TY - JOUR
T1 - Synthesis, Structures and Conformational Studies of 1,2-Dimethyl[2.10]metacyclophan-1-enes
AU - Akther, Thamina
AU - Islam, Md Monarul
AU - Rahman, Shofiur
AU - Georghiou, Paris E.
AU - Matsumoto, Taisuke
AU - Tanaka, Junji
AU - Thuéry, Pierre
AU - Redshaw, Carl
AU - Yamato, Takehiko
N1 - Funding Information:
We would like to thank the OTEC at Saga University and the International Collaborative Project Fund of Guizhou province at Guizhou University for financial support. We also would like to thank the EPSRC (overseas travel grant to C.R.) for financial support. The computational work has been assisted by the use of computing facilities provided by and with the on-going support of Dr. G. Shamov of Compute/Calcul Canada via the West-grid and Acenet facilities.
Publisher Copyright:
© 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
PY - 2016/8/16
Y1 - 2016/8/16
N2 - A series of 1,2-dimethyl[2.10]metacyclophan-1-enes (MCP-1-enes) containing different substituent groups has been synthesized to illustrate their conformational behavior. 4,22-dimethoxy-1,2-dimethyl[2.10]MCP-1-ene 3 was synthesized by a Grignard coupling reaction, Friedel-Crafts acylation reactions and McMurry coupling reaction from 1,10-dibromodecane. The formation of 4,22-dihydroxy-1,2-dimethyl[2.10]MCP-1-ene 4 was carried out by demethylation of compound 3 with boron tribromide at room temperature. The syn type conformation of 4 was characterized by X-ray diffraction and was found to form both intramolecular and intermolecular hydrogen bonds between the two hydroxyl groups. From this reaction an interesting compound [10]tetrahydrobenzofuranophane 5 was afforded on prolonging the reaction time. 5,21-diformyl-4,22-dihydroxy-1,2-dimethyl[2.10]MCP-1-ene 6 has been prepared from 4,22-dihydroxy-1,2-dimethyl[2.10]MCP-1-ene 4 by using the Duff method in the presence of hexamethylenetetramine. Structural analysis by 1H NMR spectroscopy and X-ray diffraction confirmed that both the solution and the crystalline state of compound 6 adopts an anti-conformation which forms an intramolecular hydrogen bond between the formyl group and the hydroxyl group, which is an interesting finding for long carbon chain MCP compounds.
AB - A series of 1,2-dimethyl[2.10]metacyclophan-1-enes (MCP-1-enes) containing different substituent groups has been synthesized to illustrate their conformational behavior. 4,22-dimethoxy-1,2-dimethyl[2.10]MCP-1-ene 3 was synthesized by a Grignard coupling reaction, Friedel-Crafts acylation reactions and McMurry coupling reaction from 1,10-dibromodecane. The formation of 4,22-dihydroxy-1,2-dimethyl[2.10]MCP-1-ene 4 was carried out by demethylation of compound 3 with boron tribromide at room temperature. The syn type conformation of 4 was characterized by X-ray diffraction and was found to form both intramolecular and intermolecular hydrogen bonds between the two hydroxyl groups. From this reaction an interesting compound [10]tetrahydrobenzofuranophane 5 was afforded on prolonging the reaction time. 5,21-diformyl-4,22-dihydroxy-1,2-dimethyl[2.10]MCP-1-ene 6 has been prepared from 4,22-dihydroxy-1,2-dimethyl[2.10]MCP-1-ene 4 by using the Duff method in the presence of hexamethylenetetramine. Structural analysis by 1H NMR spectroscopy and X-ray diffraction confirmed that both the solution and the crystalline state of compound 6 adopts an anti-conformation which forms an intramolecular hydrogen bond between the formyl group and the hydroxyl group, which is an interesting finding for long carbon chain MCP compounds.
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U2 - 10.1002/slct.201600670
DO - 10.1002/slct.201600670
M3 - Article
AN - SCOPUS:85017174961
VL - 1
SP - 3594
EP - 3600
JO - ChemistrySelect
JF - ChemistrySelect
SN - 2365-6549
IS - 13
ER -