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Synthetic Exploration of α‐Diazo γ‐Butyrolactams
Author(s) -
Zhukovsky Daniil,
Dar'in Dmitry,
Kantin Grigory,
Krasavin Mikhail
Publication year - 2019
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.201900133
Subject(s) - diazo , chemistry , trifluoromethanesulfonate , alkyl , aryl , metal , nitrogen , decomposition , nitrogen atom , medicinal chemistry , conjugated system , organic chemistry , catalysis , polymer
DIazo transfer reaction onto γ‐butyrolactams (activated by α‐ethyloxalylation) gave rare α‐diazo γ‐butyrolactams. Decomposition of the latter by Rh 2 (OAc) 4 in the presence of alcohols and water gave products of O–H insertion of the respective metal‐cabene species. Silver triflate (1 mol‐%) was found to convert the γ‐butyrolactams investigated into 1,5‐dihydro‐2 H ‐pyrrol‐2‐ones which represent versatile building blocks. Particular instability was noted for α‐diazo γ‐butyrolactams bearing alkyl or o ‐substituted aryl substituents on the nitrogen atom. These were found to dimerize in solution or upon storage at room temperature to give fully conjugated bis‐hydrazones along with the loss of a nitrogen molecule.