Asymmetric synthesis of a chiral buckybowl, trimethylsumanene
Asymmetric synthesis of a chiral buckybowl, trimethylsumanene
复制标题
DOI：
10.1021/ja802822k
复制
发表时间：
2008-07-09
影响因子：
15
通讯作者：
Sakurai, Hidehiro
中科院分区：
文献类型：
--
作者：
Higashibayashi, Shuhei;Sakurai, Hidehiro
手性巴基碗，一个C-3对称的（C）-8，13，18-三甲基苏曼烯（1）的第一个不对称合成，通过采用一种合成策略，在sp（3）中心的手性转化为碗手性。该合成的特征在于对映体纯卤代降冰片烯衍生物的顺式选择性环三聚、串联的开环/闭环烯烃复分解反应和低温下的DDQ氧化。通过圆二色光谱测量，确定1的碗到碗的反转能为21.6kcal/mol。
The first asymmetric synthesis of a chiral buckybowl, a C-3 symmetric (C)-8,13,18-trimethylsumanene (1), was achieved by employing a synthetic strategy that translates chirality at sp(3) centers into bowl chirality. The synthesis features a syn selective cyclotrimerization of an enantiopure halonorbornene derivative, tandem ring-opening/closing olefin metathesis reactions, and DDQ oxidation at low temperature. The bowl-to-bowl inversion energy of 1 was determined as 21.6 kcal/mol by circular dichroism spectra measurement.