[123]Tetramantane: parent of a new family of sigma-helicenes.
[123]Tetramantane: parent of a new family of sigma-helicenes.
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[123]四金刚烷：西格玛螺烯新家族的母体。
DOI：
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发表时间：
2009
影响因子：
15
通讯作者：
R. Carlson
中科院分区：
文献类型：
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作者：
P. Schreiner;A. Fokin;H. Reisenauer;B. Tkachenko;E. Vass;M. Olmstead;D. Bläser;R. Boese;J. Dahl;R. Carlson
我们提出了一种基于类金刚石（纳米金刚石）框架的新型西格玛螺旋结构，C（2）-对称[123]四金刚烷，其（+）和（-）异构体可以通过HPLC技术进行对映分离。对映体纯烃的溴化导致分离出(+)-7-溴-[123]四金刚烷，其可以结晶并进行X射线结构分析。利用反常色散，我们确定该化合物为烃部分的 P 异构体。实验和计算的旋光色散 (ORD) 和振动圆二色性 (VCD) 光谱独立且与 X 射线结构分析一致，得出 M-(-) 作为第二洗脱母体烃异构体的构型。
We present a new type of sigma-helical structure based on a diamondoid (nanodiamond) framework, C(2)-symmetric [123]tetramantane, whose (+) and (-) isomers could be enantioseparated by HPLC techniques. Bromination of the enantiopure hydrocarbon led to the isolation of (+)-7-bromo-[123]tetramantane, which could be crystallized and subjected to X-ray structure analysis. Using the anomalous dispersion, we have identified this compound as the P isomer for the hydrocarbon moiety. Experimental and computed optical rotatory dispersion (ORD) and vibrational circular dichroism (VCD) spectra independently and in agreement with the X-ray structure analysis gave M-(-) as the configuration of the second eluted parent hydrocarbon isomer.