Organocatalytic Trapping of Elusive Carbon Dioxide Based Heterocycles by a Kinetically Controlled Cascade Process

被引：22

作者：

Qiao, Chang ^{[1
]}

Villar-Yanez, Alba ^{[1
]}

Sprachmann, Josefine ^{[1
]}

Limburg, Bart ^{[1
]}

Bo, Carles ^{[1
,2
]}

Kleij, Arjan W. ^{[1
,3
]}

机构：

[1] Barcelona Inst Sci & Technol, Inst Chem Res Catalonia ICIQ, Av Paisos Catalans 16, Tarragona 43007, Spain

[2] Univ Rovira & Virgili, Dept Quim Fis & Inorgan, Marcel Li Domingo S-N, Tarragona 43007, Spain

[3] Catalan Inst Res & Adv Studies ICREA, Pg Lluis Companys 23, Barcelona 08010, Spain

来源：

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION | 2020年 / 59卷 / 42期

关键词：

carbon dioxide; heterocycles; homogeneous catalysis; organocatalysis; reaction mechanisms; RING-OPENING POLYMERIZATION; CYCLIC CARBONATES; SUSTAINABLE CONVERSION; ATMOSPHERIC-PRESSURE; ORGANIC CARBONATES; CO2; CATALYST; COPOLYMERIZATION; EPOXIDES; POLYMERS;

D O I：

10.1002/anie.202007350

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

A conceptually novel approach is described for the synthesis of six-membered cyclic carbonates derived from carbon dioxide. The approach utilizes homoallylic precursors that are converted into five-membered cyclic carbonates having a beta-positioned alcohol group in one of the ring substituents. The activation of the pendent alcohol group through an N-heterocyclic base allows equilibration towards a thermodynamically disfavored six-membered carbonate analogue that can be trapped by an acylating agent. Various control experiments and computational analysis of this manifold are in line with a process that is primarily dictated by a kinetically controlled acylation step. This cascade process delivers an ample diversity of six-membered cyclic carbonates in excellent yields and chemoselectivities under mild reaction conditions.

引用

页码：18446 / 18451

页数：6