Importance of Open Structure of Nonmetal Based Catalyst in Hydrogen Bond Promoted Methanolysis of Activated Amide: Structure Dynamics between Monomer and Dimer Enabling Recombinant Covalent, Dative, and Hydrogen Bonds

摘要

The importance of an opened structure such as an open dimer or monomer in organometallic reactions is now gaining recognition among chemists. Formation of open dimers from the more stable closed dimers (Figure 1, left) or releasing the monomers from those species is believed to be a key step to push forward chemical entities into a favorable transition state. However, the significance of such an open structure in metal-free catalysis, namely in hydrogen bond promoted catalysis, remains totally obscured. We report here that the open structure is important for catalysis involving subtle interplay of multiple hydrogen bonds. Open structures were elaborated by controlling novel structural dynamics of aminoorga-noboron (AOB) compounds undergoing the monomer-recombinant dimer equilibrium (Figure 1, right).