TY - JOUR
T1 - Synthesis and Structures of [2.n]Metacyclophan-1-enes and their Conversion to Highly Strained [2.n]Metacyclophane-1-ynes
AU - Akther, Thamina
AU - Islam, Md Monarul
AU - Kowser, Zannatul
AU - Matsumoto, Taisuke
AU - Tanaka, Junji
AU - Rahman, Shofiur
AU - Alodhayb, Abdullah
AU - Georghiou, Paris E.
AU - Redshaw, Carl
AU - Yamato, Takehiko
N1 - Funding Information:
We would like to thank the OTEC at Saga University for financial support. This work was performed under the Cooperative Research Program of “Network Joint Research Center for Materials and Devices (Institute for Materials Chemistry and Engineering, Kyushu University)”. CR thanks the EPSRC for an Overseas Travel Grant (EP/R023816/1).
Publisher Copyright:
© 2020 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
PY - 2020/7/23
Y1 - 2020/7/23
N2 - The syntheses of syn-[2.n]metacyclophan-1-enes (n = 5, 6, 8) in good yields using the McMurry cyclization of 1,n-bis(3-formyl-4-methoxyphenyl)alkanes are reported. Conversion of syn-[2.6]- and [2.8]metacyclophan-1-enes to the corresponding highly strained syn-type [2.6]- and [2.8]metacyclophane-1-ynes was achieved by successive bromination and dehydrobromination reactions. An attempted trapping reaction of the putative corresponding [2.5]metacyclophane-1-yne by Diels–Alder reaction with 1,3-diphenylisobenzofuran failed due to its smaller ring size and strained structure. X-ray crystallographic analyses show that the triple bonds in syn-[2.6]- and [2.8]metacyclophane-1-ynes are distorted from linearity with bond angles of 156.7° and 161.4°, respectively. A DFT (Density Functional Theory) computational study was conducted to determine the stabilities of different conformations of the target compounds.
AB - The syntheses of syn-[2.n]metacyclophan-1-enes (n = 5, 6, 8) in good yields using the McMurry cyclization of 1,n-bis(3-formyl-4-methoxyphenyl)alkanes are reported. Conversion of syn-[2.6]- and [2.8]metacyclophan-1-enes to the corresponding highly strained syn-type [2.6]- and [2.8]metacyclophane-1-ynes was achieved by successive bromination and dehydrobromination reactions. An attempted trapping reaction of the putative corresponding [2.5]metacyclophane-1-yne by Diels–Alder reaction with 1,3-diphenylisobenzofuran failed due to its smaller ring size and strained structure. X-ray crystallographic analyses show that the triple bonds in syn-[2.6]- and [2.8]metacyclophane-1-ynes are distorted from linearity with bond angles of 156.7° and 161.4°, respectively. A DFT (Density Functional Theory) computational study was conducted to determine the stabilities of different conformations of the target compounds.
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U2 - 10.1002/ejoc.202000548
DO - 10.1002/ejoc.202000548
M3 - Article
AN - SCOPUS:85087732356
SN - 1434-193X
VL - 2020
SP - 4167
EP - 4175
JO - European Journal of Organic Chemistry
JF - European Journal of Organic Chemistry
IS - 27
ER -