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Issue 6, 2017
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Mechanistic studies for dirhodium-catalyzed ring expansion reactions

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Abstract

The mechanisms for dirhodium-catalyzed ring expansion reactions of azide tethered methylenecyclopropanes and their analogues were systematically investigated by DFT calculations. The calculation results indicate that the dirhodium catalyst is essential for generating a reactive Rh2–nitrene intermediate having radical character; however, it is not essential for controlling final product selectivities. For substrates involving a three-membered ring, the experimentally obtained C–N bond formation product is a thermodynamically favored product. In contrast, for substrates having a larger ring, the kinetically favored product is the main product. The DFT calculations presented here account for previous experimental findings, and throw light on other dirhodium-catalyzed reactions involving nitrene or carbene intermediates.

Graphical abstract: Mechanistic studies for dirhodium-catalyzed ring expansion reactions

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Publication details

The article was received on 15 Nov 2016, accepted on 06 Feb 2017 and first published on 09 Feb 2017


Article type: Research Article
DOI: 10.1039/C6QO00713A
Citation: Org. Chem. Front., 2017,4, 986-994
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    Mechanistic studies for dirhodium-catalyzed ring expansion reactions

    Y. Wei, X. Hu, K. Chen and M. Shi, Org. Chem. Front., 2017, 4, 986
    DOI: 10.1039/C6QO00713A

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