Litcius/Paper detail

Characterization of the Zwitterionic Intermediate in 1,1‐Carboboration of Alkynes

Alessandro Bismuto, Gary S. Nichol, Fernanda Duarte, Michael J. Cowley, Stephen P. Thomas

2020Angewandte Chemie International Edition32 citationsDOIOpen Access PDF

Abstract

Abstract The reaction of a Lewis acidic borane with an alkyne is a key step in a diverse range of main group transformations. Alkyne 1,1‐carboboration, the Wrackmeyer reaction, is an archetypal transformation of this kind. 1,1‐Carboboration has been proposed to proceed through a zwitterionic intermediate. We report the isolation and spectroscopic, structural and computational characterization of the zwitterionic intermediates generated by reaction of B(C 6 F 5 ) 3 with alkynes. The stepwise reactivity of the zwitterion provides new mechanistic insight for 1,1‐carboboration and wider B(C 6 F 5 ) 3 catalysis. Making use of intramolecular stabilization by a ferrocene substituent, we have characterized the zwitterionic intermediate in the solid state and diverted reactivity towards alkyne cyclotrimerization.

Topics & Concepts

AlkyneZwitterionReactivity (psychology)ChemistryBoraneSubstituentIntramolecular forceMedicinal chemistryCatalysisCombinatorial chemistryStereochemistryMoleculeOrganic chemistryPathologyMedicineAlternative medicineOrganoboron and organosilicon chemistrySynthesis and characterization of novel inorganic/organometallic compoundsChemical Synthesis and Analysis