Changing Course With Carbenes | Chemical & Engineering News
Volume 92 Issue 49 | p. 30 | Concentrates
Issue Date: December 8, 2014

Changing Course With Carbenes

Modifying an NHC catalyst’s electronic and steric properties switches reaction selectivity to produce 1,2-diazepines or pyrazoles
Department: Science & Technology
News Channels: Organic SCENE, JACS In C&EN
Keywords: N-heterocyclic carbene, catalysis, selectivity, cycloaddition

As chemists have come to better understand the correlation between catalyst design and selectivity, a theme has emerged in which researchers seek to make different products from the same reactants simply by altering the catalyst. In a new example, Frank Glorius and coworkers at the University of Münster, in Germany, switched the reactivity of enals with hydrazones in cycloaddition reactions to make 1,2-diazepines or pyrazoles, depending on the choice of N-heterocyclic carbene organocatalyst (J. Am. Chem. Soc. 2014, DOI: 10.1021/ja510737n). The team discovered that a bulkier mesityl-substituted catalyst leads to [4+3] annulation, whereas a less bulkier methoxyphenyl-substituted catalyst leads to [4+1] annulation (shown). “The electronic and steric properties of the N-heterocyclic carbene organocatalyst play a vital role in controlling the reaction pathway, allowing selective access to diverse 1,2-diazepine and pyrazole derivatives from identical substrates,” the researchers note. These compounds are important heterocycles present in a range of natural products and bioactive synthetic compounds.

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