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Updated: Jul 17, 2026

Development of Heterogeneous Enantioselective Catalysts using Chiral Metal-Organic Frameworks (MOFs)
Published on: January 17, 2020
Variable Markovnikov orientation and "cis effect" in ene reactions of nitrosocarbonyl intermediates
Paolo Quadrelli1, Mariella Mella, Andrea Piccanello
1Dipartimento di Chimica Organica, Università degli Studi di Pavia, Viale Taramelli 10, 27100 Pavia, Italy. paolo.quadrelli@unipv.it
Abstract:
Nitrosocarbonyl intermediates, generated at room temperature by the mild oxidation of nitrile oxides, undergo clean ene reactions with trisubstituted olefins. Allylic hydrogens on the more congested side of the alkene are exclusively abstracted (the "cis effect"), thus resembling singlet oxygen behavior. Nitrosocarbonyl benzene follows a Markovnikov orientation and abstracts preferentially the twix hydrogens over the lone ones. With the more sterically demanding nitrosocarbonyl mesitylene, the Markovnikov directing effect is relieved, and comparable twix and lone abstraction are observed.
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