Synthesis, structure, and functionalization of homo heterocalix[2]arene[2]triazines: versatile conformation and cavity structures regulated by the bridging elements.
Synthesis, structure, and functionalization of homo heterocalix[2]arene[2]triazines: versatile conformation and cavity structures regulated by the bridging elements.
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DOI：
10.1021/jo100571c
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发表时间：
2010-05
期刊：
影响因子：
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通讯作者：
Yin Chen;De‐Xian Wang;Zhi-tang Huang;Mei-Xiang Wang
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文献类型：
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作者：
Yin Chen;De‐Xian Wang;Zhi-tang Huang;Mei-Xiang Wang
以三聚氰酸卤化物、芳香族和脂肪族二醇、二胺为起始原料，通过一种普遍的、产率较高的片段偶联方法，在非常温和的反应条件下合成了许多高[2]和高[4]杂杯[2]芳烃[2]三嗪类化合物。而同[2]四氮杂杯[2]芳烃[2]三嗪的1，2-交替扭曲构象，几乎所有的同[2]杂杯[2]芳烃[2]三嗪在固态下都采用不同的部分锥形构象。Homo[4]杂杯[2]芳烃[2]三嗪类化合物根据桥联基团的性质不同，产生了不同的构象结构，包括部分锥体、被挤压的部分锥体、1，2-交替和扭曲的1，2-交替。根据(1)~1H核磁共振谱，高[2]和高[4]杂杯[2]芳烃[2]三嗪在溶液中是流动的大环，它们在不同温度下发生了快速构象转换。高效、直接的亲核芳香取代反应和钯催化的氯三氮环上的交叉偶联反应，以及桥氮原子上的亲核烷基化反应，导致了各种高官能化的高杂杯[2]芳烃[2]三嗪衍生物的构建。
A number of homo[2] and homo[4] heterocalix[2]arene[2]triazines were synthesized through a general and good-yielding fragment coupling approach starting from cyanuric halides, aromatic and aliphatic diols, and diamines under very mild reaction conditions. While homo[2] tetraazacalix[2]arene[2]triazine gave a twisted and pinched 1,2-alternate conformer, almost all homo[2] heterocalix[2]arene[2]triazines adopted different partial cone conformations in the solid state. Homo[4] heterocalix[2]arene[2]triazines yielded more diverse conformational structures including partial cone, pinched partial cone, 1,2-alternate and twisted 1,2-alternate, depending on the nature of bridging moieties. On the basis of (1)H NMR spectra, homo[2] and homo[4] heterocalix[2]arene[2]triazines were fluxional macrocycles in solution, and they underwent rapid conformation interconversion at different temperatures. Efficient and straightforward nucleophilic aromatic substitution reaction and palladium-catalyzed cross-coupling reactions on chlorotriazine rings, and the nucleophilic alkylation reaction on the bridging nitrogen atoms led to the construction of various highly functionalized homo heterocalix[2]arene[2]triazine derivatives.