Probing the Regioselectivity with Encapsulated H2: Diels-Alder Reaction of an Open-Cage C60 Derivative with Anthracene
Probing the Regioselectivity with Encapsulated H2: Diels-Alder Reaction of an Open-Cage C60 Derivative with Anthracene
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DOI：
10.1002/chem.201806030
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发表时间：
2019-02-18
影响因子：
4.3
通讯作者：
Murata, Yasujiro
中科院分区：
文献类型：
--
作者：
Hashikawa, Yoshifumi;Murata, Yasujiro
研究了不对称开笼C-60衍生物与蒽的Diels-Alder反应的区域选择性。通过使用包封的H-2分子作为磁性探针，成功地详细评价了产物群体，表明形成了约10种化合物作为主要组分。核独立化学位移（NICS）的计算表明，所观察到的H-1 NMR谱，这使得一个简单的表征产品的密切相似。还对所有29种可能的蒽加合物的形成进行了理论研究。结果表明，区域选择性受空间位阻因子、前线轨道系数和热力学稳定性的影响。主要化合物的单晶X-射线分析揭示了蒽部分和相邻分子的π-球之间的超分子结构。
The regioselectivity in the Diels-Alder reaction of an unsymmetrical open-cage C-60 derivative with anthracene was studied. By using an encapsulated H-2 molecule as a magnetic probe, the product population was successfully evaluated in detail, indicating the formation of approximately ten compounds as major components. The nucleus-independent chemical shift (NICS) calculations showed a close resemblance to the observed H-1 NMR spectrum, which allowed for a facile characterization of the products. Theoretical studies on the formation of all 29 possible anthracene adducts were also performed. The results indicated that the regioselectivity is strongly governed by steric factors, values of the frontier orbital coefficients, and thermodynamic stabilities. Single-crystal X-ray analysis of the dominant compound revealed the supramolecular architecture between the anthracene moiety and the pi-sphere of a neighboring molecule.