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

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Presentation on theme: "1 Applications of Atropisomerism: the Use and the Versatility of Enantioenriched BINOL Reagent in Organic Chemistry Literature Meeting, January 13 th 2009."— Presentation transcript:

1 1 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

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

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

4 4

5 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 6 Introduction: Easy Access to BINOL First racemic synthesis in 1873 by von Richter 1 Then the preparation of racemic BINOL has been widely studied… here few methods Oxidative coupling of 2-naphthol using FeCl 3, K 3 Fe(CN) 6 Mn(acac) 3, Cu-amine complexes or TiCl 4 are commonly used with yields up to 90% (Brunel, J. M., Chem. Rev., 2005, 105, 857)

7 7 Introduction: Easy Access to BINOL Mechanistic example with FeCl 3 1 1 Iwata, 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 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) Enzymatic procedure can be used too on a multigram scale using Bovine Pancreatic active 3,4 component but… Usually, the chirality is not induced by the oxidative dimerization but by the stereoselective crystallization of the complex (partial racemization), but… 3 Radical species directed by complexation with chiral amine! 1

9 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 best 4,5

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

11 11 Atropisomerism: Introduction Racemization kinetics of optically active 1,1’-binaphthyl was studied by Cooke and Harris in 1963 1 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 DMF 2

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

13 13 BINOL in Chemical Reactions First applied as a chiral phase transfert by Cram in 1978 1 Its potential as chiral ligand for metal-mediated catalysis was first recognized by Noyori in 1979 2 Since 1990, enantioenriched BINOL have become among the most widely used ligands for both stoichiometric and catalytic asymmetric reactions 3 1 Cram, D. et al. J. M. Acc. Chem. Res., 1978, 11, 8 2 Noyori, R. J. Am. Chem. Soc., 1979, 101, 3129 for reduction of aromatic ketones and aldehydes 3 Brunel, 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 Few attractions in BINOL’s antecedents

14 14 BINOL in Kinetic Resolution Strategies Yamamoto reported for the first time the use of chiral binaphthyl organoaluminum reagent (1988) 1 Via Matched / Mismatched aluminocomplexation Then, there is several examples of Natural alkaloids in kinetic resolution 3,4,5 Via Steric complementary (matched chirality) and specific intermolecular forces

15 15 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…) 1 Harris, W. W. et al. Tetrahedron Lett., 1996, 37, 7623 – 7626; Nguyen, S. T. et al. Angew. Chem. Int. Ed., 2002, 41, 1020 BINOL in Kinetic Resolution Strategies

16 16 1 Kurti L. and Czako B. Strategic Application of Named Reaction in Organic Synthesis, Elsevier Academic Press, 2005 2 Jackman, L. M. and J. A. Mills. Mechanism of the Meerwein–Ponndorf Reduction, Nature, 164, 1949, 789-790 3 Nguyen, S. T. et al. J. Am. Chem. Soc., 2006, 128, 12596-12597 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… BINOL in Kinetic Resolution Strategies

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

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

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

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

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

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

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

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

25 25 Nonlinear Effect (NLE) with BINOL Mikami and Nakai’s explanation of the diastereoisomers stabilisation 1,2 1 Mikami, K.; Nakai, T. et al. J. Chem. Soc., Chem. Commun., 1994, 833 2 Matsumoto, Y. and Mikami, K. Chem. Commun., 1997, 281 3 Kagan, H. B. Angew. Chem. Int. Ed., 1998, 37, 2922-2959 3D Representations Of Titanium complex 1 (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

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

27 27 In attempt to find a mechanism, Shibasaki’s group studied some additives 1,2,3 1 Sasai, H.; Bougauchi, M.; Shibasaki, M. Tetrahedron Lett., 1998, 39, 7353 2 Shibasaki, M. et al. Tetrahedron Lett., 2000, 41, 9569-9574 Enantioselective epoxidation reactions - 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%

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

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

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

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

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

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

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

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

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

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

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

39 39 1 Maruoka, K. and Yamamoto, H. J. Am. Chem. Soc., 1983, 105, 6154 2 Maruoka, K. and Yamamoto, H. Tetrahedron, 1986, 42, 2193 3 Cho, J. H. et al. Bull. Korean Chem. Soc., 1989, 10, 323 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 This part blocks The front face Chemistry of BINOL as a Chiral Auxiliary

40 40 1 Hosoi, D.; Fuji, K. et al. Tetrahedron Lett., 1989, 30, 2825 2 Fuji, K. J. Am. Chem. Soc., 1995, 117, 12159 3 Ireland, R. E. et al. J. Am. Chem. Soc., 1976, 98, 2868 In 1989, Hosoi and coworkers introduced BINOL in Aldol reactions 1,2 : 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.) Chemistry of BINOL as a Chiral Auxiliary

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

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

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

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

45 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 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 47 Thank you Do not ask what BINOL can do for you But what you can do with some BINOL


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