Armengol-Relats Helena, Mato Mauro, Echavarren Antonio M
Institute of Chemical Research of Catalonia (ICIQ), Barcelona Institute of Science and Technology, Av. Països Catalans 16, 43007, Tarragona, Spain.
Departament de Química Analítica i Química Orgànica, Universitat Rovira i Virgili, C/ Marcel⋅lí Domingo s/n, 43007, Tarragona, Spain.
Angew Chem Int Ed Engl. 2021 Jan 25;60(4):1916-1922. doi: 10.1002/anie.202012092. Epub 2020 Nov 24.
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.
分别由乙烯基环庚三烯或烷氧基烯炔生成的1,3 - 二烯与铑（II）和金（I）非受体乙烯基卡宾进行的形式上的（4 + 3）环加成反应，生成了具有复杂多样取代模式的1,4 - 环庚二烯，包括天然的双硫杂环戊二烯C'和胡萝卜素 - 1,4 - 二烯的羟基化衍生物。文中给出了完整的机理图，其中金（I）和铑（II）非受体乙烯基卡宾被证明会发生乙烯基环丙烷化/Cope重排或非协同方式进行的直接（4 + 3）环加成反应。
