Iridium-catalyzed asymmetric allylic substitutions -: Very high regioselectivity and air stability with a catalyst derived from dibenzo[a,e]cyclooctatetraene and a phosphoramidite

被引：107

作者：

Spiess, Stephanie ^{[1
]}

Welter, Carolin ^{[1
]}

Franck, Geraldine ^{[1
]}

Taquet, Jean-Philippe ^{[1
]}

Helmchen, Guenter ^{[1
]}

机构：

[1] Univ Heidelberg, Inst Organ Chem, D-69120 Heidelberg, Germany

来源：

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION | 2008年 / 47卷 / 40期

关键词：

allylic amines; allylic substitution; asymmetric catalysis; cyclization; iridium;

D O I：

10.1002/anie.200802480

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

A final tweak: A new phosphoramidite iridium catalyst (see scheme) allows allylic substitutions to be run with a higher degree of regioselectivity than with other iridium catalysts and under aerobic conditions. Mechanistic aspects, in particular, the reversibility of the catalyst formation by C-H activation, are also presented. LL=dibenzocyclooctatetraene. © 2008 Wiley-VCH Verlag GmbH & Co. KGaA.

引用

页码：7652 / 7655

页数：4

共 14 条

[1] METALATION-RESISTANT LIGANDS - SOME PROPERTIES OF DIBENZOCYCLOOCTATETRAENE COMPLEXES OF MOLYBDENUM, RHODIUM, AND IRIDIUM [J].

ANTON, DR ;

CRABTREE, RH .

ORGANOMETALLICS, 1983, 2 (05) :621-627

[2]

Chaffins S, 2002, SYNTHESIS-STUTTGART, P1191

[3] Iridium-catalysed asymmetric allylic substitutions [J].

Helmchen, Guenter ;

Dahnz, Axel ;

Duebon, Pierre ;

Schelwies, Mathias ;

Weihofen, Robert .

CHEMICAL COMMUNICATIONS, 2007, (07) :675-691

[4] Identification of an activated catalyst in the iridium-catalyzed allylic amination and etherification. Increased rates, scope, and selectivity [J].

Kiener, CA ;

Shu, CT ;

Incarvito, C ;

Hartwig, JF .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2003, 125 (47) :14272-14273

[5] Resting state and kinetic studies on the asymmetric allylic substitutions catalyzed by iridium-phosphoramidite complexes [J].

Markovic, Dean ;

Hartwig, John F. .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2007, 129 (38) :11680-+

[6]

Pfaltz A., 1999, COMPREHENSIVE ASYMME, P833, DOI DOI 10.1021/CR0683515

[7] Phosphoramidite Ligands in iridium-catalyzed allylic substitution [J].

Polet, D ;

Alexakis, A ;

Tissot-Croset, K ;

Corminboeuf, C ;

Ditrich, K .

CHEMISTRY-A EUROPEAN JOURNAL, 2006, 12 (13) :3596-3609

[8]

Shu C., 2004, ANGEW CHEM, V116, P4901

[9] Carbocycles via enantioselective inter- and intramolecular iridium-catalysed allylic alkylations [J].

Streiff, S ;

Welter, C ;

Schelwies, M ;

Lipowsky, G ;

Miller, N ;

Helmchen, G .

CHEMICAL COMMUNICATIONS, 2005, (23) :2957-2959

[10] Iridium-catalyzed formation of carbon-carbon and carbon-heteroatom bonds [J].

Takeuchi, Ryo ;

Kezuka, Satoko .

SYNTHESIS-STUTTGART, 2006, (20) :3349-3366

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