期刊
NATURE CHEMISTRY
卷 10, 期 6, 页码 615-624出版社
NATURE PORTFOLIO
DOI: 10.1038/s41557-018-0043-6
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资金
- University of Sydney
- Australian Research Council [DP0666378, DP0773847, DP150103137]
- National Natural Science Foundation of China (NSFC) [11674212]
- Shanghai High-End Foreign Experts Grant
- Australian Research Council [DP0666378, DP0773847] Funding Source: Australian Research Council
Isomerism is a fundamental chemical concept, reflecting the fact that the arrangement of atoms in a molecular entity has a profound influence on its chemical and physical properties. Here we describe a previously unclassified fundamental form of conformational isomerism through four resolved stereoisomers of a transoid (BF)O(BF)-quinoxalinoporphyrin. These comprise two pairs of enantiomers that manifest structural relationships not describable within existing IUPAC nomenclature and terminology. They undergo thermal diastereomeric interconversion over a barrier of 104 +/- 2 kJ mol(-1), which we term 'akamptisomerization'. Feasible interconversion processes between conceivable synthesis products and reaction intermediates were mapped out by density functional theory calculations, identifying bond-angle inversion (BAI) at a singly bonded atom as the reaction mechanism. We also introduce the necessary BAI stereodescriptors parvo and amplo. Based on an extended polytope formalism of molecular structure and stereoisomerization, BAI-driven akamptisomerization is shown to be the final fundamental type of conformational isomerization.
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