8. Transition State Modelling of Reactions

The computational development of a force field model for the transition state of the boron aldol reaction has allowed an understanding of the origins of stereocontrol in many synthetically important situations. Moreover, these models have been used in a predictive sense to design useful new chiral boron reagents to direct asymmetric aldol reactions. A related approach has been adopted for the allylboration reaction, which like the boron aldol reaction proceeds through a highly ordered cyclic transition state.

Selected publications

  1. Bernardi, A.; Gennari, C.; Goodman, J. M.; Paterson, I. The rational design and systematic analysis of asymmetric aldol reactions using enol borinates: applications of transition state computer modelling. Tetrahedron: Asymmetry 1995, 6, 2613.
  2. Bernardi, A.; Comotti, A.; Gennari, C.; Hewkin, C. T.; Goodman, J. M.; Schlapbach, A.; Paterson, I. Computer-assisted design of chiral boron enolates: the role of ate complexes in determining aldol stereoselectivity. Tetrahedron 1994, 50, 1227.
  3. Vulpetti, A.; Bernardi, A.; Gennari, C.; Goodman, J. M.; Paterson, I. Origins of π-face selectivity in the aldol reactions of chiral E—enol borinates: a computational study using transition state modelling. Tetrahedron 1993, 49, 685.
  4. Bernardi, A.; Capelli, A. M.; Comotti, A.; Gennari, C.; Gardner, M.; Goodman, J. M.; Paterson, I. Origins of stereoselectivity in chiral boron enolate aldol reactions: a computational study using transition state modelling. Tetrahedron 1991, 47, 3471.

Current Projects

  1. Synthesis of Bioactive Marine Metabolides.
  2. New Methods for the Synthesis of Polyketide Natural Products.
  3. Expanding Polyketide Diversity.
  4. New Reagents for Asymmetric Aldol Reactions.
  5. Biomimetic Total Synthesis of Polyether Ionophores.
  6. Designed Synthesis of Lophotoxin Analogues.
  7. Designed Synthesis of Novel Macrolide Antibiotics Related to Erythromycin.
  8. Transition State Modelling of Reactions (with Dr J. M. Goodman and Prof C. Gennari)