N-Heterocyclic Carbene Stabilized 1-Bora-1,3-butadienes.

Deprotonation of [(NHC)(Fmes)B-allyl]+ borenium cations (NHC, IMes (a) or IMe2 (b); Fmes, 2,4,6-(CF3)3C6H2) provides an easy entry to the NHC-stabilized 1-bora-1,3-butadienes. They feature a planar s-trans-conformation just like 1,3-butadiene. The 1-borabutadiene 7a undergoes hydroboration reactions; the HB(C6F5)2 hydroboration product is trapped with CO or an isonitrile to give the respective cyclic zwitterionic borenium-borate enolate or enamide products. 1-Borabutadiene 7b undergoes 1,4-chalcogenation with elemental sulfur or selenium, and it gives the six-membered heterocyclic 1,4-addition product with the S═O bond of sulfur dioxide. Compound 7b served as a precursor for the formation of a borylated η3-allyl ligand at Ru. 7b formed a Rh complex by reaction with [Rh(ethylene)2Cl]2. It subsequently underwent an intramolecular C-H activation reaction to a mixture of η3-methyl-boraallyl Rh complex isomers.