Enantioselective synthesis of 2,5-dihydrobenzo[b]azepine derivatives via iridium-catalyzed asymmetric allylic amination with 2-allylanilines and ring-closing-metathesis reaction

被引：35

作者：

Ye, Ke-Yin ^{[1
]}

Dai, Li-Xin ^{[1
]}

You, Shu-Li ^{[1
]}

机构：

[1] Chinese Acad Sci, Shanghai Inst Organ Chem, State Key Lab Organometall Chem, Shanghai 200032, Peoples R China

来源：

ORGANIC & BIOMOLECULAR CHEMISTRY | 2012年 / 10卷 / 30期

关键词：

PHOSPHORAMIDITE LIGAND; SUBSTITUTION-REACTION; BUILDING-BLOCKS; ALLYLATION; ALKYLATION; DEAROMATIZATION; ETHERIFICATION; REARRANGEMENT; HETEROCYCLES; ANTAGONISTS;

D O I：

10.1039/c2ob00036a

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

Iridium-catalyzed asymmetric allylic amination of allylic carbonates with 2-allylanilines was realized. With a catalyst generated from 2 mol% of [Ir(dbcot)Cl](2) (dbcot = dibenzo[a,e]cyclooctatetraene) and 4 mol% of phosphoramidite ligand (L3), the amination products were obtained in up to 99% yield and 99% ee. Subjecting amination products to trifluoroacetyl protection and ring-closing-metathesis reaction provided an efficient synthesis of enantioenriched 2,5-dihydrobenzo[b]azepine derivatives.

引用

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页码：5932 / 5939

页数：8

相关论文

共 74 条

[1] A simple two-step sequence for the synthesis of novel 4-aryl-4,5-dihydro-6H-[1,3]dioxolo[4,5-h]pyrrolo[1,2-a][1]benzazepin-6-ones from 6-amino-3,4-methylenedioxyacetophenone [J].

Abonia, Rodrigo ;

Cuervo, Paola ;

Insuasty, Braulio ;

Quiroga, Jairo ;

Nogueras, Manuel ;

Cobo, Justo .

EUROPEAN JOURNAL OF ORGANIC CHEMISTRY, 2008, 2008 (27) :4684-4689

[2] Very efficient phosphoramidite ligand for asymmetric iridium-catalyzed allylic alkylation [J].

Alexakis, A ;

Polet, D .

ORGANIC LETTERS, 2004, 6 (20) :3529-3532

[3]

Alexakis A, 2001, SYNLETT, P1375

[4] Sequential amino-claisen rearrangement/intramolecular 1,3-dipolar cycloaddition/reductive cleavage approach to the stereoselective synthesis of cis-4-hydroxy-2-aryl-2,3,4,5-tetrahydro-1(1H)-benzazepines [J].

Ayala, Sandra Liliana Gomez ;

Stashenko, Elena ;

Palma, Alirio ;

Bahsas, Ali ;

Amaro-Luis, Juan Manuel .

SYNLETT, 2006, (14) :2275-2277

[5] Solid-phase preparation of a pilot library derived from the 2,3,4,5-tetrahydro-1H-benzo[b]azepin-5-amine scaffold [J].

Boeglin, Damien ;

Bonnet, Dominique ;

Hibert, Marcel .

JOURNAL OF COMBINATORIAL CHEMISTRY, 2007, 9 (03) :487-500

[6] Application of iridium catalyzed allylic substitution reactions in the synthesis of branched tryptamines and homologues via tandem hydroformylation-Fischer indole synthesis [J].

Bondzic, Bojan P. ;

Farwick, Andreas ;

Liebich, Jens ;

Eilbracht, Peter .

ORGANIC & BIOMOLECULAR CHEMISTRY, 2008, 6 (20) :3723-3731

[7] Diastereoselective synthesis of substituted 2,3,4,5-tetrahydro-1H-1-benzazepine-5-carboxylic esters by a tandem reduction-reductive amination reaction [J].

Bunce, RA ;

Johnson, LB ;

Holt, EM .

JOURNAL OF HETEROCYCLIC CHEMISTRY, 2004, 41 (04) :563-568

[8] Catalytic Asymmetric Pictet-Spengler-Type Reaction for the Synthesis of Optically Active Indolo[3,4-cd][1]benzazepines [J].

Cheng, Dao-Juan ;

Wu, Hai-Bian ;

Tian, Shi-Kai .

ORGANIC LETTERS, 2011, 13 (20) :5636-5639

[9] Iridium-catalyzed enantioselective allylic substitutions with aliphatic nitro compounds as prenucleophiles [J].

Dahnz, A ;

Helmchen, G .

SYNLETT, 2006, (05) :697-700

[10] Iridium-catalyzed synthesis of primary allylic amines from allylic alcohols: Sulfamic acid as amonia equivalent [J].

Defieber, Christian ;

Ariger, Martin A. ;

Moriel, Patricia ;

Carreira, Erick M. .

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2007, 46 (17) :3139-3143

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