Synthesis, Molecular Structure and Fluxional Behavior of (R)-7-p-Tolyldinaphtho[2,1-b;1′,2′-d]stibole: The First Isolated Example of Optically Active Group 15 Dinaphthoheteroles.
Synthesis, Molecular Structure and Fluxional Behavior of (R)-7-p-Tolyldinaphtho[2,1-b;1′,2′-d]stibole: The First Isolated Example of Optically Active Group 15 Dinaphthoheteroles.
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(R)-7-p-Tolyldinaphtho[2,1-b;1,2-d]stibole 的合成、分子结构和流动行为：光学活性第 15 族二萘杂醇的第一个孤立实例。
DOI：
10.1002/chin.200115180
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发表时间：
2001
期刊：
影响因子：
--
通讯作者：
J. Kurita
中科院分区：
文献类型：
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作者：
Shuji Yasuike;Tomoyasu Iida;K. Yamaguchi;H. Seki;J. Kurita
摘要光学活性2，2‘-二溴-1，1’-联萘(R)-(+)-2经叔丁基锂处理后，与2，2‘-二锂硫代-1，1’-联萘3原位缩合生成光学活性(R)-(−)-7-p-tolyldinaphtho[2，1-b；1′，2′-d]stibole 1c，在高温下在核磁共振时间尺度上是流动的。两个萘环的翻转能垒(ΔG‡)为85±1kJ−1，在20℃下苯中消旋的半衰期(t1/2)为5.2h。
Abstract The condensation of dibromo-p-tolylstibane with 2,2′-dilithio-1,1′-binaphthyl 3 , generated in situ from optically active 2,2′-dibromo-1,1′-binaphthyl (R)-(+)-2 by treatment with tert-butyllithium, afforded optically active (R)-(−)-7-p-tolyldinaphtho[2,1-b;1′,2′-d]stibole 1c , which is fluxional in the NMR time scale at elevated temperatures. The energy barrier (ΔG‡) resulting from the flipping of the two naphthalene rings was estimated to be 85±1 kJ mol−1 and its half life (t1/2) for racemization was determined to be 5.2 h in benzene at 20°C.