Novel Formal [3+3] Cycloaddition of Silyl Nitronates with Activated Cyclo­propanes and Its Application in the Synthesis of Pyrroline-N-oxides

Abstract

1,1-Cyclopropane diesters with donor substituents undergo formal [3+3] cycloaddition with various silyl nitronates under Yb(OTf)₃ catalysis in the presence of a proton scavenger to give target N-silyloxy tetrahydro-1,2-oxazines in 56–98% yield. The reasons determining the reaction diastereoselectivity are discussed. The resulting tetrahydro-1,2-oxazines are transformed into pyrroline-N-oxides via a novel TfOH-promoted silanol elimination reaction.

Key words

formal [3+3] cycloaddition - silyl nitronates - donor–acceptor cyclopropanes - nitrogen heterocycles - ring contraction

• References and Notes


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