ZnI2/NEt3-Catalyzed Cycloaddition of CO2 with Propargylic Alcohols: Computational Study on Mechanism

doi:10.1002/cctc.201700771

CORC > 化学研究所 > 中国科学院化学研究所

	ZnI2/NEt3-Catalyzed Cycloaddition of CO2 with Propargylic Alcohols: Computational Study on Mechanism
	Ma, Jun1 ; Lu, Lu 1,2; Mei, Qingqing 1; Zhu, Qinggong 1; Hu, Jiayin 1; Han, Buxing 1,2
刊名	CHEMCATCHEM
	2017-11-09
卷号	9 期号:21 页码:4090-4097
关键词	Carbon Dioxide Fixation Cycloaddion Density Functional Calculations Reaction Mechanism Zinc
ISSN号	1867-3880
DOI	10.1002/cctc.201700771
英文摘要	The ZnI2(NEt3)/NEt3-catalyzed cycloaddition of CO2 with propargylic alcohols to alpha-alkylidene cyclic carbonates was studied by DFT calculations for the first time to explore the detailed reaction mechanism. By comparing the distinct CO2-activated and OH-activated pathways as well as the solvent effects of reactants and products, a complete picture of the metal-salt/base-catalyzed mechanism is provided, which involves four steps: deprotonation of propargylic alcohol, CO2 electrophilic attack, concerted metalation and intramolecular cyclization, and protonation to form the cyclic carbonates. With the polar solvent effects of reactants or products, the third step is the rate-determining step. The role of ZnII is activating the hydroxyl group, balancing of the charge of the alkylcarbonate anion and leading to the metalation. The base NEt3 acts as the proton-transfer bridge to promote the transfer of the proton. In addition, the selectivity of the five-membered cyclic carbonates has been investigated.
语种	英语
出版者	WILEY-V C H VERLAG GMBH
WOS记录号	WOS:000417441400011
内容类型	期刊论文
源URL	[http://ir.iccas.ac.cn/handle/121111/45205]
专题	中国科学院化学研究所
通讯作者	Ma, Jun; Han, Buxing
作者单位	1.Chinese Acad Sci, Inst Chem, Beijing Natl Lab Mol Sci, CAS Key Lab Colloid Interface & Chem Thermodynam, Beijing 100190, Peoples R China 2.Univ Chinese Acad Sci, Sch Chem & Chem Engn, Beijing 100049, Peoples R China
推荐引用方式 GB/T 7714	Ma, Jun,Lu, Lu,Mei, Qingqing,et al. ZnI2/NEt3-Catalyzed Cycloaddition of CO2 with Propargylic Alcohols: Computational Study on Mechanism[J]. CHEMCATCHEM,2017,9(21):4090-4097.
APA	Ma, Jun,Lu, Lu,Mei, Qingqing,Zhu, Qinggong,Hu, Jiayin,&Han, Buxing.(2017).ZnI2/NEt3-Catalyzed Cycloaddition of CO2 with Propargylic Alcohols: Computational Study on Mechanism.CHEMCATCHEM,9(21),4090-4097.
MLA	Ma, Jun,et al."ZnI2/NEt3-Catalyzed Cycloaddition of CO2 with Propargylic Alcohols: Computational Study on Mechanism".CHEMCATCHEM 9.21(2017):4090-4097.