Flow Heck Reactions Using Extremely Low Loadings of Phosphine-Free Palladium Acetate

被引：16

作者：

Cyr, Patrick ^{[1
]}

Deng, Stella T. ^{[1
]}

Hawkins, Joel M. ^{[1
]}

Price, Kristin E. ^{[1
]}

机构：

[1] Pfizer Inc, Worldwide Res & Dev, Groton, CT 06340 USA

来源：

ORGANIC LETTERS | 2013年 / 15卷 / 17期

关键词：

FREE CATALYST SYSTEM; PRACTICAL SYNTHESIS; ORGANIC-SYNTHESIS; ARYL BROMIDES; TECHNOLOGY; ARYLATION; HALIDES; OLEFINS; ACID;

D O I：

10.1021/ol4018134

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

High-yielding Heck reactions are demonstrated using 0.05 mol % Pd(OAc)(2) without phosphine ligands. These reactions are run in a mesoscale flow reactor which allows precise control of reaction times and temperatures. Profiling yield and selectivity versus Pd loading shows 500 ppm to be optimal for aryl iodides; higher loadings favor side reactions caused by Pd(II) species. Aryl halides are examined via concise Design of Experiment to expand the scope and optimize conditions.

引用

页码：4342 / 4345

页数：4

共 26 条

[1] The heck reaction as a sharpening stone of palladium catalysis
Beletskaya, IP
Cheprakov, AV
[J]. CHEMICAL REVIEWS, 2000, 100 (08) : 3009 - 3066
[2] The Use of Copper Flow Reactor Technology for the Continuous Synthesis of 1,4-Disubstituted 1,2,3-Triazoles
Bogdan, Andrew R.
Sach, Neal W.
[J]. ADVANCED SYNTHESIS & CATALYSIS, 2009, 351 (06) : 849 - 854
[3] Efficient synthesis of [6-chloro-2-(4-chlorobenzoyl)-1H-indol-3-yl]-acetic acid, a novel COX-2 inhibitor
Caron, S
Vazquez, E
Stevens, RW
Nakao, K
Koike, H
Murata, Y
[J]. JOURNAL OF ORGANIC CHEMISTRY, 2003, 68 (10) : 4104 - 4107
[4] Development of an Efficient Pd-Catalyzed Coupling Process for Axitinib
Chekal, Brian P.
Guinness, Steven M.
Lillie, Brett M.
McLaughlin, Robert W.
Palmer, Charles W.
Post, Ronald J.
Sieser, Janice E.
Singer, Robert A.
Sluggett, Gregory W.
Vaidyanathan, Rajappa
Withbroe, Gregory J.
[J]. ORGANIC PROCESS RESEARCH & DEVELOPMENT, 2014, 18 (01) : 266 - 274
[5] Homeopathic ligand-free palladium as a catalyst in the Heck reaction. A comparison with a palladacycle
de Vries, AHM
Mulders, JMCA
Mommers, JHM
Henderickx, HJW
de Vries, JG
[J]. ORGANIC LETTERS, 2003, 5 (18) : 3285 - 3288
[6] Diek H. A., 1974, J AM CHEM SOC, V96, P1133
[7] Structural characterisation of solution species implicated in the palladium-catalysed Heck reaction by PdK-edge X-ray absorption spectroscopy: palladium acetate as a catalyst precursor
Evans, J
O'Neill, L
Kambhampati, VL
Rayner, G
Turin, S
Genge, A
Dent, AJ
Neisius, T
[J]. JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS, 2002, (10): : 2207 - 2212
[8] Heterogeneous Versus Homogeneous Palladium Catalysts for Ligandless Mizoroki-Heck Reactions: A Comparison of Batch/Microwave and Continuous-Flow Processing
Glasnov, Toma N.
Findenig, Silvia
Kappe, C. Oliver
[J]. CHEMISTRY-A EUROPEAN JOURNAL, 2009, 15 (04) : 1001 - 1010
[9] Gürtler C, 1999, CHEM-EUR J, V5, P3107, DOI 10.1002/(SICI)1521-3765(19991105)5:11<3107::AID-CHEM3107>3.0.CO
[10] 2-#

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