Intramolecular ring-opening from a CO2-derived nucleophile as the origin of selectivity for 5-substituted oxazolidinone from the (salen)Cr-catalyzed [aziridine + CO2] coupling

被引：53

作者：

Adhikari, Debashis ^{[1
,2
,3
]}

Miller, Aaron W. ^{[1
,2
]}

Baik, Mu-Hyun ^{[3
,4
]}

Nguyen, SonBinh T. ^{[1
,2
]}

机构：

[1] Northwestern Univ, Dept Chem, Evanston, IL 60208 USA

[2] Northwestern Univ, Int Inst Nanotechnol, Evanston, IL 60208 USA

[3] Indiana Univ, Dept Chem, Bloomington, IN 47405 USA

[4] Korea Univ, Dept Mat Chem, Jochiwon Eup 339700, Sejong Si, South Korea

来源：

CHEMICAL SCIENCE | 2015年 / 6卷 / 02期

关键词：

ANTI-ALDOL REACTIONS; CARBON-DIOXIDE; HIGHLY EFFICIENT; ALTERNATING COPOLYMERIZATION; N-ACYLOXAZOLIDINONES; DENSITY FUNCTIONALS; CHEMICAL FIXATION; SALEN COMPLEXES; PROPYLENE-OXIDE; CATALYSTS;

D O I：

10.1039/c4sc02785j

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

The (salen) Cr-catalyzed [aziridine + CO2] coupling to form oxazolidinone was found to exhibit excellent selectivity for the 5-substituted oxazolidinone product in the absence of any cocatalyst. Quantum mechanical calculations suggest that the preferential opening of the substituted C-N bond of the aziridine over the unsubstituted C-N bond is a key factor for this selectivity, a result that is supported by experiment with several phenyl-substituted aziridines. In the presence of external nucleophile such as dimethyl aminopyridine (DMAP), the reaction changes pathway and the ring-opening process is regulated by the steric demand of the nucleophile.

引用

页码：1293 / 1300

页数：8

共 42 条

[1] A computational study of the mechanism of the [(salen)Cr + DMAP]-catalyzed formation of cyclic carbonates from CO2 and epoxide [J].

Adhikari, Debashis ;

Nguyen, SonBinh T. ;

Baik, Mu-Hyun .

CHEMICAL COMMUNICATIONS, 2014, 50 (20) :2676-2678

[2] 1,2-amino alcohols and their heterocyclic derivatives as chiral auxiliaries in asymmetric synthesis [J].

Ager, DJ ;

Prakash, I ;

Schaad, DR .

CHEMICAL REVIEWS, 1996, 96 (02) :835-875

[3] Silver(I)-Diene Complexes as Versatile Catalysts for the C-Arylation of N-Tosylaziridines: Mechanistic Insight from In Situ Diagnostics [J].

Bera, Milan ;

Roy, Sujit .

JOURNAL OF ORGANIC CHEMISTRY, 2010, 75 (13) :4402-4412

[4] A linear, O-coordinated η1-CO2 bound to uranium [J].

Castro-Rodriguez, I ;

Nakai, H ;

Zakharov, LN ;

Rheingold, AL ;

Meyer, K .

SCIENCE, 2004, 305 (5691) :1757-1759

[5] Single-site β-diiminate zinc catalysts for the alternating copolymerization of CO2 and epoxides:: Catalyst synthesis and unprecedented polymerization activity [J].

Cheng, M ;

Moore, DR ;

Reczek, JJ ;

Chamberlain, BM ;

Lobkovsky, EB ;

Coates, GW .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2001, 123 (36) :8738-8749

[6] Alternating copolymerization of propylene oxide and carbon dioxide with highlv efficient and selective (salen)Co(III) catalysts: Effect of ligand and cocatalyst variation [J].

Cohen, Claire T. ;

Coates, Geoffrey W. .

JOURNAL OF POLYMER SCIENCE PART A-POLYMER CHEMISTRY, 2006, 44 (17) :5182-5191

[7] Transformation of Carbon Dioxide with Homogeneous Transition-Metal Catalysts: A Molecular Solution to a Global Challenge? [J].

Cokoja, Mirza ;

Bruckmeier, Christian ;

Rieger, Bernhard ;

Herrmann, Wolfgang A. ;

Kuehn, Fritz E. .

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2011, 50 (37) :8510-8537

[8] Cross-linking in the living cell locates the site of action of oxazolidinone antibiotics [J].

Colca, JR ;

McDonald, WG ;

Waldon, DJ ;

Thomasco, LM ;

Gadwood, RC ;

Lund, ET ;

Cavey, GS ;

Mathews, WR ;

Adams, LD ;

Cecil, ET ;

Pearson, JD ;

Bock, JH ;

Mott, JE ;

Shinabarger, DL ;

Xiong, LQ ;

Mankin, AS .

JOURNAL OF BIOLOGICAL CHEMISTRY, 2003, 278 (24) :21972-21979

[9] Making plastics from carbon dioxide:: Salen metal complexes as catalysts for the production of polycarbonates from epoxides and CO2 [J].

Darensbourg, Donald J. .

CHEMICAL REVIEWS, 2007, 107 (06) :2388-2410

[10] Quaternary ammonium bromide functionalized polyethylene glycol: A highly efficient and recyclable catalyst for selective synthesis of 5-aryl-2-oxazolidinones from carbon dioxide and aziridines under solvent-free conditions [J].

Du, Ya ;

Wu, Ying ;

Liu, An-Hua ;

He, Liang-Nian .

JOURNAL OF ORGANIC CHEMISTRY, 2008, 73 (12) :4709-4712

← 1 2 3 4 5 →