkanes and aldehydes with aryl alkenes [J].

Cao, Hui ;

Kuang, Yulong ;

Shi, Xiangcheng ;

Wong, Koi Lin ;

Tan, Boon Beng ;

Kwan, Jeric Mun Chung ;

Liu, Xiaogang ;

Wu, Jie .

NATURE COMMUNICATIONS, 2020, 11 (01)

[10] Photocatalytic hydrogen atom transfer: the philosopher's stone for late-stage functionalization? [J].

Capaldo, Luca ;

Quadri, Lorenzo Lafayette ;

Ravelli, Davide .

GREEN CHEMISTRY, 2020, 22 (11) :3376-3396

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