Department of Chemistry, University at Buffalo, the State University of New York, Amherst, New York 14260, United States.
J Org Chem. 2022 Nov 4;87(21):14078-14092. doi: 10.1021/acs.joc.2c01678. Epub 2022 Oct 12.
The ene-yne metathesis of alkenyl boronates with terminal alkynes is reported. These challenging metatheses were accomplished using a Grubbs catalyst bearing the cyclic alkyl amino carbene (CAAC) ligand, whereas -heterocyclic carbene (NHC) derived catalysts gave lower yields. Subsequent dienyl isomerization via a cobalt-catalyzed hydrogen atom transfer (HAT) furnished the more substituted dienyl boronate with high / ratios. Finally, the resulting dienyl boronate products were successfully used in Suzuki-Miyaura cross-coupling reactions and in a Diels-Alder cycloaddition.
报道了烯基硼酸酯与末端炔烃的烯炔复分解反应。这些具有挑战性的复分解反应是使用带有环状烷基氨基卡宾（CAAC）配体的 Grubbs 催化剂完成的，而 -杂环卡宾（NHC）衍生的催化剂产率较低。随后通过钴催化的氢原子转移（HAT）进行二烯基异构化，得到高 / 比的取代基更多的二烯基硼酸酯。最后，所得的二烯基硼酸酯产物成功地用于 Suzuki-Miyaura 交叉偶联反应和 Diels-Alder 环加成反应。
