Catalytic Asymmetric Synthesis of α-Tetrasubstituted α-Trifluoromethyl Homoallylic Amines by Ir-Catalyzed Umpolung Allylation of Imines

被引：48

作者：

Wang, Yingwei ^{[1
,2
,3
]}

Deng, Li-Fan ^{[1
,2
,3
]}

Zhang, Xia ^{[1
]}

Niu, Dawen ^{[1
]}

机构：

[1] Sichuan Univ, Dept Emergency, State Key Lab Biotherapy, Chengdu 610041, Sichuan, Peoples R China

[2] Sichuan Univ, Ctr Canc, West China Hosp, Chengdu 610041, Sichuan, Peoples R China

[3] Sichuan Univ, Sch Chem Engn, Chengdu 610041, Sichuan, Peoples R China

来源：

ORGANIC LETTERS | 2019年 / 21卷 / 17期

关键词：

BOND-FORMING REACTIONS; ENANTIOSELECTIVE ISOMERIZATION; DECARBOXYLATIVE GENERATION; REGIOSELECTIVE ARYLATION; ALLYLIC ALKYLATION; COPE REARRANGEMENT; 2-AZAALLYL ANIONS; AMINOALLYLATION; CARBON; DERIVATIVES;

D O I：

10.1021/acs.orglett.9b02550

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

A general and mild method to prepare enantioenriched alpha-trifluoromethyl, alpha-stereogenic homoallylic amines is established. This reaction, which involves an Ir-catalyzed umpolung allylation of imines and a 2-aza-Cope rearrangement cascade, could yield both tetrasubstituted and trisubstituted stereocenters. This transformation employs readily available starting materials and displays broad substrate scope. The isolation and structural determination of reaction intermediates revealed factors critical for the efficiency and stereoselectivity of this transformation.

引用

页码：6951 / 6956

页数：6

共 79 条

[1] Enantioselective iridium catalyzed α-alkylation of azlactones by a tandem asymmetric allylic alkylation/aza-Cope rearrangement [J].

Bai, Xue-Dan ;

Zhang, Qing-Feng ;

He, Ying .

CHEMICAL COMMUNICATIONS, 2019, 55 (39) :5547-5550

[2] Iridium-catalysed asymmetric allylic alkylation of benzofuran γ-lactones followed by heteroaromatic Cope rearrangement: study of an unusual reaction sequence [J].

Bos, Maxence ;

Riguet, Emmanuel .

CHEMICAL COMMUNICATIONS, 2017, 53 (36) :4997-5000

[3] Synthesis of homoallylic amines via the palladium-catalyzed decarboxylative coupling of amino acid derivatives [J].

Burger, Erin C. ;

Tunge, Jon A. .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2006, 128 (31) :10002-10003

[4] Phosphine-Catalyzed Asymmetric Synthesis of α-Quaternary Amine via Umpolung γ-Addition of Ketimines to Allenoates [J].

Chen, Peng ;

Zhang, Junliang .

ORGANIC LETTERS, 2017, 19 (24) :6550-6553

[5] Phosphine-Catalyzed Asymmetric Umpolung Addition of Trifluoromethyl Ketimines to Morita-Baylis-Hillman Carbonates [J].

Chen, Peng ;

Yue, Zhenting ;

Zhang, Junyou ;

Lv, Xi ;

Wang, Lei ;

Zhang, Junliang .

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2016, 55 (42) :13316-13320

[6] Catalytic Carbon-Carbon Bond-Forming Reactions of Aminoalkane Derivatives with Imines [J].

Chen, Yi-Jing ;

Seki, Kazutaka ;

Yamashita, Yasuhiro ;

Kobayashi, Shu .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2010, 132 (10) :3244-+

[7] ELECTROPHILIC SUBSTITUTION AT SATURATED CARBON .27. CARBANIONS AS INTERMEDIATES IN BASE-CATALYZED METHYLENE-AZOMETHINE REARRANGEMENT [J].

CRAM, DJ ;

GUTHRIE, RD .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1966, 88 (24) :5760-&

[8] Palladium-Catalyzed Synthesis of α-Trifluoromethyl Benzylic Amines via Fluoroarylation of gem-Difluoro-2-azadienes Enabled by Phosphine-Catalyzed Formation of an Azaallyl-Silver Intermediate [J].

Daniel, Paige E. ;

Onyeagusi, Chibueze I. ;

Ribeiro, Anthony A. ;

Li, Kangnan ;

Malcolmson, Steven J. .

ACS CATALYSIS, 2019, 9 (01) :205-210

[9] Umpolung Synthesis of 1,3-Amino Alcohols: Stereoselective Addition of 2-Azaallyl Anions to Epoxides [J].

Daniel, Paige E. ;

Weber, Alexandria E. ;

Malcolmson, Steven J. .

ORGANIC LETTERS, 2017, 19 (13) :3490-3493

[10] Synthesis of (diarylmethyl)amines using Ni-catalyzed arylation of C(sp3)-H bonds [J].

Fernandez-Salas, Jose A. ;

Marelli, Enrico ;

Nolan, Steven P. .

CHEMICAL SCIENCE, 2015, 6 (08) :4973-4977

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