Department of Chemistry, Princeton University , Princeton, New Jersey 08544, United States.
J Am Chem Soc. 2016 Jan 27;138(3):766-9. doi: 10.1021/jacs.5b12249. Epub 2016 Jan 12.
Cobalt dialkyl and bis(carboxylate) complexes bearing α-diimine ligands have been synthesized and demonstrated as active for the C(sp(3))-H borylation of a range of substituted alkyl arenes using B2Pin2 (Pin = pinacolate) as the boron source. At longer reaction times, rare examples of polyborylation were observed, and in the case of toluene, all three benzylic C-H positions were functionalized. Coupling benzylic C-H activation with alkyl isomerization enabled a base-metal-catalyzed method for the borylation of remote, unactivated C(sp(3))-H bonds.
合成了含α-二亚胺配体的钴二烷基和双(羧酸盐)配合物,并证明它们在使用 B2Pin2(Pin = 频哪醇)作为硼源时对一系列取代的烷基芳基的 C(sp(3))-H 硼化反应具有活性。在较长的反应时间内,观察到了罕见的多硼化实例,而在甲苯的情况下,三个苄位 C-H 位置都被官能化了。将苄基 C-H 活化与烷基异构化偶联,为远程、非活化的 C(sp(3))-H 键的硼化提供了一种基底金属催化方法。