Rhodium-catalyzed substitution reaction of aryl fluorides with disulfides:: p-orientation in the polyarylthiolation of polyfluorobenzenes
Rhodium-catalyzed substitution reaction of aryl fluorides with disulfides:: p-orientation in the polyarylthiolation of polyfluorobenzenes
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DOI：
10.1021/ja8049996
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发表时间：
2008-09-17
影响因子：
15
通讯作者：
Yamaguchi, Masahiko
中科院分区：
文献类型：
--
作者：
Arisawa, Mieko;Suzuki, Takaaki;Yamaguchi, Masahiko
在催化量的RhH（PPh 3）（4）和1，2-双（二苯基膦基）苯的存在下，芳族氟化物、有机二硫化物（0.5当量）和三苯基膦（0.5当量）在三氯苯中反应，以高产率得到芳基硫醚。由于三苯基膦捕获氟原子形成二氟化膦，二硫化物的两个有机硫基有效地反应，并且氟取代基比氯和溴更容易反应。六氟苯与二芳基二硫醚反应，分步得到1，4-二芳硫基-2，3，5，6-四氟苯、1，2，4，5-四芳硫基-3，6-二氟苯和六芳硫基苯，五氟苯得到1-芳硫基-2，3，5，6-四氟苯，1，2，3，4-四氟苯得到1，2-二芳硫基-3，6-二氟苯，六氟苯得到1，4-二芳硫基-2，3，5，6-四氟苯，六氟苯得到1，4-二芳硫基-2，3，4-四氟苯，六氟苯得到1，4-二芳硫基-2，3，6-二氟苯。与1，2，4，5-四氟苯反应得到1，4-二芳硫基-2-5-二氟苯。多氟苯的多芳基硫醇化反应表现出强烈的生成1，4-二氟苯的倾向。
In the presence of a catalytic amount of RhH(PPh3)(4) and 1,2-bis (diphenylphosphino)benzene, an aromatic fluoride, an organic disulfide (0.5 equiv), and triphenylphosphine (0.5 equiv) reacted in refluxing chlorobenzene to give an aryl sulfide in high yield. Since triphenylphosphine trapped fluoride atoms forming phosphine difluoride, both organothio groups of the disulfide reacted effectively, and the fluoride substituent reacted more readily than the chloride and bromide. The reaction of hexafluorobenzene and a diaryl disulfide gave 1,4-diarylthio-2,3,5,6-tetrafluorobenzene, 1,2,4,5-tetraarylthio-3,6-difluorobenzene, and hexaarylthiobenzene in a stepwise manner; pentafluorobenzene gave 1-arthio-2,3,5,6-tetrafluorobenzene; 1,2,3,4-tetrafluorobenzene gave 1,2-diarylthio-3,6-difluorobenzene; and 1,2,4,5-tetrafluorobenzene gave 1,4-diarylthio-2-5-difluorobenzene. The polyarylthiolation reaction of polyfluorobenzenes exhibited a strong tendency to form 1,4-difiuorobenzenes.