Direct Observation of C-H Cyclopalladation at Tertiary Positions Enabled by an Exo-Directing Group

被引：30

作者：

Ren, Zhi ^{[1
]}

Dong, Guangbin ^{[1
]}

机构：

[1] Univ Texas Austin, Dept Chem, Austin, TX 78712 USA

来源：

ORGANOMETALLICS | 2016年 / 35卷 / 08期

关键词：

CATALYZED DIRECT ARYLATION; QUATERNARY CARBON CENTERS; INSERTION REACTIONS; PALLADIUM; BOND; FUNCTIONALIZATION; ACTIVATION; REACTIVITY; CYCLOPROPANES; ME;

D O I：

10.1021/acs.organomet.6b00185

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

Here we describe the first preparation of tertiary alkyl palladium complexes via C-H activation. Enabled by an exo-type oxime directing group, cyclopalladation occurred smoothly at the bridgehead position. Treatment of the resulting complex with iodine led to C-H iodination at the methine carbon. This study provides important mechanistic information for palladium-catalyzed functionalization of methine C-H bonds.

引用

收藏

页码：1057 / 1059

页数：3

相关论文

共 34 条

[1]

[Anonymous], ANGEW CHEM

[2] TRANSITION-METAL ENOLATE CHEMISTRY - FORMATION OF A PALLADIUM ALKYL COMPLEX FROM A HIGHLY REACTIVE ENOLATOPALLADIUM COMPLEX [J].

BALEGROUNE, F ;

GRANDJEAN, D ;

LAKKIS, D ;

MATT, D .

JOURNAL OF THE CHEMICAL SOCIETY-CHEMICAL COMMUNICATIONS, 1992, (15) :1084-1085

[3] Transition metal-catalyzed arylation of unactivated C(sp3)-H bonds [J].

Baudoin, Olivier .

CHEMICAL SOCIETY REVIEWS, 2011, 40 (10) :4902-4911

[4] Carbon-oxygen bond formation at organopalladium centers:: The reactions of PdMeR(L2) (R = Me, 4-tolyl; L2= tmeda, bpy) with diaroyl peroxides and the involvement of organopalladium(IV) species [J].

Canty, AJ ;

Denney, MC ;

Skelton, BW ;

White, AH .

ORGANOMETALLICS, 2004, 23 (05) :1122-1131

[5] Palladium-Catalyzed Direct Arylation of C-H Bond To Construct Quaternary Carbon Centers: The Synthesis of Diarylfluorene [J].

Cao, Xiao ;

Yang, Weidong ;

Liu, Chao ;

Wei, Fuliang ;

Wu, Kun ;

Sun, Wei ;

Song, Juan ;

Xie, Linghai ;

Huang, Wei .

ORGANIC LETTERS, 2013, 15 (12) :3102-3105

[6] Palladium(II)-Catalyzed C-H Activation/C-C Cross-Coupling Reactions: Versatility and Practicality [J].

Chen, Xiao ;

Engle, Keary M. ;

Wang, Dong-Hui ;

Yu, Jin-Quan .

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2009, 48 (28) :5094-5115

[7] THE SYNTHESIS AND REACTIVITY OF PERFLUORINATED UNDECAFLUOROBICYCLO[2,2,1]-HEPTAN-1-YL PLATINUM(II), PALLADIUM(II) AND RHENIUM(V) COMPLEXES AND THE X-RAY CRYSTAL-STRUCTURE OF CIS-PTCL(C7F11)(PPH3)2 [J].

CLAIRE, PPK ;

JONES, CJ ;

MCCLEVERTY, JA ;

COE, PL ;

DREW, MGB .

JOURNAL OF ORGANOMETALLIC CHEMISTRY, 1992, 424 (01) :105-114

[8] Synthesis and Reactivity of a Nucleophilic Palladium(II) Carbene [J].

Comanescu, Cezar C. ;

Iluc, Vlad M. .

ORGANOMETALLICS, 2014, 33 (21) :6059-6064

[9] Frustrated Lewis pair-like reactions of nucleophilic palladium carbenes with B(C6F5)3 [J].

Cui, Peng ;

Comanescu, Cezar C. ;

Iluc, Vlad M. .

CHEMICAL COMMUNICATIONS, 2015, 51 (28) :6206-6209

[10] 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

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