Unexpected Zwitterionic Allenyls from Silylenes and a Fischer Alkynylcarbene: A Remarkable Silylene‐Promoted Rearrangement. Issue 9 (16th January 2019)

• Record Type: Journal Article
• Authors: Cabeza, Javier A.; García‐Álvarez, Pablo; Gómez‐Gallego, Mar; González‐Álvarez, Laura; Merinero, Alba D.; Sierra, Miguel A.
• Is Part Of: Chemistry. Volume 25:Issue 9(2019)
• Page Start: 2222
• Page End: 2225
• Publication Date: 2019-01-16
• Subjects: 1, 3-metal shift -- allenyl ligands -- Fischer carbenes -- silicon -- silylenes; Chemistry -- Periodicals; 540
• DOI: 10.1002/chem.201806275
• Languages: English
• ISSNs: 0947-6539

Abstract

Abstract: The silylenes Si( t Bu2 bzam)R ( t Bu2 bzam= N, N′ ‐bis(tertbutyl)benzamidinate; R=mesityl, CH2 SiMe3 ) attack the Ccarbene atom of the Fischer alkynyl(ethoxy)carbene complex [W(CO)5 {C(OEt)C2 Ph}] 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. Abstract : A striking stereoselective rearrangement, which ends in unprecedented zwitterionic allenyls having one end of the allene C3 fragment inserted into a Si−N bond, takes place in reactions of amidinatosilylenes with a Fischer alkynylcarbene.