Rhodium(III)-Catalyzed imidoyl C-H Activation for Annulations to Azolopyrimidines

被引：94

作者：

Halskov, Kim Soholm ^{[1
]}

Witten, Michael R. ^{[1
]}

Hoang, Gia L. ^{[1
]}

Mercado, Brandon Q. ^{[1
]}

Ellman, Jonathan A. ^{[1
]}

机构：

[1] Yale Univ, Dept Chem, New Haven, CT 06520 USA

来源：

ORGANIC LETTERS | 2018年 / 20卷 / 08期

关键词：

INTERMOLECULAR HYDROACYLATION; SULFOXONIUM YLIDES; BOND; ALKYNES; FUNCTIONALIZATION; COMPLEXES; RHODIUM; REACTIVITY; INSERTION; ALDEHYDE;

D O I：

10.1021/acs.orglett.8b00816

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

Azolopyrimidines are efficiently prepared by direct imidoyl C-H bond activation. Annulations of N-azolo imines with sulfoxonium ylides and diazoketones under redoxneutral conditions and alkynes under oxidizing conditions provide products with various arrangements of nitrogen atoms and carbon substituents. We have also probed the mechanism of this first example of Rh(III)-catalyzed direct imidoyl C-H activation by structural characterization of a catalytically competent rhodacycle obtained after C-H activation and by kinetic isotope effects.

引用

收藏

页码：2464 / 2467

页数：4

相关论文

共 26 条

[1] SYNTHESIS, STRUCTURE AND NMR-SPECTROSCOPY OF SOME RHODIUM(III) CYCLOMETALLATED SCHIFF-BASE COMPLEXES DERIVED FROM 2-BENZYLIDENE-3-METHYLPYRIDINES - CRYSTAL-STRUCTURE OF [RHHI(2-(3-NITROBENZYLIDENE)-3-METHYLPYRIDINE)(PPH3)2] [J].

ALBINATI, A ;

ARZ, C ;

PREGOSIN, PS .

JOURNAL OF ORGANOMETALLIC CHEMISTRY, 1987, 335 (03) :379-394

[2] Combined Experimental and Computational Investigations of Rhodium- and Ruthenium-Catalyzed C-H Functionalization of Pyrazoles with Alkynes [J].

Algarra, Andres G. ;

Cross, Warren B. ;

Davies, David L. ;

Khamker, Qudsia ;

Macgregor, Stuart A. ;

McMullin, Claire L. ;

Singh, Kuldip .

JOURNAL OF ORGANIC CHEMISTRY, 2014, 79 (05) :1954-1970

[3] Cross-Coupling of α-Carbonyl Sulfoxonium Ylides with C-H Bonds [J].

Barday, Manuel ;

Janot, Christopher ;

Halcovitch, Nathan R. ;

Muir, James ;

Aissa, Christophe .

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2017, 56 (42) :13117-13121

[4] Rhodium-catalyzed oxidative coupling of aromatic imines with internal alkynes via regioselective C-H bond cleavage [J].

Fukutani, Tatsuya ;

Umeda, Nobuyoshi ;

Hirano, Koji ;

Satoh, Tetsuya ;

Miura, Masahiro .

CHEMICAL COMMUNICATIONS, 2009, (34) :5141-5143

[5] Metal-Catalyzed Annulations through Activation and Cleavage of C-H Bonds [J].

Gulias, Moises ;

Luis Mascarenas, Jose .

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2016, 55 (37) :11000-11019

[6] Synthesis of [5,6]-Bicyclic Heterocycles with a Ring-Junction Nitrogen Atom: Rhodium(III)-Catalyzed C-H Functionalization of Alkenyl Azoles [J].

Halskov, Kim Soholm ;

Roth, Howard S. ;

Ellman, Jonathan A. .

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2017, 56 (31) :9183-9187

[7] Chelation-assisted intermolecular hydroacylation: Direct synthesis of ketone from aldehyde and 1-alkene [J].

Jun, CH ;

Lee, H ;

Hong, JB .

JOURNAL OF ORGANIC CHEMISTRY, 1997, 62 (05) :1200-1201

[8] Ruthenium-catalyzed benzimidazoisoquinoline synthesis via oxidative coupling of 2-arylbenzimidazoles with alkynes [J].

Kavitha, Nerella ;

Sukumar, Genji ;

Kumar, Vemula Praveen ;

Mainkar, Prathama S. ;

Chandrasekhar, Srivari .

TETRAHEDRON LETTERS, 2013, 54 (32) :4198-4201

[9] Rhodium(III)-Catalyzed Oxidative Coupling of 5-Aryl-1H-pyrazoles with Alkynes and Acrylates [J].

Li, Xingwei ;

Zhao, Miao .

JOURNAL OF ORGANIC CHEMISTRY, 2011, 76 (20) :8530-8536

[10] Ruthenium-Catalyzed Alkyne Annulations with Substituted 1H-Pyrazoles by C-H/N-H Bond Functionalizations [J].

Ma, Wenbo ;

Graczyk, Karolina ;

Ackermann, Lutz .

ORGANIC LETTERS, 2012, 14 (24) :6318-6321