Stereospecific α-Hydrogen Exchange in Camphor, Isofenchone, and Carvonecamphor
Stereospecific α-Hydrogen Exchange in Camphor, Isofenchone, and Carvonecamphor
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樟脑、异芬酮和碳樟脑中的立体特异性 α-氢交换
DOI：
10.1021/ja00977a014
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发表时间：
1967
影响因子：
15
通讯作者：
J. Meinwald
中科院分区：
文献类型：
--
作者：
Alan F. Thomas;R. A. Schneider;J. Meinwald
mfo-a-氘樟脑 (8) 和 ew/oa-氘代异茴香酮 (11) 是通过碱催化从相应的二氘代酮中除去一个氘原子而获得。这些结果证实了这两种双环的趋势[2.2。 1]庚烷-2-酮用于选择性交换外型-α-氢原子。就樟脑而言，涉及一些未被识别的空间或立体电子因子的运作。类似的技术可以制备具有高度立体特异性的 exo- 和 ew/oa-氘化香芹酮樟脑（13 和 14）。作为偶然的结果，几个单氘代双环的核磁共振谱[2.2。 1] heptan-2-ol 衍生物表明，观察到的邻位耦合常数 (72, 3) 与基于未失真双环的预期一致 [2.2。 1]庚基核。
mfo-a-Deuteriocamphor (8) and ew/oa-deuterioisofenchone (11) are obtained by base-catalyzed removal of one deuterium atom from the corresponding dideuterated ketones. These results confirm the tendency in both of these bicyclo [2.2. 1] heptan-2-ones for the exo-a-hydrogen atom to be exchanged selectively. In the case of camphor, the operation of some unrecognized steric or stereoelectronic factor is implicated. Analogous techniques allow the preparation of exo- and ew/oa-deuteriocarvonecamphors (13 and 14) with a high degree of stereospecificity. As an incidental result, the nmr spectra of several monodeuterated bicyclo [2.2. 1] heptan-2-ol derivatives show that the observed vicinal coupling constants (72, 3) are consistent with expectations based on an undistorted bicyclo [2.2. 1] heptyl nucleus.