Department of Chemistry, University of Illinois at Chicago , 845 West Taylor Street, Chicago, Illinois 60607-7061, United States.
Org Lett. 2018 Jan 19;20(2):357-360. doi: 10.1021/acs.orglett.7b03591. Epub 2018 Jan 5.
The efficient Pd-catalyzed Heck reaction of diverse tertiary alkyl halides with alkenes has been developed. Unactivated tertiary alkyl halides efficiently react at room temperature under visible light irradiation with no exogenous photosensitizers required. For activated tertiary alkyl halides, the same catalytic system works well without light. These methods offer a general access to electronically diverse alkenes possessing quaternary and functionalized tertiary allylic carbon centers. The substituents at these centers include alkyl-, carbalkoxy-, tosyl-, phosphonyl-, and boronate groups. It was also shown that the end-game mechanism of this transformation may vary depending on the type of the substrates used.
发展了一种高效的 Pd 催化的各种叔卤代烃与烯烃的 Heck 反应。在可见光照射下，无需外加光敏剂，未活化的叔卤代烃在室温下即可高效反应。对于活化的叔卤代烃，相同的催化体系在没有光照的情况下也能很好地发挥作用。这些方法为具有季碳和功能化的叔烯丙基碳中心的电子多样性的烯烃提供了一种通用的合成途径。这些中心的取代基包括烷基、碳烷氧基、对甲苯磺酰基、膦酰基和硼酸酯基。还表明，这种转化的终态机制可能取决于所用底物的类型而有所不同。
