Silver-Catalyzed Carbon Dioxide Incorporation and Rearrangement on Propargylic Derivatives
Silver-Catalyzed Carbon Dioxide Incorporation and Rearrangement on Propargylic Derivatives
复制标题
DOI：
10.1246/bcsj.20110078
复制
发表时间：
2011-07-15
影响因子：
4
通讯作者：
Yamada, Tohru
中科院分区：
文献类型：
--
作者：
Kikuchi, Satoshi;Yoshida, Shunsuke;Yamada, Tohru
以CO2为原料，分别与炔丙醇和炔丙胺反应，制备了一种银/DBU催化剂体系，在温和的条件下，高产率地合成了环状碳酸酯和恶唑烷酮。结果表明，在DMF中，炔丙醇发生[3，3]-σ迁移Meyer Schuster重排反应，得到相应的α，β-不饱和羰基化合物，产率较高。该银盐与手性Schiff碱配体的结合可用于CO2与各种双炔丙醇的对映选择性化学结合，以高产率和高对映选择性合成相应的环状碳酸酯。的绝对配置确定VCD光谱以及通过X-射线分析。发现这些产物对于氨解反应是活性的，以高产率提供相应的氨基甲酸酯衍生物而没有任何光学纯度损失。
A silver/DBU catalyst system was developed for the effective synthesis of cyclic carbonate and oxazolidinone from the reaction of CO2 with propargylic alcohols and propargylic amines, respectively, in high yields under mild conditions. It was found that the [3,3]-sigmatropic Meyer Schuster-type rearrangement of the propargylic alcohol was mediated by CO2 in DMF to afford the corresponding alpha,beta-unsaturated carbonyl compounds in high yields. The silver salt combined with the chiral Schiff base ligand could be applied to enantioselective chemical CO2 incorporation into various bispropargylic alcohols to produce the corresponding cyclic carbonate in high yields with high enantioselectivity. The absolute configuration was determined by VCD spectroscopy as well as by X-ray analysis. These products were found to be active for the aminolysis reaction to afford the corresponding carbamate derivatives in high yields without any loss of optical purity.