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Effective Guanidine‐Catalyzed Synthesis of Carbonate and Carbamate Derivatives from Propargyl Alcohols in Supercritical Carbon Dioxide
Advanced Synthesis & Catalysis ( IF 4.4 ) Pub Date : 2011-01-20 , DOI: 10.1002/adsc.201000607
Nicola Della Ca' , Bartolo Gabriele , Giuseppe Ruffolo , Lucia Veltri , Tito Zanetta , Mirco Costa

The reactions of propargyl alcohols with carbon dioxide in supercritical carbon dioxide or in acetonitrile with gaseous carbon dioxide in the presence of organic bases as catalysts have been examined. Bicyclic guanidines are effective catalysts for the formation of α‐methylene cyclic carbonates under mild reaction conditions. Oxoalkyl carbonates, oxoalkyl carbamates or α‐methyleneoxazolidinones are obtained in high yields and good selectivities in one‐step starting from propargyl alcohols and an external nucleophile (alcohols or amines) using bicyclic guanidines as catalysts in supercritical carbon dioxide. Propargylic diols under the same reaction conditions underwent a rearrangement process instead of carbon dioxide insertion whereas in the presence of an external nucleophile the formation of oxocarbonates, oxocarbamates or cyclic carbamates was achieved in satisfactory yields.

中文翻译:

在超临界二氧化碳中由丙炔醇有效胍催化催化合成碳酸盐和氨基甲酸酯衍生物

在有机碱作为催化剂存在下,研究了炔丙醇与二氧化碳在超临界二氧化碳中或在乙腈与气态二氧化碳中的反应。双环胍是在温和的反应条件下形成α-亚甲基环状碳酸酯的有效催化剂。碳酸氧烷基酯,氨基甲酸氧代烷基酯或α-亚甲基恶唑烷酮可从炔丙基醇和外部亲核试剂(醇或胺)开始,一步一步获得高收率和良好的选择性,其中双环胍作为催化剂在超临界二氧化碳中使用。在相同反应条件下,丙炔二醇经过重排过程,而不是二氧化碳的插入,而在存在外部亲核试剂的情况下,形成了碳酸氧根,
更新日期:2011-01-20
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