1363391-59-6Relevant academic research and scientific papers
Chemical behaviour of a prototype boryl(phosphino)carbene
Lavigne, Florie,Maerten, Eddy,Alcaraz, Gilles,Saffon-Merceron, Nathalie,Baceiredo, Antoine
, p. 297 - 303 (2014)
We recently disclosed the synthesis of a novel push-pull boryl(phosphino)carbene. To determine the influence of this substitution pattern on the chemical behaviour, a study into the reactivity of the prototype (1) of this new family of B(sp2)-substituted phosphinocarbenes was undertaken. Carbene 1 exhibits one of the most common intramolecular rearrangements of singlet carbenes, involving a 1,2-mesityl shift, and typical [2+1] cycloaddition reactions with electron-poor acrylonitrile. A pronounced α,β-ambiphilic character was also shown by the reaction of 1 with benzaldehyde, leading to phosphorylalkene 4. Due to its specific electronic properties, carbene 1 also exhibits unprecedented reactivity with chloroacrylonitrile, enabling the formation of bicyclo[1.1.0]phosphetanium salt 6 and borylcyclopropene 9, which have been fully characterised by NMR spectroscopy and X-ray crystallography. The reactivity of stable boryl(phosphino)carbene 1 has been investigated. It showed the typical reactivity of transient singlet carbenes (1,2-migration and [2+1] cycloaddition), together with marked α,β-ambiphilic character (see scheme). Due to its specific electronic properties, carbene 1 enabled the formation of an original bicyclo[1.1.0]phosphetanium salt and a borylcyclopropene. Copyright
Borylated methylenephosphonium salts: Precursors of elusive boryl(phosphino)carbenes
Lavigne, Florie,Maerten, Eddy,Alcaraz, Gilles,Saffon-Merceron, Nathalie,Acosta-Silva, Carles,Branchadell, Vicenc,Baceiredo, Antoine
supporting information; experimental part, p. 8864 - 8865 (2010/08/21)
The synthesis of a new family of boryl-substituted methylenephosphonium derivatives, the phosphorus analogues of iminium salts, has been developed. They were used in the preparation of the first stable boryl(phosphino)carbene, which has been fully characterized by NMR spectroscopy and X-ray crystallography. Density functional theory calculations indicate that these carbenes can be classified as push-pull carbenes with a relatively small singlet-triplet energy gap.
