Unexpected Zwitterionic Allenyls from Silylenes and a Fischer Alkynylcarbene: A Remarkable Silylene-Promoted Rearrangement |
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| Authors: | Prof Dr Javier A Cabeza Dr Pablo García-Álvarez Prof Dr Mar Gómez-Gallego Laura González-Álvarez Alba D Merinero Prof Dr Miguel A Sierra |
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| Institution: | 1. Centro de Innovación en Química Avanzada (ORFEO-CINQA), Departamento de Química Orgánica e Inorgánica, Universidad de Oviedo, 33071 Oviedo, Spain;2. Centro de Innovación en Química Avanzada (ORFEO-CINQA), Departamento de Química Orgánica, Universidad Complutense, 28040 Madrid, Spain |
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| Abstract: | The silylenes Si(tBu2bzam)R (tBu2bzam=N,N′-bis(tertbutyl)benzamidinate; R=mesityl, CH2SiMe3) attack the Ccarbene atom of the Fischer alkynyl(ethoxy)carbene complex W(CO)5{C(OEt)C2Ph}] to give, after a striking rearrangement, zwitterionic σ-allenyl complexes in which the original carbene C atom forms part of the allene C3 fragment and also of a Si-C-N-C-N five-membered ring after insertion into a Si−N bond of the original amidinatosilylene. These remarkable allenyl products, which contain two stereogenic groups, are selectively formed as single diastereomers. |
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| Keywords: | 1 3-metal shift allenyl ligands Fischer carbenes silicon silylenes |
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