Practical Electrochemical Anodic Oxidation of Polycyclic Lactams for Late Stage Functionalization

被引：68

作者：

Frankowski, Kevin J. ^{[1
]}

Liu, Ruzhang ^{[1
]}

Milligan, Gregory L. ^{[2
]}

Moeller, Kevin D. ^{[3
]}

Aube, Jeffrey ^{[1
]}

机构：

[1] Univ Kansas, Dept Med Chem, Lawrence, KS 66047 USA

[2] St Martins Univ, Dept Chem, Lacey, WA 98503 USA

[3] Washington Univ, Dept Chem, St Louis, MO 63130 USA

来源：

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION | 2015年 / 54卷 / 36期

关键词：

anodic oxidation; diversity-oriented synthesis; heterocycles; lactams; N-acyliminium ions; N-ACYLIMINIUM IONS; INTRAMOLECULAR SCHMIDT REACTION; NATURAL-PRODUCT SYNTHESIS; ELECTROORGANIC CHEMISTRY; PROLINE DERIVATIVES; ALKYL AZIDES; CONSTRUCTION; ANALOGS; PEPTIDOMIMETICS; NEOTHRAMYCIN;

D O I：

10.1002/anie.201504775

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Electrochemistry provides a powerful tool for the late-stage functionalization of complex lactams. A two-stage protocol for converting lactams, many of which can be prepared through the intramolecular Schmidt reaction of keto azides, is presented. In the first step, anodic oxidation in MeOH using a repurposed power source provides a convenient route to lactams bearing a methoxy group adjacent to nitrogen. Treatment of these intermediates with a Lewis acid in dichloromethane permits the regeneration of a reactive acyliminium ion that is then reacted with a range of nucleophilic species.

引用

页码：10555 / 10558

页数：4

共 60 条

[11] Electrolytic Macrocyclizations: Scalable Synthesis of a Diazonamide-Based Drug Development Candidate [J].

Ding, Hui ;

DeRoy, Patrick L. ;

Perreault, Christian ;

Larivee, Alexandre ;

Siddiqui, Arshad ;

Caldwell, Charles G. ;

Harran, Susan ;

Harran, Patrick G. .

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2015, 54 (16) :4818-4822

[12] Building constrained peptidomimetics: a convenient approach to 3-phenyl-5-vinyl substituted proline derivatives [J].

Duan, SQ ;

Moeller, KD .

TETRAHEDRON, 2001, 57 (30) :6407-6415

[13] Organocatalyzed Anodic Oxidation of Aldehydes [J].

Finney, Eric E. ;

Ogawa, Kelli A. ;

Boydston, Andrew J. .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2012, 134 (30) :12374-12377

[14] Recent advances in the electrochemical construction of heterocycles [J].

Francke, Robert .

BEILSTEIN JOURNAL OF ORGANIC CHEMISTRY, 2014, 10 :2858-2873

[15] Explorations of Stemona alkaloid-inspired analogues:: Skeletal modification and functional group diversification [J].

Frankowski, Kevin J. ;

Neuenswander, Benjamin ;

Aube, Jeffrey .

JOURNAL OF COMBINATORIAL CHEMISTRY, 2008, 10 (05) :721-725

[16] Synthesis and receptor profiling of Stemona alkaloid analogues reveal a potent class of sigma ligands [J].

Frankowski, Kevin J. ;

Setola, Vincent ;

Evans, Jon M. ;

Neuenswander, Ben ;

Roth, Bryan L. ;

Aube, Jeffrey .

PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA, 2011, 108 (17) :6727-6732

[17] Anodic electrochemistry and the use of a 6-volt lantern battery: A simple method for attempting electrochemically based synthetic transformations [J].

Frey, DA ;

Wu, N ;

Moeller, KD .

TETRAHEDRON LETTERS, 1996, 37 (46) :8317-8320

[18] Electrochemically Initiated Oxidative Amination of Benzoxazoles Using Tetraalkylammonium Halides As Redox Catalysts [J].

Gao, Wei-Jing ;

Li, Wei-Cui ;

Zeng, Cheng-Chu ;

Tian, Hong-Yu ;

Hu, Li-Ming ;

Little, R. Daniel .

JOURNAL OF ORGANIC CHEMISTRY, 2014, 79 (20) :9613-9618

[19] The Shono-type electroorganic oxidation of unfunctionalised amides. Carbon-carbon bond formation via electrogenerated N-acyliminium ions [J].

Jones, Alan M. ;

Banks, Craig E. .

BEILSTEIN JOURNAL OF ORGANIC CHEMISTRY, 2014, 10 :3056-3072

[20] Expedient Preparation of Nazlinine and a Small Library of Indole Alkaloids Using Flow Electrochemistry as an Enabling Technology [J].

Kabeshov, Mikhail A. ;

Musio, Biagia ;

Murray, Philip R. D. ;

Browne, Duncan L. ;

Ley, Steven V. .

ORGANIC LETTERS, 2014, 16 (17) :4618-4621

← 1 2 3 4 5 6 →