Yoshida Masahiro, Fujita Mika, Ishii Tooru, Ihara Masataka
Department of Organic Chemistry, Graduate School of Pharmaceutical Sciences, Tohoku University, Aobayama, Sendai 980-8578, Japan.
J Am Chem Soc. 2003 Apr 23;125(16):4874-81. doi: 10.1021/ja0340681.
A palladium-catalyzed CO(2)-recycling reaction has been developed. Reaction of 4-methoxycarbonyloxy-2-butyn-1-ols with phenols, carried out in the presence of a palladium catalyst, produces phenoxy-substituted cyclic carbonates by way of a pathway involving a CO(2) elimination-fixation. A variety of propargylic alcohols and phenols participate in these reactions which yield cyclic carbonates with high efficiencies. Stereoselective construction of trans-cyclic carbonates is achieved by using nonsymmetric substrates. Highly enantioselective reactions occur when (S)-BINAP is used as a ligand. Reaction of 4-phenoxycarbonyloxy-2-butyn-1-ol in the presence of the palladium catalyst yields the corresponding cyclic carbonates via a three-component decomposition-reconstruction process.
已开发出一种钯催化的二氧化碳循环反应。在钯催化剂存在下，4-甲氧基羰氧基-2-丁炔-1-醇与酚反应，通过涉及二氧化碳消除-固定的途径生成苯氧基取代的环状碳酸酯。多种炔丙醇和酚参与这些反应，能高效生成环状碳酸酯。使用不对称底物可实现反式环状碳酸酯的立体选择性构建。当使用(S)-联萘二苯膦作为配体时，会发生高度对映选择性反应。4-苯氧基羰氧基-2-丁炔-1-醇在钯催化剂存在下反应，通过三组分分解-重构过程生成相应的环状碳酸酯。
