The treatment of unsaturated amines with electrophiles presents issues with chemoselectivity as the nitrogen lone pair and the olefinic bond are both potential sites for reaction. We have developed a range of methodologies to combat this problem and developed several stereoselective processes, such as the chemo- and diastereoselective cyclopropanation protocols described below, that have proven useful in total synthesis.
We have also developed a chemo- and stereoselective cyclopropanation reaction of allylic amines, and a stereodivergent, diastereoselective cyclopropanation protocol of allylic carbamates using the Wittig-Furukawa reagent [Zn(CH2I)2] or Shi’s carbenoid [CF3CO2ZnCH2I].
- Chemo- and diastereoselective cyclopropanation of allylic amines and carbamates
Csatayová, K.; Davies, S. G.; Lee, J. A.; Ling, K. B.; Roberts, P. M.; Russell, A. J.; Thomson, J. E. Tetrahedron 2010, 66, 8420 [View Journal Page]
- Syntheses of trans-SCH-A and cis-SCH-A via a stereodivergent cyclopropanation protocol
Csatayová, K.; Davies, S. G.; Lee, J. A.; Ling, K. B.; Roberts, P. M.; Russell, A. J.; Thomson, J. E. Org. Lett. 2010, 12, 3152 [View Journal Page]
- Diastereoselective Simmons-Smith cyclopropanations of allylic amines and carbamates
Davies, S. G.; Ling, K. B.; Roberts, P. M.; Russell, A. J.; Thomson, J. E. Chem. Commun. 2007, 4029
[View Journal Page]