Stereoselective formation of α-alkylidene cyclic carbonates via carboxylative cyclization of propargyl alcohols in supercritical carbon dioxide
Stereoselective formation of α-alkylidene cyclic carbonates via carboxylative cyclization of propargyl alcohols in supercritical carbon dioxide
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DOI：
10.1021/jo062094m
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发表时间：
2007-01-19
影响因子：
3.6
通讯作者：
Ikariya, Takao
中科院分区：
文献类型：
--
作者：
Kayaki, Yoshihito;Yamamoto, Masafumi;Ikariya, Takao
以P（n-C_4 H_9）（3）为催化剂，在超临界CO_2（scCO（2））中，炔丙醇的羧化环化反应顺利进行，得到了α-亚烷基-1，3-二氧戊环-2-酮。内炔丙醇仅得到Z-亚烷基环状碳酸酯。在超临界条件下，CO2的掺入显著促进，这可能是由于容易形成推定的P（n-C4 H9）（3）-CO2加合物作为关键中间体。
Carboxylative cyclization of propargyl alcohols in supercritical carbon dioxide (scCO(2)) containing P(n-C4H9)(3) as a catalyst proceeded smoothly to give alpha-alkylidene-1,3-dioxolan-2-ones. Internal propargyl alcohols afforded Z-alkyl-idene cyclic carbonates exclusively. CO2 incorporation was markedly promoted under supercritical conditions, possibly due to the facile formation of a putative P(n-C4H9)(3)-CO2 adduct as a key intermediate.