Selective Reductive Elimination at Alkyl Palladium(IV) by Dissociative Ligand Ionization: Catalytic C(sp3)-H Amination to Azetidines

被引：59

作者：

Nappi, Manuel ^{[1
]}

He, Chuan ^{[1
]}

Whitehurst, William G. ^{[1
]}

Chappell, Ben G. N. ^{[1
]}

Gaunt, Matthew J. ^{[1
]}

机构：

[1] Univ Cambridge, Dept Chem, Lensfield Rd, Cambridge CB2 1EW, England

来源：

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION | 2018年 / 57卷 / 12期

基金：

英国工程与自然科学研究理事会; 欧洲研究理事会;

关键词：

azetidines; C-H activation; hypervalent compounds; palladium; reaction mechanisms; C-H ACTIVATION; NITROGEN-CONTAINING HETEROCYCLES; HYPERVALENT IODINE REAGENTS; PD-IV; BOND FUNCTIONALIZATION; METHYL-GROUPS; OXIDATION; COMPLEXES; CHEMISTRY; INDOLINES;

D O I：

10.1002/anie.201800519

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

A palladium(II)-catalyzed -C-H amination of cyclic alkyl amines to deliver highly substituted azetidines is reported. The use of a benziodoxole tosylate oxidant in combination with AgOAc was found to be crucial for controlling a selective reductive elimination pathway to the azetidines. The process is tolerant of a range of functional groups, including structural features derived from chiral -amino alcohols, and leads to the diastereoselective formation of enantiopure azetidines.

引用

页码：3178 / 3182

页数：5

共 49 条

[1]

Alcaide B, 2010, CURR OPIN DRUG DISC, V13, P685

[2] Carbon-Nitrogen Bond Formation Through Cross-Dehydrogenative Coupling Reactions [J].

Baeten, Mattijs ;

Maes, Bert U. W. .

ADVANCES IN ORGANOMETALLIC CHEMISTRY, VOL 67, 2017, 67 :401-481

[3] Benziodoxole-based hypervalent iodine reagents for atom-transfer reactions [J].

Brand, Jonathan P. ;

Gonzalez, Davinia Fernandez ;

Nicolai, Stefano ;

Waser, Jerome .

CHEMICAL COMMUNICATIONS, 2011, 47 (01) :102-115

[4] Novel syntheses of azetidines and azetidinones [J].

Brandi, Alberto ;

Cicchi, Stefano ;

Cordero, Franca M. .

CHEMICAL REVIEWS, 2008, 108 (09) :3988-4035

[5]

Camasso NM, 2014, J AM CHEM SOC, V136, P12771, DOI [10.1021/Ja507056u, 10.1021/ja507056u]

[6] Computational study of C(sp3)-O bond formation at a PdIV centre [J].

Canty, Allan J. ;

Ariafard, Alireza ;

Camasso, Nicole M. ;

Higgs, Andrew T. ;

Yates, Brian F. ;

Sanford, Melanie S. .

DALTON TRANSACTIONS, 2017, 46 (11) :3742-3748

[7] Organopalladium and platinum chemistry in oxidising milieu as models for organic synthesis involving the higher oxidation states of palladium [J].

Canty, Allan J. .

DALTON TRANSACTIONS, 2009, (47) :10409-10417

[8] Palladium-catalyzed alkylation of sp2 and sp3 C-H bonds with methylboroxine and alkylboronic acids:: Two distinct C-H activation pathways [J].

Chen, Xiao ;

Goodhue, Charles E. ;

Yu, Jin-Quan .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2006, 128 (39) :12634-12635

[9] Azetidines: New Tools for the Synthesis of Nitrogen Heterocycles [J].

Couty, Francois ;

Evano, Gwilherm .

SYNLETT, 2009, (19) :3053-3064

[10] IBX-mediated oxidation of unactivated cyclic amines: application in highly diastereoselective oxidative Ugi-type and aza-Friedel-Crafts reactions [J].

de Graaff, C. ;

Bensch, L. ;

van Lint, Matthijs J. ;

Ruijter, E. ;

Orru, R. V. A. .

ORGANIC & BIOMOLECULAR CHEMISTRY, 2015, 13 (40) :10108-10112

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