Non-Enzymatic Enantioselective Polyene Cyclizations. Adam Hill Chem 535 May, 2 nd 2013
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1 Non-Enzymatic Enantioselective Polyene Cyclizations Adam Hill Chem 535 May, 2 nd 2013
2 Enantioselective Polyene Cyclization (?) General Method to Rapidly Build Molecular Complexity (+) Exquisite Stereo- and Regio- Control (-) Single Substrate
3 Methods for Polyene Cyclization Squalene Cyclase Mechanism: Chiral Bronsted Acid Catalysis: Transition Metal Catalysis: Organocatalysis:
4 Squalene Cyclization
5 2,3-Oxidosqualene Cyclization Mechanism
6 Stork-Eschenmoser Hypothesis Stork Studies: Eschenmoser Studies: Cyclization occurs by stereospecific and concerted anti-addition Gamboni, G.; Schinz, H.; Eschenmoser, A. Helv. Chima. Acta 1954, 37, 964
7 Concerted A-Ring Formation Relative Rates of Cyclization: Epoxide protonation and A-ring closure occurs by a concerted anti-addition Corey, E.J.; Cheng, H.; Baker, C.H.; Matsuda, S.P.T.; Li, D.; Song, X. J. Am. Chem. Soc. 1997, 119,
8 B- and C-Ring Cyclization Cyclization of Truncated Oxidosqualene Analogs: C-ring closure gives a system which rearranges to the system in lanosterol Corey, E.J.; Virgil, S.C.; Cheng, H.; Baker, C.H.; Matsuda, S.P.T.; Singh, V.; Sarshar, S. J. Am. Chem. Soc. 1995, 117,
9 C-Ring Expansion and Elimination to Lanosterol Corey, E.J.; Virgil, S.C.; Cheng, H.; Baker, C.H.; Matsuda, S.P.T.; Singh, V.; Sarshar, S. J. Am. Chem. Soc. 1995, 117,
10 Squalene Cyclization Mechanism Corey, E.J.; Virgil, S.C.; Cheng, H.; Baker, C.H.; Matsuda, S.P.T.; Singh, V.; Sarshar, S. J. Am. Chem. Soc. 1995, 117,
11 Conformational Restriction of Squalene 2-azasqualene bound to oxidoqualene cyclase Reinert, D.J.; Balliano, G.; Schulz G.E. Chem. Biol. 2004, 11,
12 Cation-Stabilization by Squalene Cyclase Mutagenesis Studies Hopene overlaid on SHC active site E.J. Corey; Cheng, H.; Baker, H.; Matsuda, S.P.T.; Li, D.; Song, X. J. Am. Chem. Soc. 1997, 119, 1289 Wendt, K.U.; Schulz, G.E.; Corey, E.J.; Liu, D.R. Angew. Chem. Int. Ed. 2000, 39,
13 Cation-Stabilization by Squalene Cyclase Mutagenesis Studies Hopene overlaid on SHC active site E.J. Corey; Cheng, H.; Baker, H.; Matsuda, S.P.T.; Li, D.; Song, X. J. Am. Chem. Soc. 1997, 119, 1289 Wendt, K.U.; Schulz, G.E.; Corey, E.J.; Liu, D.R. Angew. Chem. Int. Ed. 2000, 39,
14 Cation-Stabilization by Squalene Cyclase Mutagenesis Studies Hopene overlaid on SHC active site E.J. Corey; Cheng, H.; Baker, H.; Matsuda, S.P.T.; Li, D.; Song, X. J. Am. Chem. Soc. 1997, 119, 1289 Wendt, K.U.; Schulz, G.E.; Corey, E.J.; Liu, D.R. Angew. Chem. Int. Ed. 2000, 39,
15 Methods for Polyene Cyclization Squalene Cyclase Mechanism: Chiral Bronsted Acid Catalysis: Transition Metal Catalysis: Three Roles of Cyclase: Enantioselective A ring formation Organocatalysis: Stabilization of the developing positive charge Conformation control of the linear precursor
16 Methods for Polyene Cyclization Squalene Cyclase Mechanism: Chiral Bronsted Acid Catalysis: Transition Metal Catalysis: Organocatalysis:
17 Lewis Acid-Assisted Chiral Bronsted Acid (LBA) First example of an enantioselective biomimetic cyclization: Ishihara, K.; Nakamura, S.; Yamamoto, H. J. Am. Chem. Soc. 1999, 121,
18 Lewis Acid-Assisted Chiral Bronsted Acid (LBA) Enantioselective Cyclization via Formal [1,3]-rearrangement: Mechanism of the Formal [1,3]-rearrangement: Ishihara, K.; Nakamura, S.; Yamamoto, H. J. Am. Chem. Soc. 1999, 121,
19 Mechanism of LBA catalysis Entry Bronsted Acid R 1 = R 2 = Yield ee % racemic 2 R 1 = OMe R 2 = Me 83% racemic 3 R 1 = OMe R 2 = OMe 65% racemic 4 R 1 = OH R 2 = Me 83% 46% 5 R 1 = OH R 2 = Bz 98% 79% SnCl 4 Catalyzed Cyclization LBA Catalyzed Cyclization Hydroxyl group is required for asymmetric cyclization Nakamura, S.; Ishihara, K.; Yamamoto, H. J. Am. Chem. Soc. 2000, 122,
20 Mechanism of LBA catalysis = 1 equiv LBA = 0.2 equiv LBA Product inhibition lowers ee when R-BINOL-Bz is used catalytically Nakamura, S.; Ishihara, K.; Yamamoto, H. J. Am. Chem. Soc. 2000, 122,
21 Calculated Transition Structure for LBA with 2-methyl-2-butene Major Enantiomer Nakamura, S.; Ishihara, K.; Yamamoto, H. J. Am. Chem. Soc. 2000, 122, Minor Enantiomer
22 Natural Product Synthesis Using LBA Total Synthesis of (-)-Chromazonarol: Total Synthesis of (-)-11 -Deoxytanodiol methyl ether: Ishibashi, H.; Ishihara, K.; Yamamoto, H. J. Am. Chem. Soc. 2004, 126,
23 LBA Using Antimony Lewis Acids 4 examples 70% - 80% yield, 87% - 92% ee pre-transition state assembly: 4 examples 70% - 78% yield, 84% - 90% ee Surendra, K.; Corey, E.J. J. Am. Chem. Soc. 2012, 134,
24 Methods for Polyene Cyclization Squalene Cyclase Mechanism: Chiral Bronsted Acid Catalysis: (+) Enantioselective cyclization of the first ring Transition Metal Catalysis: Organocatalysis: (-) No stabilization of developing cationic charge (-) Requires low temperatures and long reaction times to control substrate conformation
25 Methods for Polyene Cyclization Squalene Cyclase Mechanism: Chiral Bronsted Acid Catalysis: Transition Metal Catalysis: Organocatalysis:
26 Platinum Catalyzed Cyclization Proposed Catalytic Cycle: Single turnover observed without trityl cation Catalyst resting state shows a single agostic complex Mullen, C.A.; Gagne, M.R. J. Am. Chem. Soc. 2007, 129,
27 Pt Catalyzed Polyene Cyclization Chiral Ligand Screen: Large aryl groups in a non-binap derived bisphosphine ligands gave the highest enantioselectivity Mullen, C.A.; Campbell, A.N.; Gagne, M.R. Angew. Chemie. Int. Ed. 2008, 47,
28 Scope Mullen, C.A.; Campbell, A.N.; Gagne, M.R. Angew. Chemie. Int. Ed. 2008, 47,
29 C3-Functionalization Post Catalytic Cycle Proposed Catalytic Cycle: Scope: 10 examples: 55% - 65% yield and 70%-80% ee Possible method to install fluorine into steroid-like frameworks Other Pt-C bond functionalization may be possible Cochrane, N.A.; Nguyen, H.; Gagne, M.R. J. Am. Chem. Soc. 2013, 135,
30 Alkyne Activation via Gold Catalysis Chiral Ligand Screen: Solvent Screen: Entry Solvent Yield ee 1 CH 2 Cl 2 71% 46% 2 benzene 76% 83% 3 toluene 77% 85% 4 m-xylene 76% 87% *Using (R)-MeO-DTB-BIPHEP Sethofer, S.G.; Mayer, T.; Toste, D.E. J. Am. Chem. Soc. 2010, 132,
31 Alkyne Activation via Gold Catalysis Substrate Scope: Sethofer, S.G.; Mayer, T.; Toste, D.E. J. Am. Chem. Soc. 2010, 132,
32 Ir-Catalyzed Activation of Allylic Alcohols Reaction Optimization: Entry Promoter Solvent Yield ee 1 P(O)(OBu) 2 OH DCE 42% 89% 2 TfOH DCE 12% 81% 3 Sc(OTf) 3 DCE 91% 80% 4 Zn(OTf) 2 DCE 90% >99.5% 5 Zn(OTf) 2 dioxane 8% >99.5% 6 Zn(OTf) 2 DMF n.r. - Schafroth, M.A.; Sarlah, D.; Krautwald, S.; Carreira, E.M. J. Am. Chem. Soc. 2012, 134,
33 Scope of Ir-Catalyzed Cyclization Heteroaryl Terminating Groups: Successful heteroaryl termination of cation-olefin cyclization Schafroth, M.A.; Sarlah, D.; Krautwald, S.; Carreira, E.M. J. Am. Chem. Soc. 2012, 134,
34 Ir-Catalyzed Tricyclization Schafroth, M.A.; Sarlah, D.; Krautwald, S.; Carreira, E.M. J. Am. Chem. Soc. 2012, 134,
35 Methods for Polyene Cyclization Squalene Cyclase Mechanism: Chiral Bronsted Acid Catalysis: Transition Metal Catalysis: Organocatalysis: (+) Increased enantioselectivities over chiral Bronsted acid catalysis (-) No mechanism by which to prevent early termination
36 Methods for Polyene Cyclization Squalene Cyclase Mechanism: Chiral Bronsted Acid Catalysis: Transition Metal Catalysis: Organocatalysis:
37 Phosphoramidite Catalyzed Halocyclization Racemic Cyclization: Entry Nucleophile Yield (%) DMAP 0 3 PPh PBu 3 99 Sakakura, A.; Ukai, A.; Ishihara, K. Nature, 2007, 445,
38 Phosphoramidite Catalyzed Halocyclization Chiral Phosphoramidite Screen: Scope: 4 examples: 50%-60% yield, 90-95% ee Sakakura, A.; Ukai, A.; Ishihara, K. Nature, 2007, 445,
39 Rendler, S.; MacMillan, D.W.C. J. Am. Chem. Soc. 2010, 132, Organo-SOMO Catalysis
40 Organo-SOMO Catalysis Entry Catalyst Additive Solvent Yield (%) ee (%) 1 Ar = Ph - MeCN Ar = Ph TFA MeCN * Ar = Ph TFA MeCN * Ar = 1-Np TFA MeCN * Ar = 1-Np TFA i-prcn/dme *with slow addition of Cu(OTf) 2 Rendler, S.; MacMillan, D.W.C. J. Am. Chem. Soc. 2010, 132,
41 Rendler, S.; MacMillan, D.W.C. J. Am. Chem. Soc. 2010, 132, Scope
42 Thiourea Catalysis Catalyst Optimization: Knowles, R.R.; Lin, S.; Jacobsen, E.N. J. Am. Chem. Soc. 2010, 132,
43 Thiourea Catalysis Reaction Scope: Knowles, R.R.; Lin, S.; Jacobsen, E.N. J. Am. Chem. Soc. 2010, 132,
44 Eyring Analysis Catalyst Structures: Knowles, R.R.; Lin, S.; Jacobsen, E.N. J. Am. Chem. Soc. 2010, 132,
45 Methods for Polyene Cyclization Squalene Cyclase Mechanism: Chiral Bronsted Acid Catalysis: Transition Metal Catalysis: (+) Aryl groups may provide a mechanism to prevent early termination (-) Requires contrived substrates or exotic activating groups Organocatalysis:
46 Methods for Polyene Cyclization Squalene Cyclase Mechanism: Chiral Bronsted Acid Catalysis: Transition Metal Catalysis: Organocatalysis:
47 Future Directions Chiral Anion Catalysis: Cavitand Based Catalysts: Chiral Anion Catalysis: Hamilton, G.L.; Kang, E.J.; Toste, F.D. Science, 2007, 317, 496 Cavitands in epoxide opening cascades: Pinacho Crisostomo, F.R.; Lledo, A.; Shenoy, S.R.; Iwasawa, T.; Rebek, J. J. Am. Chem. Soc. 2009, 131,
48 Acknowledgements CHEM 535 Class Professor Zimmerman Burke Group Professor Burke
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