Miyazaki Mayu, Ura Yasuyuki
Department of Chemistry, Biology, and Environmental Science, Faculty of Science, Nara Women's University, Kitauoyanishi-machi, Nara 630-8506, Japan.
ACS Omega. 2023 Oct 23;8(44):41983-41990. doi: 10.1021/acsomega.3c07577. eCollection 2023 Nov 7.
The Wacker-type oxidation of aliphatic terminal alkenes proceeds using a Pd/Fe catalyst system under mild reaction conditions using 1 atm O without other additives. The use of 1,2-dimethoxyethane/HO as a mixed solvent was effective. The slow addition of alkenes is also important for improving product yields. Fe(III) citrate was the most efficient cocatalyst among the iron complexes examined, whereas other complexes such as FeSO, Fe(SO), Fe(NO), and FeO were also operative. This method is also applicable to aliphatic internal alkenes, which are generally difficult to oxidize using conventional Pd/Cu catalyst systems. The gram-scale synthesis and reuse of the Pd catalysts were also demonstrated.
脂肪族末端烯烃的瓦克型氧化反应在温和的反应条件下，使用钯/铁催化剂体系，在1个大气压的氧气氛围中且无需其他添加剂即可进行。使用1,2 - 二甲氧基乙烷/水作为混合溶剂是有效的。缓慢加入烯烃对于提高产物产率也很重要。在所研究的铁配合物中，柠檬酸铁（III）是最有效的助催化剂，而其他配合物如硫酸亚铁、硫酸铁（III）、硝酸铁和氧化铁也有催化作用。该方法也适用于脂肪族内烯烃，而脂肪族内烯烃通常难以使用传统的钯/铜催化剂体系进行氧化。同时也展示了钯催化剂的克级合成及重复使用。
