Assembly of Complex 1,4-Cycloheptadienes by (4+3) Cycloaddition of Rhodium(II) and Gold(I) Non-Acceptor Carbenes

Helena Armengol-Relats; Mauro Mato; Antonio M Echavarren

doi:10.1002/anie.202012092

Assembly of Complex 1,4-Cycloheptadienes by (4+3) Cycloaddition of Rhodium(II) and Gold(I) Non-Acceptor Carbenes

Angew Chem Int Ed Engl. 2021 Jan 25;60(4):1916-1922. doi: 10.1002/anie.202012092. Epub 2020 Nov 24.

Authors

Helena Armengol-Relats^{1

2}, Mauro Mato^{1

2}, Antonio M Echavarren^{1

2}

Affiliations

¹ Institute of Chemical Research of Catalonia (ICIQ), Barcelona Institute of Science and Technology, Av. Països Catalans 16, 43007, Tarragona, Spain.
² Departament de Química Analítica i Química Orgànica, Universitat Rovira i Virgili, C/ Marcel⋅lí Domingo s/n, 43007, Tarragona, Spain.

Abstract

The formal (4+3) cycloaddition of 1,3-dienes with Rh(II) and Au(I) non-acceptor vinyl carbenes, generated from vinylcycloheptatrienes or alkoxyenynes, respectively, leads to 1,4-cycloheptadienes featuring complex and diverse substitution patterns, including natural dyctiopterene C' and a hydroxylated derivative of carota-1,4-diene. A complete mechanistic picture is presented, in which Au(I) and Rh(II) non-acceptor vinyl carbenes were shown to undergo a vinylcyclopropanation/Cope rearrangement or a direct (4+3) cycloaddition that takes place in a non-concerted manner.

Keywords: cycloadditions; cycloheptadienes; decarbenation reactions; enyne cycloisomerizations; metal carbenes.

Abstract

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