Trofimov Boris A, Volkov Pavel A, Telezhkin Anton A, Khrapova Kseniya O, Ivanova Nina I, Albanov Alexander I, Gusarova Nina K
A.E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences, 1 Favorsky St., Irkutsk 664033, Russian Federation.
J Org Chem. 2020 Apr 3;85(7):4927-4936. doi: 10.1021/acs.joc.0c00084. Epub 2020 Mar 25.
Quinolines undergo catalyst-free double CH-functionalization upon treatment with secondary phosphine oxides (70-75 °C, 20-48 h) followed by oxidation of the intermediate 2,4-bisphosphoryltetrahydroquinolines with chloranil. The yields of the target 2,4-bisphosphorylated quinolines are up to 77%. Thus, a double-SAr reaction sequence in the same molecule of quinoline has been realized. In the case of 2,4-bisphenylphosphoryltetrahydroquinolines, the aromatization occurs with elimination of one molecule of diphenylphosphine oxide to afford the products of monofunctionalization, 4-diphenylphosphorylquinolines, in 40-45% yields.
喹啉在与仲膦氧化物反应（70 - 75 °C，20 - 48 h）后进行无催化剂的双CH官能化反应，随后用四氯对苯醌氧化中间体2,4 - 双磷酰基四氢喹啉。目标2,4 - 双磷酰化喹啉的产率高达77%。因此，在喹啉的同一分子中实现了双亲核芳环取代反应序列。对于2,4 - 双苯基磷酰基四氢喹啉，芳构化过程中消除一分子二苯基氧化膦，得到单官能化产物4 - 二苯基磷酰基喹啉，产率为40 - 45%。
