期刊
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
卷 141, 期 5, 页码 2104-2110出版社
AMER CHEMICAL SOC
DOI: 10.1021/jacs.8b11797
关键词
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资金
- European FP7-ITN MOLESCO [606728]
- Swiss National Science Foundation (SNF) [200020-178808, PZ00P2_174175]
- Swiss Nanoscience Institute (SNI)
- 111 project [90002-18011002]
- Swiss National Science Foundation (SNF) [PZ00P2_174175] Funding Source: Swiss National Science Foundation (SNF)
We introduce a design principle to stabilize helically chiral structures from an achiral tetrasubstituted [2.2]paracyclophane by integrating it into a macrocycle. The [2.2]paracyclophane introduces a three-dimensional perturbation into a nearly planar macrocyclic oligothiophene. The resulting helical structure is stabilized by two bulky substituents installed on the [2.2]paracyclophane unit. The increased enantiomerization barrier enabled the separation of both enantiomers. The synthesis of the target helical macrocycle 1 involves a sequence of halogenation and cross-coupling steps and a high-dilution strategy to close the macrocycle. Substituents tuning the energy of the enantiomerization process can be introduced in the last steps of the synthesis. The chiral target compound 1 was fully characterized by NMR spectroscopy and mass spectrometry. The absolute configurations of the isolated enantiomers were assigned by comparing the data of circular dichroism spectroscopy with TD-DFT calculations. The enantiomerization dynamics was studied by dynamic HPLC and variable-temperature 2D exchange spectroscopy and supported by quantum-chemical calculations.
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