Regiocontrolled Synthesis and Optical Resolution of Mono-, Di-, and Trisubstituted Tribenzotriquinacene Derivatives: Key Building Blocks for Further Assembly into Molecular Squares and Cubes
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- 作者：Wen-Rong Xu ; Hak-Fun Chow ; Xiao-Ping Cao ; Dietmar Kuck
- 刊名：Journal of Organic Chemistry
- 出版年：2014
- 出版时间：October 3, 2014
- 年：2014
- 卷：79
- 期：19
- 页码：9335-9346
- 全文大小：689K
- ISSN：1520-6904
文摘
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, (卤)-18 and (卤)-20; 2,6-(OH)2, (卤)-19; and 2,6,10-(OMe)3, (卤)-21] by two different synthesis protocols are reported. Compounds (卤)-19, (卤)-20, and (卤)-21 and two (already-known) monosubstituted C1-symmetrical TBTQ analogues [2-OH (卤)-23 and 2-OMe (卤)-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, (卤)-18; 2-OMe, (卤)-22; and 2-OH, (卤)-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.