当前位置：
X-MOL 学术
›
ACS Catal.
›
论文详情
Our official English website, www.x-mol.net, welcomes your
feedback! (Note: you will need to create a separate account there.)
Valorization of CO2: Preparation of 2-Oxazolidinones by Metal–Ligand Cooperative Catalysis with SCS Indenediide Pd Complexes
ACS Catalysis ( IF 11.3 ) Pub Date : 2017-03-17 00:00:00 , DOI: 10.1021/acscatal.7b00209 Paul Brunel 1 , Julien Monot 1 , Christos E. Kefalidis 2 , Laurent Maron 2 , Blanca Martin-Vaca 1 , Didier Bourissou 1
ACS Catalysis ( IF 11.3 ) Pub Date : 2017-03-17 00:00:00 , DOI: 10.1021/acscatal.7b00209 Paul Brunel 1 , Julien Monot 1 , Christos E. Kefalidis 2 , Laurent Maron 2 , Blanca Martin-Vaca 1 , Didier Bourissou 1
Affiliation
|
The capture and utilization of CO2 to prepare high-value compounds is very attractive chemically and highly desirable socially. Indenediide-based Pd SCS pincer complexes are shown here to promote the carboxylative cyclization of propargylamines leading to 2-oxazolidinones under mild conditions (0.5–1 bar of CO2, DMSO, 40–80 °C, 1–5 mol % Pd loading). The indenediide Pd complex is competitive with known catalysts. It proved successful for a wide range of propargylamines, including hitherto challenging substrates such as secondary propargylamines bearing tertiary alkyl groups at nitrogen, primary propargylamines, and propargylanilines. Thorough experimental (NMR) and computational (DFT) investigations were undertaken to gain mechanistic insights. Accordingly, (i) the resting state of the catalytic cycle is a Pd DMSO complex; (ii) the indenediide backbone and Pd center act in concert to activate the carbamic acid intermediate and promote its cyclization; (iii) proton shuttling is essential to lower the activation barriers of the initial amine carboxylation as well as of the proton transfers between the ligand backbone and the organic fragments at Pd.
中文翻译：
CO 2的平衡化：SCS茚二酮钯配合物的金属-配体协同催化制备2-恶唑烷酮
捕获和利用CO 2制备高价值化合物在化学上是非常有吸引力的，在社会上是非常合乎需要的。此处显示的基于茚二酮的Pd SCS钳形配合物可在温和的条件下（0.5-1 bar CO 2）促进炔丙基胺的羧基环化反应，生成2-恶唑烷酮，DMSO，40–80°C，1-5 mol％的Pd负载）。茚二酮Pd配合物与已知的催化剂竞争。事实证明，它可用于各种炔丙基胺，包括迄今具有挑战性的底物，例如在氮原子上带有叔烷基的仲炔丙基胺，伯炔丙基胺和炔丙基苯胺。进行了彻底的实验（NMR）和计算（DFT）研究，以获取机械方面的见解。因此，（i）催化循环的静止状态是Pd DMSO络合物；（ii）茚二酮主链和Pd中心共同作用以激活氨基甲酸中间体并促进其环化；（iii）质子穿梭对于降低初始胺羧化的活化势垒以及在Pd的配体主链与有机片段之间的质子转移是必不可少的。
更新日期：2017-03-17
中文翻译：
CO 2的平衡化：SCS茚二酮钯配合物的金属-配体协同催化制备2-恶唑烷酮
捕获和利用CO 2制备高价值化合物在化学上是非常有吸引力的，在社会上是非常合乎需要的。此处显示的基于茚二酮的Pd SCS钳形配合物可在温和的条件下（0.5-1 bar CO 2）促进炔丙基胺的羧基环化反应，生成2-恶唑烷酮，DMSO，40–80°C，1-5 mol％的Pd负载）。茚二酮Pd配合物与已知的催化剂竞争。事实证明，它可用于各种炔丙基胺，包括迄今具有挑战性的底物，例如在氮原子上带有叔烷基的仲炔丙基胺，伯炔丙基胺和炔丙基苯胺。进行了彻底的实验（NMR）和计算（DFT）研究，以获取机械方面的见解。因此，（i）催化循环的静止状态是Pd DMSO络合物；（ii）茚二酮主链和Pd中心共同作用以激活氨基甲酸中间体并促进其环化；（iii）质子穿梭对于降低初始胺羧化的活化势垒以及在Pd的配体主链与有机片段之间的质子转移是必不可少的。
京公网安备 11010802027423号