A route to 2-substituted tetrahydroquinolines via palladium-catalyzed intramolecular hydroamination of anilino-alkynes.
A route to 2-substituted tetrahydroquinolines via palladium-catalyzed intramolecular hydroamination of anilino-alkynes.
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DOI：
10.1021/jo0708137
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发表时间：
2007-07
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影响因子：
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通讯作者：
N. Patil;Huanyou Wu;Yoshinori Yamamoto
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文献类型：
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作者：
N. Patil;Huanyou Wu;Yoshinori Yamamoto
使用催化量的Pd（PPh 3）4和苯甲酸在甲苯中在120 ℃下顺利地进行其中氨基连接到芳环的氨基-炔1的环化，导致形成2-取代的四氢喹啉2。还探索了使用手性钯催化剂（通过混合Pd 2（dba）3.CHCl3和（R，R）-RENORPHOS原位制备）的反应的不对称变体。通过将以这种方式获得的对映体富集的四氢喹啉转化为已知化合物来确定其绝对构型，并且发现其为R。以该反应为关键步骤合成了（+/-）-galipinine、（+/-）-angustureine等生物碱及其光学活性形式。
The cyclization of amino-alkynes 1 in which an amino group is attached to the aromatic ring, proceeded smoothly using a catalytic amount of Pd(PPh3)4 and benzoic acid in toluene at 120 degrees C, leading to the formation of the 2-substituted tetrahydroquinolines 2. An asymmetric variant of the reaction using the chiral palladium catalyst (prepared in situ by mixing Pd2(dba)3.CHCl3 and (R,R)-RENORPHOS) was also explored. The absolute configuration of the enantiomerically enriched tetrahydroquinolines, obtained in this way, was determined by converting them to the known compounds and was found to be R. The alkaloids such as (+/-)-galipinine, (+/-)-angustureine, and their optically active form were synthesized by using this reaction as a key step.