Versatility of BINOL Reagent in Organic Chemistry: Problem Set Answers January 20th 2009 By Sebastien F.Vanier

Question #1 1,7- asymmetric induction in Grignard reactions of keto esters Miyano, S. et al. J. Chem. Soc., Perkin Trans. 1, 1999, 1685

Question #1 Note: MgBr2 in the reaction is critical because its strong Lewis acidity with four vacant coordination sites Miyano, S. et al. J. Chem. Soc., Perkin Trans. 1, 1999, 1685

Question #1 1,9- and 1,10- asymmetric induction in Grignard reactions of ω-keto esters1,2,3 Conclusion: Absolute stereochemistry depends on the ester and the chelating ‘BINOL’ ester (called Optimal Chelating Group) 1Miyano, S. et al. J. Chem. Soc., Perkin Trans. 1, 1999, 1141 2Miyano, S. et al. J. Chem. Soc., Perkin Trans. 1, 1999, 1685 3Miyano, S. et al. J. Chem. Soc., Chem. Commun., 1992, 687

Question #2 Minatti, A.; Doetz, K. H. Eur. J. Org. Chem., 2006, 268

Question #2 Asymmetric amplification has been observed in these conditions Minatti, A.; Doetz, K. H. Eur. J. Org. Chem., 2006, 268

Question #3 Maier, P.; Redlich, H.; Richter, J. Tetrahedron: Asymmetry, 2005, 16, 3848

Question #3 Maier, P.; Redlich, H.; Richter, J. Tetrahedron: Asymmetry, 2005, 16, 3848

Question #4 Catalytic enantioselective Mannich-type reaction Kobayachi, I; Shitani, H.; Ueno, M.; Kobayashi, S. J. Am. Chem. Soc., 1997, 119, 7153-7154

Question #4 Up to 83% yield and 95% ee can be obtained by using 6,6’-dibromo-1,1’-BINOL Kobayachi, I; Shitani, H.; Ueno, M.; Kobayashi, S. J. Am. Chem. Soc., 1997, 119, 7153-7154

Question #5 Sawada, D.; Kanai, M.; Shibasaki, M. J. Am. Chem. Soc., 2000, 122 (43), 10521-10532

Question #5 Lewis Base Lewis Acid Sawada, D.; Kanai, M.; Shibasaki, M. J. Am. Chem. Soc., 2000, 122 (43), 10521-10532