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Literature Meeting, January 13 th 2009 By Sebastien F.Vanier

Applications of Atropisomerism: the Use and the Versatility of Enantioenriched BINOL Reagent in Organic Chemistry. Literature Meeting, January 13 th 2009 By Sebastien F.Vanier. Optically Active Metal Complex in Asymmetric Reaction: more then useful.

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Literature Meeting, January 13 th 2009 By Sebastien F.Vanier

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  1. Applications of Atropisomerism: the Use and the Versatility of Enantioenriched BINOL Reagent in Organic Chemistry Literature Meeting, January 13th 2009 By Sebastien F.Vanier

  2. Optically Active Metal Complex in Asymmetric Reaction: more then useful

  3. Chiral 1,1’-Binaphthyl-2,2’-diol in Organic Reactions: Few Examples…

  4. Chiral 1,1’-Binaphthyl-2,2’-diol in Organic Reactions: Few Examples…

  5. Presentation Overview • Introduction: BINOL’s synthesis and chirality • Enantiomeric resolution strategies: Metal complex catalyst • Reduction and epoxidation reactions: Chiral reagent • C-C Bond formation: Chiral Lewis Acid • BINOL as a Chiral auxiliary • Conclusion

  6. Introduction: Easy Access to BINOL First racemic synthesis in 1873 by von Richter1 Then the preparation of racemic BINOLhas been widely studied… here few methods Oxidative coupling of 2-naphthol using FeCl3, K3Fe(CN)6 Mn(acac)3, Cu-amine complexes or TiCl4 are commonly used with yields up to 90% (Brunel, J. M., Chem. Rev., 2005, 105, 857)

  7. Introduction: Easy Access to BINOL Mechanistic example with FeCl31 1Iwata, S. et al. J. Org. Chem., 1989, 54, 3007; Wu, S. H. et al. Chin. J. Chem., 1996, 14, 561 See also Matsuura, T. et al. Tetrahedron, 1996, 52, 1005

  8. Introduction: Easy Access to BINOL Asymmetric synthesis… Most commonly, a chiral amine is used for the oxidative dimerization… (8 equiv. needed / 2 equiv. Metal) Usually, the chirality is not induced by the oxidative dimerization but by the stereoselective crystallization of the complex (partial racemization), but…3 Enzymatic procedure can be used too on a multigram scale using Bovine Pancreatic active3,4 component but… Radical species directed by complexation with chiral amine!1

  9. Introduction: Easy Access to BINOL Resolution methods (all based on diastereoselective isolation with a chiral auxiliary) Jacques and coworkers were the first but… (90% ee and 26% yield for (S)-BINOL) But attempts with (L)-Menthol derivatives are the best4,5

  10. Introduction: Easy Access to BINOL Resolution methods Simplest and very efficient technique

  11. Atropisomerism: Introduction Racemization kinetics of optically active 1,1’-binaphthyl was studied by Cooke and Harris in 19631 Substituants introduced into the 2,2’-positions stabilize drastically the chiral configuration Ex.: (S)-1,1’-binaphthyl-2,2’-dicarboxylic acid could not be racemized at 175°C in DMF2

  12. Atropisomerism: Introduction Absolute configurations of chiral binaphthyl compounds were originally proposed by Mislow1 (optical analysis) (R)-BINOL 1Mislow, K. et al. Angew. Chem., 1958, 70, 683 2Mason, S. F. et al. J. Chem. Soc., Perkin Trans. 2,1981, 167 3Curtin, D.Y. et al. J. Am. Chem. Soc., 1980, 102, 7709; Pu, L. Chem. Rev., 1998, 98, 2405

  13. BINOL in Chemical Reactions Few attractions in BINOL’s antecedents • First applied as a chiral phase transfert by Cram in 19781 • Its potential as chiral ligand for metal-mediated catalysis was first recognized by Noyori in 19792 • Since 1990, enantioenriched BINOL have become among the most widely used ligands for both stoichiometric and catalytic asymmetric reactions3 1Cram, D. et al. J. M. Acc. Chem. Res., 1978, 11, 8 2Noyori, R. J. Am. Chem. Soc., 1979, 101, 3129 for reduction of aromatic ketones and aldehydes 3Brunel, J. M. Chem. Rev., 2005, 105, 857; Yudin, A. K. et al. Chem. Rev., 2003, 103, 3155 Pu, L. Chem. Rev., 1998, 98, 2405; Salvadori, P. et al. Synthesis (Rev.), 1991, 503

  14. BINOL in Kinetic Resolution Strategies Yamamoto reported for the first time the use of chiral binaphthyl organoaluminum reagent (1988)1 Then, there is several examples of Natural alkaloids in kinetic resolution3,4,5 Via Matched / Mismatched aluminocomplexation Via Steric complementary (matched chirality) and specific intermolecular forces

  15. BINOL in Kinetic Resolution Strategies In 2006, Berkessel’s group claimed a highly selective chemoenzymatic DKR of secondary alcohols using Nguyen’s works in the field… The BINOL-Al catalyst acts as a Racemizative Reagent in this Meerwein–Ponndorf–Verley / Oppenauer reaction (1-phenylvinyl acetate as the acylating agent gives acetophenone as the by-product, which acts as a hydrogen acceptor…) 1Harris, W. W. et al. Tetrahedron Lett., 1996, 37, 7623 – 7626; Nguyen, S. T. et al. Angew. Chem. Int. Ed., 2002, 41, 1020

  16. BINOL in Kinetic Resolution Strategies Here, (R)-BINOL is used but rac-BINOL has also been tested As the acylating agent has the same core than the s.m., Acylation can directly be done… 1Kurti L. and Czako B. Strategic Application of Named Reaction in Organic Synthesis, Elsevier Academic Press, 2005 2Jackman, L. M. and J. A. Mills. Mechanism of the Meerwein–Ponndorf Reduction, Nature, 164, 1949, 789-790 3Nguyen, S. T. et al. J. Am. Chem. Soc., 2006, 128, 12596-12597

  17. Reduction reaction: BINOL as a chiral reagent Prochiral carbonyl reduction is one of the most studied transformation1: Metal complex as hydride reagent are use widely Easily prepared from (R)-BINOL First introduce by Noyori in 19792,3 But first attempts were disappointing (2% ee)… (the two Hydrogen were homotopic) 1Deloux, L.; Srebnik, M. et al. Chem. Rev., 1993, 93, 763 2Noyori, R. et al. J. Am. Chem. Soc., 1979, 101, 5843;Noyori, R.; Takaya, H. et al. Chem. Scr., 1985, 25, 83 3Noyori, R. et al. J. Am. Chem. Soc., 1984, 106, 6709-6717; Noyori, R. Chem. Soc. Rev., 1989, 18, 187

  18. Reduction reaction: BINOL as a chiral reagent Modifications were taken by adding an alcohol on the reagent Now the chiral information can be efficiently transferred to the hydride3 High Enantioselectivities were obtained for several carbonyl compounds 1Noyori, R. et al. J. Am. Chem. Soc., 1979, 101, 5843;Noyori, R.; Takaya, H. et al. Chem. Scr., 1985, 25, 83 2Noyori, R. et al. J. Am. Chem. Soc., 1984, 106, 6709-6717; Noyori, R. Chem. Soc. Rev., 1989, 18, 187 3Suter, M. et al. J. Organomet. Chem., 2001, 621, 231

  19. Reduction reaction: BINOL as a chiral reagent Only unsaturated and aromatic Compound are used… 1Brunel, J. M. Chem. Rev., 2005, 105, 857 2Noyori, R. et al. J. Am. Chem. Soc., 1984, 106, 6709-6717 3Noyori, R. Chem. Soc. Rev., 1989, 18, 187

  20. Reduction reaction: BINOL as a chiral reagent Reductive ‘phospholidine-borane’ system developed by Tang and coworkers1 1Tang, C. et al. Tetrahedron: Asymmetry,1999, 10, 3259

  21. Reduction reaction: BINOL as a chiral reagent Reductive Ti-BINOL system developed by Nakai and coworkers1 1Emma, H.; Mori, M.; Nakai, T. Synlett, 1996, 1229

  22. Reduction reaction: BINOL as a chiral reagent But further examination of the reaction showed some enantioselective autoinduction1 1Emma, H.; Mori, M.; Nakai, T. Synlett, 1996, 1229

  23. Reduction reaction: BINOL as a chiral reagent In 2006, Nguyen’s group reported an efficient asymmetric Imine reduction1 (Enantioselective Meerwein-Schmidt-Ponndorf-Werley reduction) Ligand-accelerated reaction (increasing Al L.A.) 1Graves, C. R.; Scheidt, K. A.; Nguyen, S. T. Org. Lett.,2006, 8, 1229

  24. Nonlinear Effect (NLE) with BINOL Mikami and Nakai reported a remarkable level of positive NLE in Ene reaction2,3: Kagan’s pioneering work on asymmetric Amplification1 (sulfide oxidation and epoxidation) Positive NLE Direct. Prop. effect Negative NLE Only 35-40% ee is good enough to provide the same level of enantiomeric excess as enantiopure BINOL! Positive NLE: Optical purity of the products of a given reaction can exceed the optical purity of the catalysts (or chiral auxiliaries) Chiral Ti complex derived from a 100% ee BINOL reacts 35 times faster! (dimers stabilisation)2,3 1Kagan, H. B. J. Am. Chem. Soc., 1986, 108, 2353; Kagan, H. B. J. Am. Chem. Soc., 1994, 116, 9430 2Mikami, K. and Nakai, T. J. Chem. Soc., Chem. Commun., 1990, 1623 3Mikami, K.; Terada, M. et al. Tetrahedron, 1992, 48, 5671

  25. Nonlinear Effect (NLE) with BINOL Mikami and Nakai’s explanation of the diastereoisomers stabilisation1,2 3D Representations Of Titanium complex1 (R,R)-BINOL-Ti dimer (S,R)-BINOL-Ti dimer More Stable from 1.08 kcal/mol Less prone to reacts! DIMER / MONOMER EQUILIBRIUM See also Mikami, K. et al. J. Chem. Soc. Chem. Commun., 1990, 1623 Mikami, K. et al. Synlett., 1992, 255; Mikami, K. Tetrahedron, 1992, 48, 5671 Mikami, K. et la. Adv. Asymmetric Synth., 1995, 1 1Mikami, K.; Nakai, T. et al. J. Chem. Soc., Chem. Commun.,1994, 833 2Matsumoto, Y. and Mikami, K. Chem. Commun., 1997, 281 3Kagan, H. B. Angew. Chem. Int. Ed., 1998, 37, 2922-2959

  26. Enantioselective epoxidation reactions In 1997, Shibasaki’s group claimed a Lanthanum-BINOL catalytic system1,2 (In attempts to develop new heterometallic chiral catalysts) Since Ln complexes are useful in Michael addition3 Also, they observed some Asymmetric amplification in the reaction! 1Shibasaki, M. et al. J. Am. Chem. Soc.,1997, 119, 2329 2Shibasaki, M. et al. Angew. Chem., Int. Ed., 2004, 43, 317 3Shibasaki, M. et al. J. Am. Chem. Soc., 1995, 117, 6194

  27. Enantioselective epoxidation reactions In attempt to find a mechanism, Shibasaki’s group studied some additives1,2,3 - Increasing the L.A. of the complex • Directing the epoxidation by attraction • with the peroxide reagent • Generating a more appropriate • chiral environment And with a single recrystallization, ee were increase to >99% 1Sasai, H.; Bougauchi, M.; Shibasaki, M. Tetrahedron Lett.,1998, 39, 7353 2Shibasaki, M. et al. Tetrahedron Lett.,2000, 41, 9569-9574

  28. Enantioselective epoxidation reactions Optimization of the last attempts with Shibasaki’s new methodology1 Based on X-Ray Of the La-complex 1Yamaguchi, K.; Shibasaki, M. et al. J. Am. Chem. Soc.,2001, 123, 2725

  29. C-C Bond Formation: Aldol reaction Utilisation of BINOL-Ti complex in C-C bond reaction are frequent

  30. C-C Bond Formation: Aldol reaction In 1990, Mukaiyama reported the use of BINOL-Ti complex in Aldol Reaction1 Usually, an acyclic antiperiplanar transition state is proposed 1Mukaiyama, T.; Inubushi, A.; Suda, S.; Hara, R.; Kobayashi, S. Chem. Lett.,1990, 1015

  31. C-C Bond Formation: Aldol reaction Then Mikami optimized the reaction by changing the BINOL-Ti complex1 When –SR1 is to much bulky, Zimmerman-Traxler model can be applied1 1Mikami, K. and Matsukawa, S. J. Am. Chem. Soc.,1994, 116, 4077

  32. C-C Bond Formation: Ene reaction Nakai and Mikami expand their system in the Mukaiyama Aldol Reaction1… 1Mikami, K.; Matsukawa, S.; Volk, T.; Terada, M. Angew. Chem. Int. Ed. Engl., 1997, 36, 2768

  33. C-C Bond Formation: Ene reaction Z and syn selectivity directed by allylic strain and steric repulsion with the carbonyl/Ti complex BINOL chirality directs the Re face attack2 1Mikami, K.; Matsukawa, S.; Volk, T.; Terada, M. Angew. Chem. Int. Ed. Engl., 1997, 36, 2768 2Yudin, A. K. et al. Chem. Rev., 2003, 103, 3155

  34. C-C Bond Formation: Ene reaction The Greatest contribution in the field done by Nakai and Mikami1,2 1Mikami, K.; Terada, M.; Nakai, T. J. Am. Chem. Soc.,1989, 111, 1940 2Mikami, K.; Terada, M.; Nakai, T. J. Am. Chem. Soc., 1990, 112, 3949

  35. BINOL in Friedel-Crafts Reaction In the development of their aldol reaction, Mikami obtained surprising results2 One of the most fundamental C-C bond formation reaction1 1Mikami, K. et al. Tetrahedron Lett.,1997, 38, 7021-7024; Meyer, C. et al. Tetrahedron Lett.,1996, 37, 375-378 2Mikami, K. et al. Org. Lett.,1999, 1, 2013

  36. BINOL in Friedel-Crafts Reaction Binaphthol is newly introduced by Mikami and coworkers1 Steric silyl group is needed (inter. attack) Aromatic group stabilize the charge 1Mikami, K. et al. Org. Lett.,1999, 1, 2013

  37. BINOL in Friedel-Crafts Reaction Few years later, the same group optimized a real Friedel-Crafts reaction1 Need of a stronger Lewis Acid2 1Mikami, K. et al. J. Org. Chem.,2000, 65, 1597-1599 2Yudin, A. K. et al. Chem. Rev., 2003, 103, 3155

  38. Chemistry of BINOL as a Chiral Auxiliary Introduced as a leaving group in limonene synthesis1,2: Main goal: mimic the biogenetic pathway Proceed via a metal-anchimeric assistance 1Maruoka, K. and Yamamoto, H. J. Am. Chem. Soc., 1983, 105, 6154 2Maruoka, K. and Yamamoto, H. Tetrahedron, 1986, 42, 2193

  39. Chemistry of BINOL as a Chiral Auxiliary This part blocks The front face Recuperation of the chiral auxiliary is also possible Since these experiments, BINOL has been consider as C.A. in Terpene synthesis, affording acceptable e.e 1,3 1Maruoka, K. and Yamamoto, H. J. Am. Chem. Soc., 1983, 105, 6154 2Maruoka, K. and Yamamoto, H. Tetrahedron, 1986, 42, 2193 3Cho, J. H. et al. Bull. Korean Chem. Soc., 1989, 10, 323

  40. Chemistry of BINOL as a Chiral Auxiliary In 1989, Hosoi and coworkers introduced BINOL in Aldol reactions1,2: Conclusion: Kinetic Control from the Naphthyl core and the directing hydroxyl group Here, a substituted phenyl group is used: other functions are also possible with high ee vinyl, crotyl,etc.) 1Hosoi, D.; Fuji, K. et al. Tetrahedron Lett., 1989, 30, 2825 2Fuji, K. J. Am. Chem. Soc., 1995, 117, 12159 3Ireland, R. E. et al. J. Am. Chem. Soc., 1976, 98, 2868

  41. Chemistry of BINOL as a Chiral Auxiliary In 1996, Fuji’s group upgraded their methodology in amino acids synthesis1,2,3: 1Fuji, K. et al. Tetrahedron: Asymmetry, 1996, 7, 1771 2Fuji, K. et al. Tetrahedron: Asymmetry, 1990, 31, 6553 3Fuji, K. et al. Tetrahedron: Asymmetry, 1991, 32, 7281

  42. Chemistry of BINOL as a Chiral Auxiliary Optically active ß-substituted carboxylic acid can be obtained1,2: (via Michael addition) Less cuprate reagent decrease both yield and ee IDEM with lower temperature (ketene formation disfavoured) 1Hosoi, D.; Fuji, K. et al. Tetrahedron Lett., 1989, 30, 2825 2Fuji, K. J. Am. Chem. Soc., 1995, 117, 12159

  43. Chemistry of BINOL as a Chiral Auxiliary Chemical Mechanistic proposed for the Gilman reagent addition: 1Hosoi, D.; Fuji, K. et al. Tetrahedron Lett., 1989, 30, 2825 2Fuji, K. J. Am. Chem. Soc., 1995, 117, 12159

  44. Chemistry of BINOL as a Chiral Auxiliary With the same starting reagents, the other isomer is accessible!1,2 1Fuji, K. J. Am. Chem. Soc., 1995, 117, 12159 2Hayashi, T.; Yamamoto, K.; Kumada, M. Tetrahedron Lett., 1989, 30, 2825

  45. Future Literature Meeting Works… • Substituted BINOLs are also possible for new or improved asymmetric reactions • Good precursor to other chiral ligand like BINAP: opening to new applications • Sky’s the limit with this excellent chirality generator

  46. Conclusion • Easily accessible, BINOL can be buy and/or synthesized in an asymmetric manner or by resolution of the racemic mixture with high recovery yields of the chiral reagents • Versatile reagent that can be use in many reactions with good to excellent yields and enantiomeric excess • BINOL shows also great selectivity in many other reactions like hydrogenation reactions and crown ethers- phase transfert reactions

  47. Thank you Do not ask what BINOL can do for you But what you can do with some BINOL

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