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

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

3. 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

4. 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

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

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

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

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

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

10. 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,

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

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