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Issue 23, 2018
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Mechanistic understanding of [Rh(NHC)]-catalyzed intramolecular [5 + 2] cycloadditions of vinyloxiranes and vinylcyclopropanes with alkynes

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Abstract

Zhang and co-workers have recently advanced the carbon [5 + 2] cycloaddition of vinylcyclopropane and alkyne (VCP–alkyne) to the hetero-[5 + 2] cycloaddition of vinyloxirane with alkyne (VOR–alkyne). Herein, we present a systematic computational study to gain insights into the detailed reaction mechanisms and origins of mechanistic differences of the two types of cycloadditions (all-carbon [5 + 2] cycloaddition vs. hetero-[5 + 2] cycloaddition). Instead of the general mechanism of rhodium-catalyzed VCP–alkyne cycloaddition that involves cyclopropane cleavage, alkyne insertion and reductive elimination, the rhodium-catalyzed VOR–alkyne cycloaddition occurs via oxidative alkyne–alkene cyclization, oxirane cleavage and reductive elimination. The cycloaddition of VOR–alkyne represents the first example of preferring the oxidative alkyne–alkene cyclization mechanism within rhodium-catalyzed [5 + 2] cycloadditions. The origins of the mechanistic difference are derived from the stabilizing effects due to the favorable ligand–substrate C–H/π dispersion interaction and the substrate–substrate C–H⋯O hydrogen-bond interaction in the oxidative alkyne–alkene cyclization step of the hetero-[5 + 2] cycloaddition. The VOR–alkyne cycloaddition gives a bicyclo[5.3.0] product featuring a 2,5-dihydrooxepin moiety, which can further undergo a [3,3]-sigmatropic rearrangement giving the final bicyclo[3.1.0] product, because a carbonyl structure is more favorable than an enolate structure.

Graphical abstract: Mechanistic understanding of [Rh(NHC)]-catalyzed intramolecular [5 + 2] cycloadditions of vinyloxiranes and vinylcyclopropanes with alkynes

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Publication details

The article was received on 14 May 2018, accepted on 16 May 2018 and first published on 16 May 2018


Article type: Paper
DOI: 10.1039/C8OB01117F
Citation: Org. Biomol. Chem., 2018,16, 4295-4303
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    Mechanistic understanding of [Rh(NHC)]-catalyzed intramolecular [5 + 2] cycloadditions of vinyloxiranes and vinylcyclopropanes with alkynes

    H. Zhou, B. Wu, J. Ma and Y. Dang, Org. Biomol. Chem., 2018, 16, 4295
    DOI: 10.1039/C8OB01117F

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