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

被引：132

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

收藏

页码：10950 / 10953

页数：4

相关论文

共 68 条

[1] Metal-catalyzed direct alkylations of (hetero)arenes via C-H bond cleavages with unactivated alkyl halides [J].

Ackermann, Lutz .

CHEMICAL COMMUNICATIONS, 2010, 46 (27) :4866-4877

[2] Ruthenium-Catalyzed Regioselective Direct Alkylation of Arenes with Unactivated Alkyl Halides through C-H Bond Cleavage [J].

Ackermann, Lutz ;

Novak, Petr ;

Vicente, Ruben ;

Hofmann, Nora .

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 [J].

Aihara, Yoshinori ;

Chatani, Naoto .

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 [J].

Aspin, Sam ;

Lopez-Suarez, Laura ;

Larini, Paolo ;

Goutierre, Anne-Sophie ;

Jazzar, Rodolphe ;

Baudoin, Olivier .

ORGANIC LETTERS, 2013, 15 (19) :5056-5059

[5] New catalytic approaches in the stereoselective Friedel-Crafts alkylation reaction [J].

Bandini, M ;

Melloni, A ;

Umani-Ronchi, A .

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2004, 43 (05) :550-556

[6] π-Activated alcohols: an emerging class of alkylating agents for catalytic Friedel-Crafts reactions [J].

Bandini, Marco ;

Tragni, Michele .

ORGANIC & BIOMOLECULAR CHEMISTRY, 2009, 7 (08) :1501-1507

[7] An Enantioselective Approach toward 3,4-Dihydroisocoumarin through the Bromocyclization of Styrene-type Carboxylic Acids [J].

Chen, Jie ;

Zhou, Ling ;

Tan, Chong Kiat ;

Yeung, Ying-Yeung .

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 [J].

Chen, Kai ;

Shi, Bing-Feng .

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 [J].

Chen, Kai ;

Hu, Fang ;

Zhang, Shuo-Qing ;

Shi, Bing-Feng .

CHEMICAL SCIENCE, 2013, 4 (10) :3906-3911

[10] Cobalt-Catalyzed ortho-Alkylation of Secondary Benzamide with Alkyl Chloride through Directed C-H Bond Activation [J].

Chen, Quan ;

Ilies, Laurean ;

Nakamura, Eiichi .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2011, 133 (03) :428-429

← 1 2 3 4 5 6 7 →