Bypassing the Inertness of Aziridine/CO2Systems to Access 5-Aryl-2-Oxazolidinones: Catalyst-Free Synthesis Under Ambient Conditions

被引：18

作者：

Bresciani, Giulio ^{[1
,2
]}

Antico, Emanuele ^{[1
]}

Ciancaleoni, Gianluca ^{[1
,2
]}

Zacchini, Stefano ^{[2
,3
]}

Pampaloni, Guido ^{[1
,2
]}

Marchetti, Fabio ^{[1
,2
]}

机构：

[1] Univ Pisa, Dipartimento Chim & Chim Ind, Via G Moruzzi 13, I-56124 Pisa, Italy

[2] CIRCC, Via Celso Ulpiani 27, I-70126 Bari, Italy

[3] Univ Bologna, Dipartimento Chim Ind Toso Montanari, Viale Risorgimento 4, I-40136 Bologna, Italy

来源：

CHEMSUSCHEM | 2020年 / 13卷 / 20期

关键词：

aziridines; carbon dioxide activation; catalyst free organic synthesis; oxazolidinones; sustainability; ONE-POT SYNTHESIS; CARBON-DIOXIDE; CARBOXYLATIVE CYCLIZATION; RECYCLABLE CATALYST; CHIRAL AUXILIARIES; REGIOSELECTIVE SYNTHESIS; OXAZOLIDINONE SYNTHESIS; CHEMICAL FIXATION; HIGHLY EFFICIENT; AZIRIDINES;

D O I：

10.1002/cssc.202001823

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

The development of sustainable synthetic routes to access valuable oxazolidinones via CO(2)fixation is an active research area, and the aziridine/carbon dioxide coupling has aroused a considerable interest. This reaction features a high activation barrier and thus requires a catalytic system, and may present some other critical issues. Here, the straightforward gram-scale synthesis of a series of 5-aryl-2-oxazolidinones was developed at ambient temperature and atmospheric CO(2)pressure, in the absence of any catalyst/co-catalyst. The key to this innovative procedure consists in the direct transfer of the pre-formed amine/CO(2)adduct (carbamate) to common aziridine precursors (dimethylsulfonium salts), replacing the classical sequential addition of amine (intermediate isolation of aziridine) and then CO2. The reaction mechanism was investigated by NMR spectroscopy and DFT calculations applied to model cases.

引用

页码：5586 / 5594

页数：9

共 82 条

[1] Cycloaddition of CO2 to challenging N-tosyl aziridines using a halogen-free niobium complex: Catalytic activity and mechanistic insights [J].