Story Behind the Well-Developed Chiral Lewis Acid in Asymmetric Diels-Alder reaction
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1 Story Behind the Well-Developed Chiral Lewis Acid in Asymmetric Diels-Alder reaction Reporter: Zhang Sulei Supervisors: Prof. Yang Zhen Prof. Chen Jiahua Prof. Tang Yefeng
2 Contents Background Development of Chiral Lewis Acid Catalyst(CLA) Design in Asymmetric Diels-alder Reaction Pioneering Work Tartaric derived CLA BINOL/VAPOL derived CLA Aminoalcohol dericed CLA Summary and Acknowledge 2
3 Background Asymmetric Diels-Alder reaction 1970s 1980-now Dienophile with chiral auxiliary Lewis Acid catalyzed D-A Chiral Lewis Acid Catalyzed D-A 3
4 Contents Background Development of Chiral Lewis Acid Catalyst(CLA) Design in Asymmetric Diels-alder Reaction Pioneering Work Tartaric derived CLA BINOL/VAPOL derived CLA Aminoalcohol dericed CLA Summary and Acknowledge 4
5 CLA in Diels-Alder Reaction Pioneering Work Tartaric derived CLA BINOL/VAPOL derived CLA Aminoalcohol dericed CLA 5
6 Pioneering Work 1979, Koga First example Steric Interaction 1987, Kaufmann Steric Interaction 1991, Hawkins two-point-binding Hashimoto, S.; Komeshima, N.; Koga, K. J. Chem. Soc., Chem. Commun. 1979, 437. Bir, G.; Kaufmann, D. Tetrahedron Lett. 1987, 28, 777. Hawkins, J. M.; Loren, S. J. Am. Chem. Soc. 1991, 113, Hawkins, J. M.; Loren, S.; Nambu, M. J. Am. Chem. Soc. 1994, 116,
7 CLA in Diels-Alder Reaction Pioneering Work Tartaric derived CLA BINOL/VAPOL derived CLA Aminoalcohol dericed CLA 7
8 L-Tartaric acid derived CAB Origin 1988, Yamamoto: Toward simple dienophile Substrate screening Generality Practicability Brown, H. C.; Stocky, T. P. J. Am. Chem. Soc. 1977, 99, Furuta, K.; Miwa, Y.; Iwanaga, K.; Yamamoto, H. J. J. Am. Chem. Soc. 1988, 110, Furuta, K.; Shimizu, S.; Miwa, Y.; Yamamoto, H. J. Org. Chem. 1989, 54,
9 Mechanistic Analysis 1. Determine the activated face (Adol reaction): Re-face attack, then Si-face shielding. 2. Detailed 1 H NMR (NOE) analysis 3. Detailed 1 H NMR (NOE) analysis π stacking Ishihara, K.; Gao, Q.; Yamamoto, H. J. Am. Chem. Soc. 1993, 115,
10 CLA in Diels-Alder Reaction Pioneering Work Tartaric derived CLA BINOL/VAPOL derived CLA Amino-alcohol derived CLA 10
11 BINOL/VAPOL-CLA concave convex 1993, William D. Wulff Helmchen, G.; Schmiere, R. Angew. Chem., Int. Ed. Engl. 1981, 20, 205. Bao J.; Wulff, W. D.; Rheingold A. L., J. Am. Chem. Soc. 1993, 115,
12 BINOL/VAPOL-CLA 1993, William D. Wulff Highest induction Lowest catalyst loading Bao J.; Wulff, W. D.; Rheingold A. L., J. Am. Chem. Soc. 1993, 115,
13 BINOL-Helical CLA 1993, Yamamoto Effective hydrogen bond Helix conformation Designed helical metal catalysts New model Moderate activity Maruoka, K.; Murase, N.; Yamamoto, H. J. Org. Chem. 1993, 58,
14 BINOL-BLA 1994, Yamamoto 1 st chiral BLA catalyst Intramolecular hydrogen bonding interaction attractive π-π donor-acceptor interaction Substrate: α-substituted enals various dienes. Ishihara, K.; Yamamoto, H. J. Am. Chem. Soc. 1994, 116,
15 Mechanism analysis Adol reaction: Re-face attack, Si-face shielded Hydroxyphenyl: Hydrogen Bonding π donor-acceptor interaction Abs. config.(s): dienophile s-trans Ishihara, K.; Yamamoto, H. J. Am. Chem. Soc. 1994, 116,
16 Mechanism analysis BLA Monoether-BLA Opposite face selectivity Ishihara, K.; Yamamoto, H. J. Am. Chem. Soc. 1994, 116,
17 BINOL-BLA 1996, Yamamoto 2 nd chiral BLA catalyst-more practical More Lewis acidic; Activate some reaction. Ishihara, K.; Kurihara, H.; Yamamoto, H. J. Am. Chem. Soc. 1996, 118, Ishihara, K.; Kurihara, H.; Matsumoto, M.; Yamamoto, H. J. Am. Chem. Soc. 1998, 120,
18 Results and Interpretation Substrate Assembly Model Ishihara, K.; Kurihara, H.; Yamamoto, H. J. Am. Chem. Soc. 1996, 118, Ishihara, K.; Kurihara, H.; Matsumoto, M.; Yamamoto, H. J. Am. Chem. Soc. 1998, 120,
19 CLA in Diels-Alder Reaction Pioneering Work Tartaric derived CLA BINOL/VAPOL derived CLA Amino-alcohol derived CLA 19
20 Tryptophan-derived oxazaborolidine catalyst Origin 1991, Corey Broad application Diene: Corey, E. J.; Bakshi, R. K.; Shibata, S. J. Am. Chem. SOC. 1987, 109, 5551 Corey, E. J.; Loh, T-P. J. Am. Chem. Soc. 1991, 113,
21 Physical and Chemical studies: Experiment support Cat. ID.: 1 H NMR, 11 B NMR, 13 C NMR 1 H 2-D NOESY: Rigid Geometry as depicted Corey, E. J.; Loh, T-P.; Roper, T. D.; Azimioara, M. D.; Noe, M. C. J. Am. Chem. Soc. 1992, 114,
22 Physical and Chemical studies: Experiment support 210K > 250K 1. Charge Transfer 2. Indole cis Dienophile Corey, E. J.; Loh, T-P.; Roper, T. D.; Azimioara, M. D.; Noe, M. C. J. Am. Chem. Soc. 1992, 114,
23 Physical and Chemical studies: Experiment support Both the indole and N-Ts are crucial: π-donor/acceptor interaction Fix the position of indole Steric repulsion/better overlap: s-cis Corey, E. J.; Loh, T-P.; Roper, T. D.; Azimioara, M. D.; Noe, M. C. J. Am. Chem. Soc. 1992, 114,
24 Proline-derived oxazaborolidine catalyst Origin 1991, Mukaiyama The HBr salt : crucial for high enantioselectivity Soai, K.; Ookawa, A.; Kaba, T.; Ogawa, K. J. Am. Chem. Soc. 1987, 109, Kobayashi, S.; Murakami, M.; Harada, T.; Mukaiyama, T. Chem. Lett. 1991,
25 Cationic oxazaborinane catalyst 1996, Corey LA: Cationic oxazaborinane >neutral 3,5-dimethylbenzyl on N is important. Hayashi, Y.; Rohde, J. J.; Corey, E. J. J. Am. Chem. Soc. 1996, 118,
26 Cationic oxazaborinane catalyst N-CH 2 Ar: block one face of dienophile; Limits the rotation of dienophile & N-CH 2 Ar Formyl C-H---O: weak hydrogen bond Supported by X-ray crystal structures Corey, E. J.; Rohde, J. J.; Fischer, A.; Azimioara, M. D. Tetrahedron Lett. 1997, 38, 33. Corey, E. J.; Rohde, J. J.; Tetrahedron Lett. 1997, 38, 37. Corey, E. J.; Barnes-Seeman, D.; Lee, T. W. Tetrahedron Lett. 1997, 38,
27 Proline derived cationic oxazaborolidine catalyst 2002, Corey A very strong protic acid is used to create a very strong lewis acid. Catalyst Screening: Corey, E. J.; Shibata T.; Lee T. W. J. Am. Chem. Soc. 2002, 124, Corey, E. J. Angew. Chem. Int. Ed. 2009, 48,
28 Proline derived cationic oxazaborolidine catalyst Substrate expanding: Ligand can be recovered for use (> 95%) after workup. Corey, E. J. Angew. Chem. Int. Ed. 2009, 48,
29 Proline derived cationic oxazaborolidine catalyst Transition state assembly and Interpretation Formyl CH----O interaction α CH----O interaction Corey, E. J. Angew. Chem. Int. Ed. 2009, 48,
30 Summary Design of Chiral Lewis Acid Intermolecular ( Strong ): Covalent bond (Lewis Acid & Base) Intermolecular ( weak ): Dipole-induced dipole interaction; Hydrogen bonding interaction; π-donor/acceptor interaction; π-stacking interaction. 30
31 Summary Design of Chiral Lewis Acid Intermolecular ( Strong ): Covalent bond (Lewis Acid & Base) Intermolecular ( weak ): Dipole-induced dipole interaction; Hydrogen bonding interaction; π-donor/acceptor interaction; π-stacking interaction. 31
32 Acknowledge Prof. Yang, Prof. Chen, Prof Tang Mr. Youlin, Mr. Luyong, Mr. LiYuanhe Mr. LiangXingting, Mr. Niuzhe All mates in B630 All members in our lab Everyone here Thanks 32
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