Developing NHC-Iridium Catalysts for the Highly Efficient Enantioselective Intramolecular Hydroamination Reaction

被引：40

作者：

Gao, Pengchao ^{[1
]}

Sipos, Gellert ^{[1
]}

Foster, Daven ^{[1
]}

Dorta, Reto ^{[1
]}

机构：

[1] Univ Western Australia, Sch Mol Sci, Dept Chem, 35 Stirling Highway, Perth, WA 6009, Australia

来源：

ACS CATALYSIS | 2017年 / 7卷 / 09期

基金：

澳大利亚研究理事会;

关键词：

chiral NHC; iridium; catalysis; hydroamination; N-heterocycles; ASYMMETRIC HYDROAMINATION; UNACTIVATED ALKENES; ALPHA-ARYLATION; COMPLEXES; AMINES; AMINOALKENES; CYCLIZATION; AMIDES; HYDROGENATION; ARYLAMINES;

D O I：

10.1021/acscatal.7b02508

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

Chiral, cationic NHC-iridium complexes are introduced as catalysts for the intramolecular hydroamination reaction of unactivated aminoalkenes. The catalysts show high activity in the construction of pyrrolidines, which are accessed with excellent optical purity. Enantiomerically enriched piperidines and indolines are also produced, and various functional groups are tolerated with this LTM system. A reaction mechanism is proposed, and a major deactivation pathway of these catalysts is presented and discussed.

引用

页码：6060 / 6064

页数：5

共 54 条

[1] Air- and water-stable catalysts for hydroamination/cyclization. Synthesis and application of CCC-NHC pincer complexes of Rh and Ir [J].

Bauer, Eike B. ;

Andavan, G. T. Senthil ;

Hollis, T. Keith ;

Rubio, Ramel J. ;

Cho, Joon ;

Kuchenbeiser, Glenn R. ;

Helgert, Theodore R. ;

Letko, Christopher S. ;

Tham, Fook S. .

ORGANIC LETTERS, 2008, 10 (06) :1175-1178

[2]

Bemoud E., 2015, CATAL SCI TECHNOL, V5, P2017

[3] Iridium(I) Complexes of π-Acidic Carboxamides [J].

Bohle, D. Scott ;

Chua, Zhijie .

ORGANOMETALLICS, 2015, 34 (06) :1074-1084

[4] An efficient method for removal of ruthenium byproducts from olefin metathesis reactions [J].

Cho, JH ;

Kim, BM .

ORGANIC LETTERS, 2003, 5 (04) :531-533

[5] CHIRAL ORGANOLANTHANIDE COMPLEXES FOR ENANTIOSELECTIVE OLEFIN HYDROGENATION [J].

CONTICELLO, VP ;

BRARD, L ;

GIARDELLO, MA ;

TSUJI, Y ;

SABAT, M ;

STERN, CL ;

MARKS, TJ .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1992, 114 (07) :2761-2762

[6] Gold(I)-Catalyzed Activation of Alkynes for the Construction of Molecular Complexity [J].

Dorel, Ruth ;

Echavarren, Antonio M. .

CHEMICAL REVIEWS, 2015, 115 (17) :9028-9072

[7] The [IrCl(diphosphine)](2)/fluoride system. Developing catalytic asymmetric olefin hydroamination [J].

Dorta, R ;

Egli, P ;

Zurcher, F ;

Togni, A .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1997, 119 (44) :10857-10858

[8] Synthesis of gem-Difluorinated Hydroxypyrrolidines [J].

Fedorov, Oleg V. ;

Struchkova, Marina I. ;

Dilman, Alexander D. .

JOURNAL OF ORGANIC CHEMISTRY, 2017, 82 (06) :3270-3275

[9] STEREOSELECTION EFFECTS IN THE CATALYTIC HYDROAMINATION CYCLIZATION OF AMINOOLEFINS AT CHIRAL ORGANOLANTHANIDE CENTERS [J].

GAGNE, MR ;

BRARD, L ;

CONTICELLO, VP ;

GIARDELLO, MA ;

STERN, CL ;

MARKS, TJ .

ORGANOMETALLICS, 1992, 11 (06) :2003-2005

[10] CHIRAL ORGANOLANTHANIDES DESIGNED FOR ASYMMETRIC CATALYSIS - A KINETIC AND MECHANISTIC STUDY OF ENANTIOSELECTIVE OLEFIN HYDROAMINATION/CYCLIZATION AND HYDROGENATION BY C-1-SYMMETRICAL ME(2)SI(ME(4)C(5))(C(5)H(3)R-ASTERISK)LN COMPLEXES WHERE R-ASTERISK=CHIRAL AUXILIARY [J].

GIARDELLO, MA ;

CONTICELLO, VP ;

BRARD, L ;

GAGNE, MR ;

MARKS, TJ .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1994, 116 (22) :10241-10254

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