Copper-Catalyzed Trifluoromethylation-Initiated Radical 1,2-Aryl Migration in ,-Diaryl Allylic Alcohols

被引：276

作者：

Liu, Xiaowu ^{[1
]}

Xiong, Fei ^{[1
]}

Huang, Xuanping ^{[1
]}

Xu, Liang ^{[2
]}

Li, Pengfei ^{[2
]}

Wu, Xiaoxing ^{[1
]}

机构：

[1] Chinese Acad Sci, Guangzhou Inst Biomed & Hlth, Guangzhou 510530, Guangdong, Peoples R China

[2] Xi An Jiao Tong Univ, Ctr Organ Chem, Frontier Inst Sci & Technol FIST, Xian 710054, Shaanxi, Peoples R China

来源：

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION | 2013年 / 52卷 / 27期

基金：

美国国家科学基金会;

关键词：

copper; migration; radical reactions; rearrangement; trifluoromethylation; ENANTIOSELECTIVE ALPHA-TRIFLUOROMETHYLATION; PD(II)-CATALYZED ORTHO-TRIFLUOROMETHYLATION; NUCLEOPHILIC TRIFLUOROMETHYLATION; MEDIATED TRIFLUOROMETHYLATION; ELECTROPHILIC TRIFLUOROMETHYLATION; OXIDATIVE TRIFLUOROMETHYLATION; CARBONYL-COMPOUNDS; IPSO-SUBSTITUTION; ROOM-TEMPERATURE; BORONIC ACIDS;

D O I：

10.1002/anie.201302673

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Not only symmetrical, but also unsymmetrical α,α-diaryl allylic alcohols are employed as substrates in the title reaction. A number of arenes and even heteroarenes underwent radical 1,2-aryl migration ("neophyl rearrangement") to produce α-aryl β-trifluoromethyl ketones. The preferential migration of electron-deficient aryl groups over electron-rich ones in unsymmetrical substrates supports the radical mechanism, which was further confirmed by DFT calculations. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

引用

页码：6962 / 6966

页数：5

共 111 条

[31] Copper-Mediated Oxidative Trifluoromethylation of Boronic Acids
Chu, Lingling
Qing, Feng-Ling
[J]. ORGANIC LETTERS, 2010, 12 (21) : 5060 - 5063
[32] BETA-IODO KETONES BY PREVOST REACTION OF VINYL CARBINOLS
CIGANEK, E
CALABRESE, JC
[J]. JOURNAL OF ORGANIC CHEMISTRY, 1995, 60 (14) : 4439 - 4443
[33] Highly Enantioselective Copper-Catalyzed Electrophilic Trifluoromethylation of β-Ketoesters
Deng, Qing-Hai
Wadepohl, Hubert
Gade, Lutz H.
[J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2012, 134 (26) : 10769 - 10772
[34] Egami H., 2013, ANGEW CHEM, V125, P4092
[35] Egami H., 2013, ANGEW CHEM INT ED, V52, P4000
[36] Oxytrifluoromethylation of multiple bonds using copper catalyst under mild conditions
Egami, Hiromichi
Shimizu, Ryo
Sodeoka, Mikiko
[J]. TETRAHEDRON LETTERS, 2012, 53 (41) : 5503 - 5506
[37] Novel 10-I-3 hypervalent iodine-based compounds for electrophilic trifluoromethylation
Eisenberger, P
Gischig, S
Togni, A
[J]. CHEMISTRY-A EUROPEAN JOURNAL, 2006, 12 (09) : 2579 - 2586
[38] Copper-catalyzed olefinic trifluoromethylation of enamides at room temperature
Feng, Chao
Loh, Teck-Peng
[J]. CHEMICAL SCIENCE, 2012, 3 (12) : 3458 - 3462
[39] Catalysis for fluorination and trifluoromethylation
Furuya, Takeru
Kamlet, Adam S.
Ritter, Tobias
[J]. NATURE, 2011, 473 (7348) : 470 - 477
[40] Medium ring synthesis by radical ipso-substitution
Harrowven, DC
L'Helias, N
Moseley, JD
Blumire, NJ
Flanagan, SR
[J]. CHEMICAL COMMUNICATIONS, 2003, (21) : 2658 - 2659

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