Pd(II)-Catalyzed Alkylation of Tertiary Carbon via Directing-Group-Mediated C(sp3)-H Activation: Synthesis of Chiral 1,1,2-Trialkyl Substituted Cyclopropanes

被引：44

作者：

Hoshiya, Naoyuki ^{[1
]}

Takenaka, Kei ^{[1
]}

Shuto, Satoshi ^{[2
,3
]}

Uenishi, Jun'ichi ^{[1
]}

机构：

[1] Kyoto Pharmaceut Univ, Dept Pharmaceut Chem, Yamashina Ku, Kyoto 6078412, Japan

[2] Hokkaido Univ, Fac Pharmaceut Sci, Kita Ku, Sapporo, Hokkaido 0600812, Japan

[3] Hokkaido Univ, Ctr Res & Educ Drug Discovery, Kita Ku, Sapporo, Hokkaido 0600812, Japan

来源：

ORGANIC LETTERS | 2016年 / 18卷 / 01期

基金：

日本学术振兴会;

关键词：

CONFORMATIONALLY RESTRICTED ANALOGS; PALLADIUM-CATALYZED ARYLATION; C-H ACTIVATION; BIOLOGICAL-ACTIVITY; NATURAL-PRODUCTS; PROTEASOME INHIBITORS; HYDROGEN BONDS; RECEPTOR; FUNCTIONALIZATION; AUXILIARY;

D O I：

10.1021/acs.orglett.5b03229

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

A Pd(OAc)(2)-catalyzed alkylation reaction of the tertiary carbon of chiral cydopropane substrates with alkyl iodides and bromides via C(sp(3))-H activation has been developed. This is an elusive example of a C-H activation-mediated alkylation of tertiary carbon to effectively construct a quaternary carbon center. The alkylation proceeded with various alkyl halides, including those of functional groups, to provide a variety of chiral cis- and trans-1,1,2,-trialkyl substituted cydopropanes of medicinal chemical importance.

引用

页码：48 / 51

页数：4

共 41 条

[1] Carboxylate-Assisted Transition-Metal-Catalyzed C-H Bond Functionalizations: Mechanism and Scope [J].

Ackermann, Lutz .

CHEMICAL REVIEWS, 2011, 111 (03) :1315-1345

[2] Palladium(II)-Catalyzed Highly Enantioselective C-H Arylation of Cyclopropylmethylamines [J].

Chan, Kelvin S. L. ;

Fu, Hai-Yan ;

Yu, Jin-Quan .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2015, 137 (05) :2042-2046

[3] C-H Activation: A Complementary Tool in the Total Synthesis of Complex Natural Products [J].

Chen, David Y. -K. ;

Youn, So Won .

CHEMISTRY-A EUROPEAN JOURNAL, 2012, 18 (31) :9452-9474

[4] Recent advances in the total synthesis of cyclopropane-containing natural products [J].

Chen, David Y. -K. ;

Pouwer, Rebecca H. ;

Richard, Jean-Alexandre .

CHEMICAL SOCIETY REVIEWS, 2012, 41 (13) :4631-4642

[5] 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

[6] 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

[7] The Mechanism of a Ligand-Promoted C(sp3)-H Activation and Arylation Reaction via Palladium Catalysis: Theoretical Demonstration of a Pd(II)/Pd(IV) Redox Manifold [J].

Dang, Yanfeng ;

Qu, Shuanglin ;

Nelson, John W. ;

Pham, Hai D. ;

Wang, Zhi-Xiang ;

Wang, Xiaotai .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2015, 137 (05) :2006-2014

[8] Bidentate, Monoanionic Auxiliary-Directed Functionalization of Carbon-Hydrogen Bonds [J].

Daugulis, Olafs ;

Roane, James ;

Tran, Ly Dieu .

ACCOUNTS OF CHEMICAL RESEARCH, 2015, 48 (04) :1053-1064

[9] Development of a Palladium-Catalyzed α-Arylation of Cyclopropyl Nitriles [J].

Dunn, Jamie M. McCabe ;

Kuethe, Jeffrey T. ;

Orr, Robert K. ;

Tudge, Matthew ;

Campeau, Louis-Charles .

ORGANIC LETTERS, 2014, 16 (24) :6314-6317

[10] Palladium-Catalyzed Arylation of Cyclopropanes via Directing Group-Mediated C(sp3)-H Bond Activation To Construct Quaternary Carbon Centers: Synthesis of cis- and trans-1,1,2-Trisubstituted Chiral Cyclopropanes [J].

Hoshiya, Naoyuki ;

Kobayashi, Takaaki ;

Arisawa, Mitsuhiro ;

Shuto, Satoshi .

ORGANIC LETTERS, 2013, 15 (24) :6202-6205

← 1 2 3 4 5 →