Ynamide Carbopalladation: A Flexible Route to Mono-, Bi- and Tricyclic Azacycles

被引：42

作者：

Campbell, Craig D. ^{[1
]}

Greenaway, Rebecca L. ^{[1
]}

Holton, Oliver T. ^{[1
]}

Walker, P. Ross ^{[1
]}

Chapman, Helen A. ^{[2
]}

Russell, C. Adam ^{[2
]}

Carr, Greg ^{[3
]}

Thomson, Amber L. ^{[1
]}

Anderson, Edward A. ^{[1
]}

机构：

[1] Univ Oxford, Chem Res Lab, 12 Mansfield Rd, Oxford OX1 3TA, England

[2] Syngenta Ltd, Jealotts Hill Int Res Ctr, Bracknell RG42 6EY, Berks, England

[3] AstraZeneca, Macclesfield SK10 4TF, Cheshire, England

来源：

CHEMISTRY-A EUROPEAN JOURNAL | 2015年 / 21卷 / 36期

基金：

英国工程与自然科学研究理事会;

关键词：

domino reactions; hetero-Diels-Alder reactions; palladium catalysis; Suzuki coupling; ynamides; CROSS-COUPLING REACTIONS; DIELS-ALDER REACTION; CATALYZED CASCADE CYCLIZATION; MIYAURA DOMINO REACTIONS; ANION CAPTURE PROCESSES; SUZUKI-MIYAURA; SUBSTITUTED INDOLINES; EFFICIENT SYNTHESIS; ALKYNYL BROMIDES; 1-ALPHA; 25-DIHYDROXYVITAMIN D-3;

D O I：

10.1002/chem.201501710

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Bromoenynamides represent precursors to a diversity of azacycles by a cascade sequence of carbopalladation followed by cross-coupling/electrocyclization, or reduction processes. Full details of our investigations into intramolecular ynamide carbopalladation are disclosed, which include the first examples of carbopalladation/cross-coupling reactions using potassium organotrifluoroborate salts; and an understanding of factors influencing the success of these processes, including ring size, and the nature of the coupling partner. Additional mechanistic observations are reported, such as the isolation of triene intermediates for electrocyclization. A variety of hetero-Diels-Alder reactions using the product heterocycles are also described, which provide insight into Diels-Alder regioselectivity.

引用

页码：12627 / 12639

页数：13

共 137 条

[1] Total Synthesis of Calothrixins A and B by Palladium-Catalyzed Tandem Cyclization/Cross-Coupling Reaction of Indolylborate [J].

Abe, Takumi ;

Ikeda, Toshiaki ;

Choshi, Tominari ;

Hibino, Satoshi ;

Hatae, Noriyuki ;

Toyata, Eiko ;

Yanada, Reiko ;

Ishikura, Minoru .

EUROPEAN JOURNAL OF ORGANIC CHEMISTRY, 2012, 2012 (26) :5018-5027

[2] 1,2-N-Migration in a Gold-Catalysed Synthesis of Functionalised Indenes by the 1,1-Carboalkoxylation of Ynamides [J].

Adcock, Holly V. ;

Langer, Thomas ;

Davies, Paul W. .

CHEMISTRY-A EUROPEAN JOURNAL, 2014, 20 (24) :7262-7266

[3] Metal-mediated reductive hydrodehalogenation of organic halides [J].

Alonso, F ;

Beletskaya, IP ;

Yus, M .

CHEMICAL REVIEWS, 2002, 102 (11) :4009-4091

[4] SIR92 - a program for automatic solution of crystal structures by direct methods [J].

ALTOMARE, A ;

CASCARANO, G ;

GIACOVAZZO, G ;

GUAGLIARDI, A ;

BURLA, MC ;

POLIDORI, G ;

CAMALLI, M .

JOURNAL OF APPLIED CRYSTALLOGRAPHY, 1994, 27 :435-435

[5] Mechanism of the carbopalladation of alkynes by aryl-palladium complexes [J].

Amatore, C ;

Bensalem, S ;

Ghalem, S ;

Jutand, A .

JOURNAL OF ORGANOMETALLIC CHEMISTRY, 2004, 689 (24) :4642-4646

[6] Cascade polycyclisations in natural product synthesis [J].

Anderson, Edward A. .

ORGANIC & BIOMOLECULAR CHEMISTRY, 2011, 9 (11) :3997-4006

[7]

[Anonymous], 2014, ANGEW CHEM

[8]

[Anonymous], ANGEW CHEM

[9] An overview of the synthetic routes to the best selling drugs containing 6-membered heterocycles [J].

Baumann, Marcus ;

Baxendale, Ian R. .

BEILSTEIN JOURNAL OF ORGANIC CHEMISTRY, 2013, 9 :2265-2319

[10] An overview of the key routes to the best selling 5-membered ring heterocyclic pharmaceuticals [J].

Baumann, Marcus ;

Baxendale, Ian R. ;

Ley, Steven V. ;

Nikbin, Nikzad .

BEILSTEIN JOURNAL OF ORGANIC CHEMISTRY, 2011, 7 :442-495

← 1 2 3 4 5 6 7 8 9 10 →