Palladium‐Catalyzed Hydroesterification of Alkynes Employing Aryl Formates without the Use of External Carbon Monoxide
Palladium‐Catalyzed Hydroesterification of Alkynes Employing Aryl Formates without the Use of External Carbon Monoxide
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DOI：
10.1002/adsc.201000750
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发表时间：
2011-02
影响因子：
5.4
通讯作者：
Yuko Katafuchi;Tetsuaki Fujihara;Tomohiro Iwai;J. Terao;Y. Tsuji
中科院分区：
文献类型：
--
作者：
Yuko Katafuchi;Tetsuaki Fujihara;Tomohiro Iwai;J. Terao;Y. Tsuji
本文报道了一种不需外加一氧化碳和常压下使用甲酸芳基酯进行炔基氢酯化反应的高效方法。在钯-xantphos催化剂体系存在下的反应以良好至高产率选择性地提供α，β-不饱和酯。甲酸芳基酯的使用是至关重要的，甲酸烷基酯根本不反应。在相似的反应条件下，异戊烯和末端烯烃的氢酯化反应也容易进行。机理研究表明，甲酸芳基酯转化为一氧化碳和苯酚衍生物发生在氢酯化。Xantphos作为配体在甲酸芳基酯的转化和加氢酯化反应中都是非常有效的。
A highly efficient hydroesterification of alkynes employing aryl formates has been developed without the use of external carbon monoxide and at ambient pressure. The reaction in the presence of a palladium-xantphos catalyst system selectively affords α,β-unsaturated esters in good to high yields. Use of an aryl formate is crucial and alkyl formates did not react at all. The hydroesterification of norbornene and terminal alkenes also readily proceeded under similar reaction conditions. A mechanistic study showed that conversion of aryl formates to carbon monoxide and phenol derivatives occurred in the hydroesterification. Xantphos is highly effective as a ligand both in the conversion of aryl formates and the hydroesterification reactions.