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Macrocyclization by Rhodium‐Catalyzed Cross‐Cyclotrimerization of L‐Shaped Diynes with Di‐ tert ‐butyl Acetylenedicarboxylate: Effect of Bent Linkers of Diynes
Author(s) -
Nishigaki Shuhei,
Miyauchi Yuta,
Noguchi Keiichi,
Ito Hideto,
Itami Kenichiro,
Shibata Yu,
Tanaka Ken
Publication year - 2016
Publication title -
european journal of organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.825
H-Index - 155
eISSN - 1099-0690
pISSN - 1434-193X
DOI - 10.1002/ejoc.201600909
Subject(s) - chemistry , aromatization , dimethyl acetylenedicarboxylate , rhodium , selectivity , catalysis , bent molecular geometry , medicinal chemistry , acetylenedicarboxylate , intermolecular force , yield (engineering) , stereochemistry , organic chemistry , cycloaddition , molecule , materials science , metallurgy
The effects of bent linkers in diynes on the efficiency and selectivity of intermolecular macrocyclization by the rhodium‐catalyzed sequential cross‐cyclotrimerization of L‐shaped diynes and di‐ tert ‐butyl acetylenedicarboxylate was investigated. A bulky triethylsilyl‐protected cyclohexa‐1,4‐dienediol‐linked diyne reacted with di‐ tert ‐butyl acetylenedicarboxylate to give the corresponding 16‐membered macrocycle as well as the 12‐membered macrocycle. Aromatization of the thus‐obtained 12‐membered macrocycle through desilylation followed by reductive aromatization with SnCl 2 and HCl afforded a [12]cycloparaphenylenehexacarboxylate. The use of a conformationally flexible methoxymethyl‐protected cyclohexanediol‐linked diyne increased the yield of the corresponding 16‐membered macrocycle, although oxidative aromatization leading to the corresponding cycloparaphenylenes was unsuccessful.