Ibragimova Regina, Lu Qiu-Lin, Wang Mei-Xiang, Zhu Jieping, Tong Shuo
Key Laboratory of Bioorganic Phosphorus Chemistry and Chemical Biology (Ministry of Education), Department of Chemistry, Tsinghua University, Beijing, 100084, China.
Laboratory of Synthesis and Natural Products (LSPN), Institute of Chemical Sciences and Engineering, Ecole Polytechnique Fédérale de Lausanne, EPFL-SB-ISIC-LSPN, BCH5304, CH-1015, Lausanne, Switzerland.
Chem Asian J. 2025 May 2;20(9):e202401621. doi: 10.1002/asia.202401621. Epub 2025 Feb 11.
Potassium phosphate-promoted cross-cyclotetramerization of 2,6-dichloro-3-nitropyridine 1 with resorcinol derivatives 2 gave rise to thermodynamically favored 1,3-alternate tetraoxacalix[2]arene[2]pyridines and kinetically controlled 1,2-alternate isomers. The kinetic product could convert into its 1,3-alternate conformational isomer by a macrocycle to macrocycle conversion pathway. Enantiomerically enriched C-symmetric inherently chiral tetraoxacalix[2]arene[2]pyridines were synthesized via a Cinchonine-derived chiral phase-transfer catalyst (PTC). This synthesis involved the cross-cyclotetramerization of 1 with 2, featuring a key enantioselective intramolecular aromatic nucleophilic substitution (SAr) step.
磷酸钾促进2,6-二氯-3-硝基吡啶1与间苯二酚衍生物2的交叉环四聚反应，生成热力学上有利的1,3-交替四氧杂杯[2]芳烃[2]吡啶和动力学控制的1,2-交替异构体。动力学产物可通过大环到大环的转化途径转化为其1,3-交替构象异构体。通过金鸡宁衍生的手性相转移催化剂（PTC）合成了对映体富集的C对称固有手性四氧杂杯[2]芳烃[2]吡啶。该合成涉及1与2的交叉环四聚反应，其特征在于关键的对映选择性分子内芳香亲核取代（SAr）步骤。
