Practical Pd(II)-Catalyzed C-H Alkylation with Epoxides: One-Step Syntheses of 3,4-Dihydroisocoumarins

被引：130

作者：

Cheng, Guolin ^{[1
]}

Li, Tuan-Jie ^{[1
]}

Yu, Jin-Quan ^{[1
]}

机构：

[1] Scripps Res Inst, Dept Chem, La Jolla, CA 92037 USA

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2015年 / 137卷 / 34期

基金：

美国国家科学基金会;

关键词：

PALLADIUM-CATALYZED ALKYLATION; METHYLENE C(SP(3))-H BONDS; ELECTRON-DEFICIENT ARENES; DIRECTED ALKYLATION; BENZOIC-ACIDS; ARYL HALIDES; AMINO-ACIDS; ARYLATION; ACTIVATION; SP(2);

D O I：

10.1021/jacs.5b07507

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Pd(II)-catalyzed ortho-alkylation of benzoic acids with both terminal and internal epoxides affords 3,4-dihydroisocoumarins in one step. The presence of potassium countercations is crucial for this reaction. Monoprotected amino acid ligands significantly promote this reaction, enabling the development of a practical C-H alkylation reaction using 0.5 mol % Pd catalyst. The inversion of stereochemistry in the C-H alkylation step is consistent with a redox-neutral S(N)2 nucleophilic ring-opening process as opposed to a Pd(II)/Pd(IV) pathway.

引用

页码：10950 / 10953

页数：4

共 68 条

[1] Metal-catalyzed direct alkylations of (hetero)arenes via C-H bond cleavages with unactivated alkyl halides
Ackermann, Lutz
[J]. CHEMICAL COMMUNICATIONS, 2010, 46 (27) : 4866 - 4877
[2] Ruthenium-Catalyzed Regioselective Direct Alkylation of Arenes with Unactivated Alkyl Halides through C-H Bond Cleavage
Ackermann, Lutz
Novak, Petr
Vicente, Ruben
Hofmann, Nora
[J]. ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2009, 48 (33) : 6045 - 6048
[3] Nickel-Catalyzed Direct Alkylation of C-H Bonds in Benzamides and Acrylamides with Functionalized Alkyl Halides via Bidentate-Chelation Assistance
Aihara, Yoshinori
Chatani, Naoto
[J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2013, 135 (14) : 5308 - 5311
[4] Palladium-Catalyzed β-Arylation of Silyl Ketene Acetals and Application to the Synthesis of Benzo-Fused δ-Lactones
Aspin, Sam
Lopez-Suarez, Laura
Larini, Paolo
Goutierre, Anne-Sophie
Jazzar, Rodolphe
Baudoin, Olivier
[J]. ORGANIC LETTERS, 2013, 15 (19) : 5056 - 5059
[5] New catalytic approaches in the stereoselective Friedel-Crafts alkylation reaction
Bandini, M
Melloni, A
Umani-Ronchi, A
[J]. ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2004, 43 (05) : 550 - 556
[6] π-Activated alcohols: an emerging class of alkylating agents for catalytic Friedel-Crafts reactions
Bandini, Marco
Tragni, Michele
[J]. ORGANIC & BIOMOLECULAR CHEMISTRY, 2009, 7 (08) : 1501 - 1507
[7] An Enantioselective Approach toward 3,4-Dihydroisocoumarin through the Bromocyclization of Styrene-type Carboxylic Acids
Chen, Jie
Zhou, Ling
Tan, Chong Kiat
Yeung, Ying-Yeung
[J]. JOURNAL OF ORGANIC CHEMISTRY, 2012, 77 (02) : 999 - 1009
[8] Sulfonamide-Promoted Palladium(II)-Catalyzed Alkylation of Unactivated Methylene C(sp3)-H Bonds with Alkyl Iodides
Chen, Kai
Shi, Bing-Feng
[J]. ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2014, 53 (44) : 11950 - 11954
[9] Pd(II)-catalyzed alkylation of unactivated C(sp3)-H bonds: efficient synthesis of optically active unnatural α-amino acids
Chen, Kai
Hu, Fang
Zhang, Shuo-Qing
Shi, Bing-Feng
[J]. CHEMICAL SCIENCE, 2013, 4 (10) : 3906 - 3911
[10] Cobalt-Catalyzed ortho-Alkylation of Secondary Benzamide with Alkyl Chloride through Directed C-H Bond Activation
Chen, Quan
Ilies, Laurean
Nakamura, Eiichi
[J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2011, 133 (03) : 428 - 429

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