N ‐Tosylhydrazones as [N,N] Synthons in Heterocyclic Chemistry: Synthesis of 3,5‐Disubstituted N ‐Alkenyl‐1 H ‐pyrazoles

A new mode of reactivity of N ‐sulfonylhydrazones towards alkynes is described: ketone‐derived N ‐tosylhydrazones (NTHs) bearing α‐H atoms behave as [NN] synthons in their reactions with alkoxy alkynyl Fischer carbene complexes (FCCs) and only the two N atoms are incorporated into the newly formed p...

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Published in:Advanced synthesis & catalysis 2024-05, Vol.366 (10), p.2334-2343
Main Authors: Velázquez‐Stavínov, Antonio, Piedra, Helena F., Gutiérrez‐Collar, Aarón, Álvarez‐Márquez, Manuel, Menéndez, M. Isabel, Merino, Isabel, Cabal, María‐Paz, Aguilar, Enrique
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container_issue 10
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container_title Advanced synthesis & catalysis
container_volume 366
creator Velázquez‐Stavínov, Antonio
Piedra, Helena F.
Gutiérrez‐Collar, Aarón
Álvarez‐Márquez, Manuel
Menéndez, M. Isabel
Merino, Isabel
Cabal, María‐Paz
Aguilar, Enrique
description A new mode of reactivity of N ‐sulfonylhydrazones towards alkynes is described: ketone‐derived N ‐tosylhydrazones (NTHs) bearing α‐H atoms behave as [NN] synthons in their reactions with alkoxy alkynyl Fischer carbene complexes (FCCs) and only the two N atoms are incorporated into the newly formed pyrazole ring. The scope of the reaction, leading to 5‐methoxy‐ N ‐alkenyl pyrazoles, proved to be wide regarding both partners; thus, a variety of aryl and primary, secondary, and tertiary alkyl substituents are tolerated within the FCC, while aryl alkyl NTHs, symmetric and asymmetric dialkyl NTHs and NTHs derived of cyclic ketones can be also employed. In addition, the reaction can be performed at large scale and applied for late‐stage diversification of natural products. A reasonable reaction mechanism is also proposed, which is supported by deuteration experiments and DFT calculations.
doi_str_mv 10.1002/adsc.202400103
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title N ‐Tosylhydrazones as [N,N] Synthons in Heterocyclic Chemistry: Synthesis of 3,5‐Disubstituted N ‐Alkenyl‐1 H ‐pyrazoles
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