Xu Wen-Rong, Chow Hak-Fun, Cao Xiao-Ping, Kuck Dietmar
Department of Chemistry, Center of Novel Functional Materials and State Key Laboratory of Synthetic Chemistry, The Chinese University of Hong Kong , Shatin, Hong Kong SAR.
J Org Chem. 2014 Oct 3;79(19):9335-46. doi: 10.1021/jo501904y. Epub 2014 Sep 23.
The regiocontrolled syntheses of four chiral C1- or C3-symmetrical tribenzotriquinacene (TBTQ) derivatives bearing methoxy or hydroxy groups at the peripheral positions [(2,6-(OMe)2, (±)-18 and (±)-20; 2,6-(OH)2, (±)-19; and 2,6,10-(OMe)3, (±)-21] by two different synthesis protocols are reported. Compounds (±)-19, (±)-20, and (±)-21 and two (already-known) monosubstituted C1-symmetrical TBTQ analogues [2-OH (±)-23 and 2-OMe (±)-24] were readily resolved by chiral HPLC, and their absolute configurations were determined by X-ray crystallography and/or circular dichroism (CD) studies. Optical resolution of three closely related TBTQ derivatives [2,6-(OMe)2, (±)-18; 2-OMe, (±)-22; and 2-OH, (±)-25] containing the same peripheral substituents but other bridgehead residues failed. Enantiopure TBTQ derivatives of this sort are considered promising structural motifs toward the construction of molecular squares and cubes.
报道了通过两种不同的合成方法对四种在外围位置带有甲氧基或羟基的手性C1或C3对称三苯并三喹啉（TBTQ）衍生物[(2,6-(OMe)2, (±)-18和(±)-20；2,6-(OH)2, (±)-19；以及2,6,10-(OMe)3, (±)-21]进行区域控制合成。化合物(±)-19、(±)-20和(±)-21以及两种（已报道过的）单取代C1对称TBTQ类似物[2-OH (±)-23和2-OMe (±)-24]通过手性高效液相色谱法很容易拆分，其绝对构型通过X射线晶体学和/或圆二色性（CD）研究确定。三种含有相同外围取代基但其他桥头残基的密切相关的TBTQ衍生物[2,6-(OMe)2, (±)-18；2-OMe, (±)-22；以及2-OH, (±)-25]的对映体拆分失败。这类对映体纯的TBTQ衍生物被认为是构建分子正方形和立方体的有前景的结构基序。
