The Development of Synthetic Routes to 1,1,n,n-Tetramethyl[n](2,11)teropyrenophanes
Kiran Sagar Unikela
Chemistry Department, Memorial University of Newfoundland, 283 Prince Philip Drive, St. John's, NL, Canada, A1E 5V7
These authors contributed equally to this work.Search for more papers by this authorBradley L. Merner
Chemistry Department, Memorial University of Newfoundland, 283 Prince Philip Drive, St. John's, NL, Canada, A1E 5V7
These authors contributed equally to this work.Search for more papers by this authorParisa Ghods Ghasemabadi
Chemistry Department, Memorial University of Newfoundland, 283 Prince Philip Drive, St. John's, NL, Canada, A1E 5V7
Search for more papers by this authorC. Chad Warford
Chemistry Department, Memorial University of Newfoundland, 283 Prince Philip Drive, St. John's, NL, Canada, A1E 5V7
Search for more papers by this authorChristopher S. Qiu
Chemistry Department, Memorial University of Newfoundland, 283 Prince Philip Drive, St. John's, NL, Canada, A1E 5V7
Search for more papers by this authorLouise N. Dawe
Department of Chemistry and Biochemistry, Wilfrid Laurier University, ON, Canada, N2L 3C5
Search for more papers by this authorYuming Zhao
Chemistry Department, Memorial University of Newfoundland, 283 Prince Philip Drive, St. John's, NL, Canada, A1E 5V7
Search for more papers by this authorCorresponding Author
Graham J. Bodwell
Chemistry Department, Memorial University of Newfoundland, 283 Prince Philip Drive, St. John's, NL, Canada, A1E 5V7
Chemistry Department, Memorial University of Newfoundland, 283 Prince Philip Drive, St. John's, NL, Canada, A1E 5V7
E-mail: [email protected]
Search for more papers by this authorKiran Sagar Unikela
Chemistry Department, Memorial University of Newfoundland, 283 Prince Philip Drive, St. John's, NL, Canada, A1E 5V7
These authors contributed equally to this work.Search for more papers by this authorBradley L. Merner
Chemistry Department, Memorial University of Newfoundland, 283 Prince Philip Drive, St. John's, NL, Canada, A1E 5V7
These authors contributed equally to this work.Search for more papers by this authorParisa Ghods Ghasemabadi
Chemistry Department, Memorial University of Newfoundland, 283 Prince Philip Drive, St. John's, NL, Canada, A1E 5V7
Search for more papers by this authorC. Chad Warford
Chemistry Department, Memorial University of Newfoundland, 283 Prince Philip Drive, St. John's, NL, Canada, A1E 5V7
Search for more papers by this authorChristopher S. Qiu
Chemistry Department, Memorial University of Newfoundland, 283 Prince Philip Drive, St. John's, NL, Canada, A1E 5V7
Search for more papers by this authorLouise N. Dawe
Department of Chemistry and Biochemistry, Wilfrid Laurier University, ON, Canada, N2L 3C5
Search for more papers by this authorYuming Zhao
Chemistry Department, Memorial University of Newfoundland, 283 Prince Philip Drive, St. John's, NL, Canada, A1E 5V7
Search for more papers by this authorCorresponding Author
Graham J. Bodwell
Chemistry Department, Memorial University of Newfoundland, 283 Prince Philip Drive, St. John's, NL, Canada, A1E 5V7
Chemistry Department, Memorial University of Newfoundland, 283 Prince Philip Drive, St. John's, NL, Canada, A1E 5V7
E-mail: [email protected]
Search for more papers by this authorGraphical Abstract
BIG BEND chimes in – this is not second hand news! Every minute detail of the synthesis of a striking series of 1,1,n,n-tetramethyl[n](2,11)teropyrenophanes (n=7–9) is described. The end-to-end bend in the teropyrene system clocks in at as much as 177.9°.
Abstract
A concise synthetic approach to 1,1,n,n-tetramethyl[n](2,11)teropyrenophanes has been developed. It involves the construction of triply-bridged pyrenophanes, during which the three bridges are installed successively using Friedel-Crafts alkylation, Wurtz coupling and McMurry reactions. At the same time, the innate regiochemical preferences of pyrene toward electrophilic aromatic substitution are relied upon to control the substitution pattern. A cyclodehydrogenation reaction is then employed to generate the teropyrene system directly in a nonplanar conformation. The crystal structure of 1,1,7,7-tetramethyl[7](2,11)teropyrenophane was determined and the teropyrene system was found to have an end-to-end bend angle of 177.9°.
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