Unprecedented synthesis of a 14-membered hexaazamacrocycle

The transformation of 3-[(ethoxymethylene)amino]-1-methyl-1 H -pyrazole-4-carbonitrile into the 14-membered macrocycle, 2,10-dimethyl-2,8,10,16-tetrahydrodipyrazolo[3,4- e :3',4'- l ][1,2,4,8,9,11]hexaazacyclotetradecine-4,12-diamine, by the reaction with excess hydrazine under various con...

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Bibliographic Details
Published in:Beilstein journal of organic chemistry 2023, Vol.19 (1), p.1728-1740
Main Authors: Fesenko, Anastasia A, Shutalev, Anatoly D
Format: Article
Language:English
Subjects:
amidrazones
Carbon
Dimerization
hexaazamacrocycles
Hydrazine
Hydrocarbons
Pyrazoles
pyrazolo[3,4-d]pyrimidines
ring contraction
self-assembly
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Summary:The transformation of 3-[(ethoxymethylene)amino]-1-methyl-1 H -pyrazole-4-carbonitrile into the 14-membered macrocycle, 2,10-dimethyl-2,8,10,16-tetrahydrodipyrazolo[3,4- e :3',4'- l ][1,2,4,8,9,11]hexaazacyclotetradecine-4,12-diamine, by the reaction with excess hydrazine under various conditions was studied in detail. The reaction proceeded through the initial formation of 4-imino-2-methyl-2,4-dihydro-5 H -pyrazolo[3,4- d ]pyrimidin-5-amine followed by dimerization to give the final macrocycle. A convenient synthesis of the latter starting from 4-imino-2-methyl-2,4-dihydro-5 H -pyrazolo[3,4- d ]pyrimidin-5-amine was developed. A plausible pathway for the macrocycle self-assembly is discussed. Some features of the structure and reactivity of the obtained macrocycle are outlined.
ISSN:1860-5397
2195-951X
1860-5397
DOI:10.3762/bjoc.19.126