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Title: Conformational behavior of dithia[n.3.3](1,3,5)cyclophanes and dithia[n.3.3](1,2,6)cyclophanes
Authors: Xu, J.-W.
Lin, T.-T.
Lai, Y.-H. 
Keywords: (1,2,6)Cyclophane
Issue Date: 28-Feb-2005
Citation: Xu, J.-W., Lin, T.-T., Lai, Y.-H. (2005-02-28). Conformational behavior of dithia[n.3.3](1,3,5)cyclophanes and dithia[n.3.3](1,2,6)cyclophanes. Tetrahedron 61 (9) : 2431-2440. ScholarBank@NUS Repository.
Abstract: The conformational behavior of a series of crown-fused dithia[n.3.3](1,2,6) cyclophanes (126-CPs) and dithia[n.3.3](1,3,5)cyclophanes (135-CPs) was investigated by variable-temperature 1H and 13C NMR spectroscopy, X-ray crystallography and density functional theory (DFT) calculations. Single crystal X-ray structure analysis showed that two thia-bridges in 126-CPs adopted a pseudochair-pseudochair (cc) conformation and the cyclophane decks underwent a ring-tilting motion in the case of [10.3.3](1,2,6)cyclophane (1a). In contrast, the thia-bridges in 135-CPs took both cc and pseudoboat-pseudochair (bc) conformations, and the ring-tilting process was also found in [10.3.3](1,3,5)cyclophane (2a). Variable temperature 1H NMR study revealed that there was no wobbling-motion for two thia-bridges in 126-CPs while thia-bridges in 135-CPs experienced a wobbling-process with a conformational barrier of 9.21 and 8.80 kcal mol -1, respectively, for 2a and [13.3.3](1,3,5)cyclophane (2b). DFT calculations for the two cyclophanes series revealed that 126-CPs preferred a cc conformation which was consistent with the experimental observation; similarly, 135-CPs took a preferential cc conformation, agreeing with 2a having a predominant cc conformer (cc:bc ratio=70:30), but not 2b having a predominant bc conformer (cc:bc ratio=15:85) in the solid state. © 2005 Elsevier Ltd. All rights reserved.
Source Title: Tetrahedron
ISSN: 00404020
DOI: 10.1016/j.tet.2005.01.027
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