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DOI: 10.1055/s-0036-1590802
1,3,4-Oxadiazole and Heteroaromatic-Fused 1,2,4-Triazole Synthesis Using Diverted Umpolung Amide Synthesis
Research reported in this publication was supported by the National Institute of General Medical Sciences of the National Institutes of Health (GM 063557).Publikationsverlauf
Received: 02. Mai 2017
Accepted after revision: 29. Mai 2017
Publikationsdatum:
07. August 2017 (online)
Published as part of the Special Topic Modern Strategies for Heterocycles Synthesis
Abstract
Umpolung Amide Synthesis (UmAS) has emerged as a superior alternative to conventional amide synthesis methods based on carbonyl electrophiles in a range of situations, particularly when epimerization-prone couplings are prescribed. In an unanticipated development during our most recent studies, we discovered that diacyl hydrazide products from UmAS were not formed as intermediates when using an acyl hydrazide as the amine acceptor. This resulted in a new preparation of 1,3,4-oxadiazoles from α-bromonitroalkane donors. We hypothesized that a key tetrahedral intermediate in UmAS was diverted toward a more direct pathway to the heterocycle product rather than through formation of the diacyl hydrazide, a typical oxadiazole progenitor. In studies reported here, diversion to 1,2,4-triazole products is described, a behavior hypothesized to also result from an analogous tetrahedral intermediate, but one formed from heteroaromatic hydrazine acceptors.
Key words
oxadiazole - triazole - diverted Umpolung Amide Synthesis - triazolopyridine - pyrazine - pyrimidine - pyridazine - hydrazineSupporting Information
- Supporting information for this article is available online at https://doi.org/10.1055/s-0036-1590802.
- Supporting Information
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Innovative exceptions: 2-amino-1,3,4-oxadiazoles from an isocyanide:
From a tetrazole, see:
For additional enantioselective syntheses of α-bromonitroalkanes, see: