Enantioselective photochemistry. Zhe Dong
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1 Enantioselective photochemistry Zhe Dong
2 Introduction of Circular Polarization Light Left-CPL- S light Chiral light -> Chiral Product? Right-CPL- R light
3 Introduction of Non-Linear Effects 20%ee of DET 45%ee of Product How can this happen? Chiral Lignand Self-assembly -> diastereoselectivity For transition metal catalysis usually means multi-metal in T.S.
4 Introduction of Non-Linear Effects
5 General Way for enatioselective synthesis Photochemistry Normal chemistry chiral auxiliary (chiral SET) chiral auxiliary (chiral arrow pushing) Kinetic resolution (by light!) Kinetic resolution (by chiral molecule) Enatioselective catalyst (chiral molecule or chiral light) Enatioselective catalyst (chiral molecule) Chiral light- just need electricity and glass 100mg 300 dollar F.W. 870
6 Introduction The direct CPL introduce the ee: The Soai reaction combine CPL and auto-tamden-catalysis Diastereoseletive Photoreactions with Chiral Auxiliaries Enantioselective Photoreactions with Chiral catalyst
7 Direct CPL introduce the ee The direct CPL introduce the ee: The Soai reaction combine CPL and auto-tamden-catalysis Diastereoseletive Photoreactions with Chiral Auxiliaries Enantioselective Photoreactions with Chiral catalyst
8 Early development : Direct CPL introduce the ee 1.This possibility was well illustrated by van t Hoff in The detection of CD by Cotton in 1896 further corroborated that CPL could induce optical activity in chemical systems. But just Point CPL has a different influence on the reaction. 3.W. Kuhn first succeed in 1929 to get some enatiopure product. 4.The interest in CPL induced photochemistry peaked again in the 1970s, when reliable spectropolarimeters for CD measurements became commercially available. G=0.02
9 Direct CPL introduce the ee g=0.1 Blume, R.; Rau, H.; Schuster, O. J. Am. Chem. Soc. 1976, 98, Nicoud, J. F.; Eskenazi, C.; Kagan, H. B. J. Org. Chem. 1977, 42, 4270.
10 Direct CPL introduce the ee Eskenazi, C.; Kagan, H. B Tetrahedron, 1975, 31, 2139 g = ε ε ε = ε R ε S ee = C R C S C R + C S = ε R ε S ε R + ε S = ε 2ε = g 2 Balavoine, G.; Moradpour, A.; Kagan, H. B. J. Am. Chem. Soc. 1974, 96, 5152.
11 Focused Laser Induced Enantioenrichment Is this one origin of the Chirality and life? Norden, B. Nature 1977, 266, 567 Shimizu, Y. J. Chem. Soc. Perkin Trans , 1275.
12 CPL react with amino acid Flores, J. J.; Bonner, W. A.; Massey, G. A. J. Am. Chem. Soc. 1977, 99, Cronin, J. R.; Pizzarello, S. Science 1997, 275, 951..
13 Soai reaction The direct CPL introduce the ee: The Soai reaction combine CPL and auto-tamden-catalysis Diastereoseletive Photoreactions with Chiral Auxiliaries Enantioselective Photoreactions with Chiral catalyst
14 Soai reaction K. Soai, T. Shibata, H. Morioka and K. Choji Nature, 1995, 378,
15 Soai reaction Sato, I.; Urabe, H.; Ishiguro, S.; Shibata, T.; Soai, K. Angew. Chem. Int. Ed. 2003, 42, 315.
16 Soai reaction Sato, I.; Sugie, R.; Matsueda, Y.; Furumura, Y.; Soai, K. Angew. Chem. Int. Ed. 2004, 43, 4490.
17 Soai reaction Sato, I.; Sugie, R.; Matsueda, Y.; Furumura, Y.; Soai, K. Angew. Chem. Int. Ed. 2004, 43, 4490.
18 Soai reaction Kawasaki, T.; Sato, M.; Ishiguro, S.; Saito, T.; Morishita, Y.; Sato, I.; Nishino, H.; Inoue, Y.; Soai, K. J. Am. Chem. Soc. 2005, 127, 3274.
19 Soai reaction Kawasaki, T.; Sato, M.; Morishita, Y.; Sato, I.; Inoue, Y.; Soai, K. Science. 2009, 324, 492.
20 Diastereoseletive Photoreactions with Chiral Auxiliaries The direct CPL introduce the ee: The Soai reaction combine CPL and auto-tamden-catalysis Diastereoseletive Photoreactions with Chiral Auxiliaries Enantioselective Photoreactions with Chiral catalyst
21 Diastereoseletive Photoreactions with Chiral Auxiliaries Tanaka, K.; Fujiwara, T. Org. Lett. 2005, 7, 1501.
22 Diastereoseletive Photoreactions with Chiral Auxiliaries Carreira, E. M.; Hastings, C. A.; Shepard, M. S.; Yerkey, L. A.;Millward, D. B. J. Am. Chem. Soc. 1994, 116,
23 Diastereoseletive Photoreactions with Chiral Auxiliaries Carreira, E. M.; Hastings, C. A.; Shepard, M. S.; Yerkey, L. A.;Millward, D. B. J. Am. Chem. Soc. 1994, 116,
24 Diastereoseletive Photoreactions with Chiral Auxiliaries de > 19:1 T. Bach, H. Bergmann, K. Harms, J. Am. Chem. Soc. 1999, 121,
25 Diastereoseletive Photoreactions with Chiral Auxiliaries Bach, T.; Bergmann, H.; Grosch, B.; Harms, K. J. Am. Chem. Soc. 2002, 124, 7982.
26 Diastereoseletive Photoreactions with Chiral Auxiliaries Bach, T.; Bergmann, H.; Grosch, B.; Harms, K. J. Am. Chem. Soc. 2002, 124, 7982.
27 Diastereoseletive Photoreactions with Chiral Auxiliaries Bach, T.; Bergmann, H.; Grosch, B.; Harms, K. J. Am. Chem. Soc. 2002, 124, 7982.
28 Diastereoseletive Photoreactions with Chiral Auxiliaries H = 11.8 kj mol G = 13.5 kj mol Urea ketone model: Has homo dimer problem. H around 8kj/mol Bach, T.; Bergmann, H.; Grosch, B.; Harms, K. J. Am. Chem. Soc. 2002, 124, 7982.
29 Diastereoseletive Photoreactions with Chiral Auxiliaries Bertrand, S.; Hoffmann, N.; Pete, J. Eur. J. Org. Chem. 2000, 2227.
30 Enantioselective Photoreactions with Chiral catalyst Bauer, A.; Westkamper, F.; Grimme, S.; Bach, T. Nature 2005, 436, 1139.
31 Enantioselective Photoreactions with Chiral catalyst Bauer, A.; Westkamper, F.; Grimme, S.; Bach, T. Nature 2005, 436, 1139.
32 Enantioselective Photoreactions with Chiral catalyst Bauer, A.; Westkamper, F.; Grimme, S.; Bach, T. Nature 2005, 436, 1139.
33 Enantioselective Photoreactions with Chiral catalyst Bauer, A.; Westkamper, F.; Grimme, S.; Bach, T. Nature 2005, 436, B. Ye, N. Cramer, J. Am. Chem. Soc. 2013, 135, What will happen if we combine this template and directing group?
34 Enantioselective Photoreactions with Chiral catalyst P. Selig, T. Bach, Angew. Chem. Int. Ed. 2008, 47
35 Enantioselective Photoreactions with Chiral catalyst P. Selig, T. Bach, Angew. Chem. Int. Ed. 2008, 47
36 Enantioselective Photoreactions with Chiral catalyst 15 steps from 5, 7% overall yield (Overman racemic 24 steps) P. Selig, T. Bach, Angew. Chem. Int. Ed. 2008, 47
37 Enantioselective Photoreactions with Chiral catalyst 5% 5 conv=50% brsm=98% 2/3=78/22 90%ee 20% 5 conv=73% brsm=78% 2/3=79/21 94%ee C. Muller. A. Bauer, T. Bach. Angew. Chem. Int. Ed. 2009, 48,
38 Enantioselective Photoreactions with Chiral catalyst C. Müller, A. Bauer, M. M. Maturi, M. C. Cuquerella, M. A. Miranda, T. Bach, J. Am. Chem. Soc. 2011, 133,
39 Enantioselective Photoreactions with Chiral catalyst S. C. Coote, T. Bach, J. Am. Chem. Soc. 2013, 135,
40 Enantioselective Photoreactions with Chiral catalyst S. C. Coote, T. Bach, J. Am. Chem. Soc. 2013, 135,
41 Enantioselective Photoreactions with Chiral catalyst E. Canales. E. J. Corey J. Am. Chem. Soc. 2007, 129,
42 Enantioselective Photoreactions with Chiral catalyst 7d: R=CF3 R1=Me H. Guo, E. Herdtweck T. Bach. Angew. Chem. Int. Ed. 2010, 49,
43 Enantioselective Photoreactions with Chiral catalyst R. Brimioulle, T. Bach, Science 2013, 342,
44 Enantioselective Photoreactions with Chiral catalyst R. Brimioulle, T. Bach, Science 2013, 342,
45 Enantioselective Photoreactions with Chiral catalyst R. Brimioulle, T. Bach, Science 2013, 342,
46 Conclusion The direct CPL introduce the ee: Low yield and low ee. The Soai reaction combine CPL and auto-tamden-catalysis: very Limited substrate Diastereoseletive Photoreactions with Chiral Auxiliaries : Not effective compared with Macmillan s SOMO system. Enantioselective Photoreactions with Chiral catalyst: Extremely High loading and limited substrate. All in all there is a great potential room to be improved!
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