Synthesis of 1-Indanols and 1-Indanamines by Intramolecular Palladium(0)-Catalyzed C(sp3)-H Arylation: Impact of Conformational Effects

被引：28

作者：

Janody, Simon ^{[1
]}

Jazzar, Rodolphe ^{[1
]}

Comte, Arnaud ^{[1
]}

Holstein, Philipp M. ^{[1
]}

Vors, Jean-Pierre ^{[2
]}

Ford, Mark J. ^{[3
]}

Baudoin, Olivier ^{[1
]}

机构：

[1] Univ Lyon 1, CNRS UMR 5246, CPE Lyon, Inst Chim & Biochim Mol & Supramol, F-69622 Villeurbanne, France

[2] Bayer SAS, F-69263 Lyon 09, France

[3] Bayer CropSci AG, D-65926 Frankfurt, Germany

来源：

CHEMISTRY-A EUROPEAN JOURNAL | 2014年 / 20卷 / 35期

关键词：

C-C coupling; C-H activation; conformation analysis; palladium; C-H ACTIVATION; SILYL ENOL ETHERS; ALKANE ARYLATION; BOND; MECHANISM; FUNCTIONALIZATION; HYDROXYLATION; ACCESS;

D O I：

10.1002/chem.201402907

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

A range of valuable 1-indanols and 1-indanamines containing a tertiary C1 atom were synthesized by intramolecular palladium(0)-catalyzed C(sp(3))-H arylation, despite unfavorable steric interactions. The efficiency of the reaction was found to correlate with the degree of substitution at C2, as expected from the Thorpe-Ingold effect. Additionally, the nature of the heteroatomic substituent at C1 had a marked influence on the diastereoselectivity at C1 and C2; indeed, 1-indanols and 1-indanamines were obtained with the opposite relative configuration. Analysis of the X-ray and DFT-optimized structures of the corresponding reactive intermediates provided useful insights into the subtle conformational effects induced by these substituents.

引用

页码：11084 / 11090

页数：7

共 55 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]

Ahrens H., 2004, US Pat. Appl., Patent No. [20040157739A1 20040812, 2004157739]

[3]

[Anonymous], 2012, Angew. Chem

[4] The palladium-catalyzed C-H activation of benzylic gem-dialkyl groups [J].

Baudoin, O ;

Herrbach, A ;

Guéritte, F .

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2003, 42 (46) :5736-5740

[5]

Baudoin O., 2003, ANGEW CHEM, V115, P5914

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

Baudoin, Olivier .

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

[7] Stereoselective benzylic hydroxylation of 2-substituted indanes using toluene dioxygenase as biocatalyst [J].

Bowers, NI ;

Boyd, DR ;

Sharma, ND ;

Goodrich, PA ;

Groocock, MR ;

Blacker, AJ ;

Goode, P ;

Dalton, H .

JOURNAL OF THE CHEMICAL SOCIETY-PERKIN TRANSACTIONS 1, 1999, (11) :1453-1461

[8] Free-radical hydroxylation reactions of alkylboronates [J].

Cadot, C ;

Dalko, PI ;

Cossy, J ;

Ollivier, C ;

Chuard, R ;

Renaud, P .

JOURNAL OF ORGANIC CHEMISTRY, 2002, 67 (21) :7193-7202

[9] Effect of 2,6-disubstituted aryl groups on acyclic conformation: Preference for an antiperiplanar orientation of the geminal and vicinal hydrogens [J].

Carlier, Paul R. ;

Zhang, Yiqun ;

Slebodnick, Carla ;

Lo, Michael M. -C. ;

Williams, Ian D. .

JOURNAL OF ORGANIC CHEMISTRY, 2006, 71 (23) :8835-8841

[10] Intramolecular benzylic C-H activation: palladium-catalyzed synthesis of hexahydromethanofluorenes [J].

Catellani, M ;

Motti, E ;

Ghelli, S .

CHEMICAL COMMUNICATIONS, 2000, (20) :2003-2004

← 1 2 3 4 5 6 →