Selective Three-Component Coupling for CO₂ Chemical Fixation to Boron Guanidinato Compounds

A selective three-component coupling was employed to fix carbon dioxide to boron guanidinato compounds. The one-pot reaction of carbon dioxide, carbodiimides, and borylamines (ArNH)BC₈H₁₄ afforded the corresponding 1,2-adducts {R(H)N}C{N(Ar)}(NR)(CO₂)BC₈H₁₄. Alternatively, the reaction with p-MeOC₆H₄NC or 2,6-Me₂C₆H₃NC gave the corresponding isocyanide 1,1-adducts { i-PrHN}C{N(p-Me-C₆H₄)}(N i-Pr){CNAr}BC₈H₁₄. The molecular structures of products (2,6- i-Pr₂C₆H₃NH)BC₈H₁₄ 7, { i-Pr(H)N}C{N(p-MeC₆H₄)}(N i-Pr)(CO₂)BC₈H₁₄ 9, {Cy(H)N}C{N( p-MeC₆H₄)}(Cy)(CO₂)BC₈H₁₄ 13, and { i-PrHN}C{N( p-MeC₆H₄)}(N i-Pr){CNR″}BC₈H₁₄ (R″ = p-MeOC₆H₄, 2,6-Me₂C₆H₃) 14 and 15 were established by X-ray diffraction. Density functional theory calculations at the M05-2X level of theory revealed that CO₂ fixation and formation of the corresponding adduct is exothermic and proceeds via a nonchelate boron guanidinato intermediate.