Iosub Andrei V, Stahl Shannon S
Department of Chemistry, University of Wisconsin-Madison, 1101 University Avenue, Madison, WI 53706, United States.
ACS Catal. 2016 Dec 2;6(12):8201-8213. doi: 10.1021/acscatal.6b02406. Epub 2016 Oct 24.
Catalytic dehydrogenation of saturated or partially saturated six-membered carbocycles into aromatic rings represents an appealing strategy for the synthesis of substituted arenes. Particularly effective methods have been developed for the dehydrogenation of cyclohexanones and cyclohexenes into substituted phenol, aniline, and benzene derivatives, respectively. In this Perspective, we present the contributions of our research group to the discovery and development of palladium-based catalysts for aerobic oxidative dehydrogenation methods, including general methods for conversion of cyclohexanones and cyclohexenones into substituted phenols and a complementary method for partial dehydrogenation cyclohexanones to cyclohexenones. The mechanistic basis for chemoselective conversion of cyclohexanones to phenols or enones is presented. These results are presented within the context of recent methods developed by others for the synthesis of aryl ethers, anilines and other substituted arenes. Overall, Pd-catalyzed dehydrogenation methods provide a compelling strategy for selective synthesis of aromatic and related unsaturated molecules.
将饱和或部分饱和的六元碳环催化脱氢转化为芳环是合成取代芳烃的一种有吸引力的策略。已经开发出特别有效的方法，分别将环己酮和环己烯脱氢转化为取代苯酚、苯胺和苯衍生物。在这篇综述中，我们介绍了我们研究小组在发现和开发用于有氧氧化脱氢方法的钯基催化剂方面所做的贡献，包括将环己酮和环己烯酮转化为取代苯酚的通用方法，以及将环己酮部分脱氢为环己烯酮的互补方法。文中还介绍了环己酮化学选择性转化为苯酚或烯酮的机理基础。这些结果是在其他人最近开发的用于合成芳基醚、苯胺和其他取代芳烃的方法的背景下呈现的。总体而言，钯催化脱氢方法为选择性合成芳香族及相关不饱和分子提供了一种引人注目的策略。
