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Synthesis of novel 2,5-substituted p-aminophenols and 2,5-substituted p-quinones in a one-pot reaction between α-alkoxyvinyl(ethoxy)carbene complexes, amines and alkynes
Journal of Organometallic Chemistry ( IF 2.3 ) Pub Date : 2020-07-21 , DOI: 10.1016/j.jorganchem.2020.121360
Alberto Feliciano , Rosa Padilla , Carlos H. Escalante , José Enrique Herbert-Pucheta , Miguel A. Vázquez , Joaquín Tamariz , Francisco Delgado

The synthesis of novel p-aminophenols 19a-o and p-quinones 21a-i was carried out by an aminolysis reaction/[3 + 2+1] cycloaddition cascade process of α-alkoxyvinyl (ethoxy) Fischer carbene complexes of group 6 metals (M = Cr, Mo, W), primary and secondary amines and terminal alkynes. The multicomponent reaction of carbenes 1a-c with morpholine (6a) and piperidine (6c), respectively, and terminal alkynes 17a-d only afforded the 4-aminophenols 19a-o in moderated yields. The products bore the terminal alkyne substituent at the ortho position of the hydroxyl group. These one-pot reactions showed highly regio- and chemoselectivity, favoring the benzannulation products. When carbene complexes 1a-c were reacted with primary amines 10a-c and alkynes 17a-c under the same conditions, the cascade process led to the formation of p-quinones 21a-21i, in moderate yields. The regiochemistry of the compounds was established by NOE experiments, and the structures of morpholinocarbene 7a, p-aminophenols 19b, 19d and p-quinone 21b were confirmed by single-crystal X-ray diffraction.



中文翻译:

在α-烷氧基乙烯基(乙氧基)卡宾配合物,胺和炔烃的一锅反应中合成新型2,5-取代的氨基苯酚和2,5-取代的对苯

新的氨基苯酚19a - o对苯21a - i的合成是通过6族金属(α-烷氧基乙烯基(乙氧基)菲舍尔卡宾配合物)的氨解反应/ [3 + 2 + 1]环加成级联过程完成的。 M = Cr,Mo,W),伯胺和仲胺以及末端炔烃。卡宾斯1a - c分别与吗啉(6a)和哌啶(6c)以及末端炔烃17a-d的多组分反应仅产生4-氨基酚19a - o产量适中。产物在羟基的邻位带有末端炔烃取代基。这些一锅反应显示出高度的区域选择性和化学选择性,有利于苯环化产物。当卡宾络合物1a - c与伯胺10a - c和炔烃17a-c在相同条件下反应时,级联过程导致以中等收率形成对21a-21i。通过NOE实验确定了化合物的区域化学性质,吗啉卡宾7a氨基酚19b通过单晶X射线衍射确认了19d对苯21b

更新日期:2020-07-21
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