Domino Reactions in Total Synthesis! Reporter: Tianhe Yang! Supervisors: Prof. Yang! Prof. Chen! Prof. Tang!
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1 1! Domino Reactions in Total Synthesis! Reporter: Tianhe Yang! Supervisors: Prof. Yang! Prof. Chen! Prof. Tang!
2 2! utline! 1. Brief Introduction! 2. ucleophilic Dominoes! 3. Electrophilc Dominoes! 4. Radical Dominoes! 5. Pericyclic Dominoes! 6. Transition-tal-Catalyzed Dominoes! 7. Summary and utlook! 8. Acknowledgement!
3 3! utline! 1. Brief Introduction! 2. ucleophilic Dominoes! 3. Electrophilc Dominoes! 4. Radical Dominoes! 5. Pericyclic Dominoes! 6. Transition-tal-Catalyzed Dominoes! 7. Summary and utlook! 8. Acknowledgement!
4 Domino Reaction! 4! A domino reaction is a process involving two or more bond-forming transformations (usually C-C bonds) which take place under the same reaction conditions without adding additional reagents and catalysts, and in which the subsequent reactions result as a consequence of the functionality formed in the previous step.! L. F. Tietze! Tietze, L. F. Chem. Rev. 1996, 96, !
5 5! Terminologies! Cascade rganic Reaction ne-pot Domino Tandem ne-pot: Without isolation and purification of products.! Cascade: Two or more bonds are formed. Latter transformations take place at the functionalities obtained in the former-bond forming process.! Tandem: Several bonds are formed in sequence, without isolating intermediates, changing reaction conditions, or adding reagents.! icolaou, K. C. et al, Angew. Chem. Int. Ed. 2006, 45, ! Tietze, L. F. Chem. Rev. 1996, 96, !
6 6! Tandem but not Domino: Chlorothricolide! Intramolecular and intermolecular Diels-Alder reaction in a same step.! TBDPS DA TBDPS TBDPS IMDA t-bu toluene, 120ºC,BT, 20h tbu + C 2 Allyl C 2 Allyl TMS MM C 2 TMS MM TMS MM 40-45% 25-30% t-bu Cl 2 C=CCl, 125ºC, BT, 28-36h 20-45% Chlorothricolide Roush, W. R. et al. J. Am. Chem. Soc. 1998, 120, 7411!
7 7! Cascade but not Domino: Vitamin B 12! With genetically engineered 12 enzymes! 2 C 2 12 enzymes 17 steps 20% 2 C 2 C C 2 C 2 4 steps Vitamin B 12 C 2 C 2 hydrogenobyrinic acid Scott, A. I. J. rg. Chem. 2003, 68, 2529!
8 Advantages! 8! Dramatic increase in molecular complexity.! Save material, time, labor, energy, resource and waste management.! Beneficial effect on the environment.! Applications! Synthesize fused and caged ring system.! Quaternary stereocenter forming! Protecting group and functional group changing!
9 istory! First domino synthesis: Tropinone by Robinson at 1917:! 9! C C C 3 2 C C 2 3 C Biomimetic synthesis of Progesterone by Johnson at 1971:! TFA, DCE, 0ºC Progesterone Robinson, R. J. Chem. Soc. Trans. 1917, ! Johnson, W. S. et al, J. Am. Chem. Soc. 1971, 93, !
10 10! utline! 1. Brief Introduction! 2. ucleophilic Dominoes! 3. Electrophilic Dominoes! 4. Radical Dominoes! 5. Pericyclic Dominoes! 6. Transition-tal-Catalyzed Dominoes! 7. Summary and utlook! 8. Acknowledgement!
11 11! ucleophilic Dominoes! Initiated by a nucleophilic attack.! Common initiator:! Conjugated addition! S 2 substitution! Grignard reaction!! Followed by:! Another nucleophilic attack! Pericyclic process: oxy-cope, [3+2] etc.! Rearrangements: Brook rearrangement, B-V rearrangement.!! Pellissier,. Chem. Rev. 2012, ASAP! icolaou, K. C. et al, Angew. Chem. Int. Ed. 2006, 45, !
12 12! Key Reaction: Michael addition! Why Michael?! First step: Conjugated addition, forming a regioselected and diastereoselected enolate intermediate.! R 2 u - u R 2 - El + R u 2 R 1 R 1 R 3 R 1 R 3 El R 3 Second step: (intramolecular) condensation, S 2 reaction, or another Michael process.!
13 13! Salvinorin A by Evans! Classical transannular michael-michael process.! Conjugated addition to a β,β-disubstuted enone.! 3 sidechains are in equatorial positions.! MB C() 2-78ºC to -5ºC TBAF 99% de=ee>99% MB () 2 C Ac 2 C salvinorin A deprotonation MB () 2 C - first michael MB () 2 C - second michael MB () 2 C - Evans, D. A. et al, J. Am. Chem. Soc. 2007, 129, 8968!
14 Michael/Mannich/Mannich! 14! Cl C 2 Ph + Bn R C 3 AgBF 4 DCM, -78ºC, 2h 76% 3 C Bn R Ph C 2 + 3:1 3 C Bn R Ph C 2 Ag + -Cl R Bn Mannich Reaction C 2 Ph 3 C Michael Addition 3 C Bn R Ph C2 Bn 3 C R Ph C 2 R= Qin, Y. et al, Synlett 2011, 907!
15 15! (+)-CP-263,114 by Shair! Grignard reaction + oxy-cope rearrangement + Dickmann condensation! Shair, M.D. et al, J. Am. Chem. Soc. 2000, 122, 7424!
16 16! utline! 1. Brief Introduction! 2. ucleophilic Dominoes! 3. Electrophilic Dominoes! 4. Radical Dominoes! 5. Pericyclic Dominoes! 6. Transition-tal-Catalyzed Dominoes! 7. Summary and utlook! 8. Acknowledgement!
17 17! Electrophilic Dominoes! Initiated by a electrophilic attack.! Based on rearrangements of carbocation.! Usually Prins reaction, Fridel-Crafts reaction, Mannich reaction and rearrangements followed.! Finally being quenched by a nucleophile or stablized by elimination of a proton.! Cationic cyclization: Biomimetic synthetic route for complicated alkaloids and terpenoids.! Pellissier,. Chem. Rev. 2012, ASAP! icolaou, K. C. et al, Angew. Chem. Int. Ed. 2006, 45, !
18 18! Key Intermediate: Iminium ion! Iminium ion: good electrophile! Enamine: good nucleophile! Iminium ion/enamine equilibrium: switching! R 1 R 3 R 2 u - R 1 R 2 R 4 R R 4 3 u R 1 R 2 R 3 R 4 R El + 1 R 2 R 3 R 4 El
19 19! (+)-CP-263,114 by Shair! Construct a highly oxygenated cage like skeleton.! Shair, M.D. et al, J. Am. Chem. Soc. 2000, 122, 7424!
20 (+)-CP-263,114 by Shair! 20! 17 longest linear steps, 0.14% overall yield.! icolaou in 1999: Intramolecular Diels-Alder reaction, 46 steps, 0.01%! Fukuyama in 2000: Intramolecular Diels-Alder reaction, 22 steps, 1.57%! Danishefsky in 1999: Aldol reaction + eck reaction, more than 30 steps.! Danishefsky, S. J. et al, Angew. Chem. Int. Ed. 1999, 38, 3197! icolaou, K. C. et al, Angew. Chem. Int. Ed. 1999, 38, 1669! Fukuyama, T. et al, J. Am. Chem. Soc. 2000, 122, 7825! Shair, M.D. et al, J. Am. Chem. Soc. 2000, 122, 7424!
21 21! ( )-Secodaphniphylline by eathcock! Forming 5 cycles, 4 carbon-carbon bonds, 2 carbonnitrogen bonds, 1 carbon-hydrogen bonds and 8 stereocenters with 2 of them are quaternary stereocenter.! Bn Bn Swern xidation 4 Ac, Ac, 75ºC, 1.5h 77% in two steps Bn 6 steps Secodaphniphylline Condensation Bn Bn Bn D-A aza-prins eathcock, C.. et al, J. rg. Chem. 1992, 57, 2566!
22 22! Aspidophytine by Corey! Previously discussed in Mr. Li Yuanheʼs report.! 2 + C C TMS C 2 ipr 1) TFA, C 2) ab 3 C 66% in two steps C 2 ipr further transformations Condensation ab 3 C aspidophytine C 2 ipr TMS Mannich C 2 ipr TMS Sakurai allylation C 2 ipr C 2 ipr Corey E. J. et al, J. Am. Chem. Soc. 1999, 121, 6711!
23 23! Asparagaemine A by verman! TIPS C 2 (C 2 ) n, 80ºC 94% Mannich TIPS asparagamine A Et TIPS [3,3] rearrangement TIPS verman, L. E. et al, J. rg. Chem. Soc. 2003, 125, 15284!
24 24! (+)-Stachyflin by Katoh! 1) DMP 2) LiAl(t-Bu) 3 96% R R R BF 3 Et 2-40ºC to r.t. + 66% 9% stachyflin R R R R= C 2 BF 3 BF 3 BF 3 Katoh, T. et al, Chem. Commun 2010, 46, !
25 25! utline! 1. Brief Introduction! 2. ucleophilic Dominoes! 3. Electrophilic Dominoes! 4. Radical Dominoes! 5. Pericyclic Dominoes! 6. Transition-tal-Catalyzed Dominoes! 7. Summary and utlook! 8. Acknowledgement!
26 26! ( )-Morphine by Parker! Br Ts SPh Bu 3 Sn, AIB 30% Ts ( )-Morphine Ts SPh Ts SPh Katoh, T. et al, Chem. Commun 2010, 46, !
27 27! utline! 1. Brief Introduction! 2. ucleophilic Dominoes! 3. Electrophilic Dominoes! 4. Radical Dominoes! 5. Pericyclic Dominoes! 6. Transition-tal-Catalyzed Dominoes! 7. Summary and utlook! 8. Acknowledgement!
28 28! Vindorosine by Boger! Constructed 4 carbon-carbon bonds, 6 stereocenters including 5 quaternary stereocenters.! 2 C MM Et Bn o-c 6 4 Cl 2 140ºC, 20h 57%, de=82% MM Et Bn C 2 ab 3 C MM Et Bn C 2 IEDDA [3+2] MM retro-[3+2] MM Et Et Bn - 2 Et Bn Ac C 2 C 2 C 2 Vindorosine Boger, D. L. et al, Angew. Chem. Int. Ed. 2006, 45, ! Boger, D. L. et al, J. Am. Chem. Soc. 2010, 132, 13533!
29 (+)-Preussin by verman! 29! Bn Mannich C 9 19 disfavored Bn C 9 19 Bn C 9 19 CSA Bn Bn E-isomer favored Z-isomer disfavored C 9 19 C 9 19 [3,3] [3,3] Mannich Bn C 9 19 Bn C 9 19 Bn favored disfavored Mannich major 61%-68%, 80% ee Bn C 9 19 C 9 19 Bn C 9 19 (+)-Preussin Mannich C 9 19 Bn Bn C 9 19 favored minor verman, L. E. et al, J. Am. Chem. Soc. 1994, 116, 11241!
30 oxy-cope/claisen/ene reaction! 30! microwave Toluene, 220ºC Et 78%, >92% de oxy-cope Et Carbonyl-ene Claisen Et Et Barriault, L. et al, J. Am. Chem. Soc. 2007, 129, 2112!
31 31! utline! 1. Brief Introduction! 2. ucleophilic Dominoes! 3. Electrophilic Dominoes! 4. Radical Dominoes! 5. Pericyclic Dominoes! 6. Transition-tal-Catalyzed Dominoes! 7. Summary and utlook! 8. Acknowledgement!
32 Palladium Polyene Cyclization! 32! Trost, B. M. et al, J. Am. Chem. Soc. 1993, 115, 9421!
33 33! eck/tsuji-trost: (-)-Capnellene! 77% yield 87% ee Tf 2.5 mol% [Pd(allyl)Cl]2 6 mol% (S)-BIAP 200 mol% abr Et 2 C C 2Et TBDPS TBDPS C 2 Et C 2 Et (-)-Capnellene Tsuji-Trost Pd eck Pd u - Pd Shibasaki, M. et al, J. Am. Chem. Soc. 1996, 118, 7108!
34 34! lefin tathesis: Cyanthiwigin U! Grubbs(II), C 2 4, Ph 43% Cyanthiwigin U [Ru] [Ru] Phillips, A. J. et al, J. Am. Chem. Soc. 2005, 127, 5334!
35 35! utline! 1. Brief Introduction! 2. ucleophilic Dominoes! 3. Electrophilic Dominoes! 4. Radical Dominoes! 5. Pericyclic Dominoes! 6. Transition-tal-Catalyzed Dominoes! 7. Summary and utlook! 8. Acknowledgement!
36 36! Disadvantages! Almost only thermodynamic stable product occurs.! MB () 2 C - Bn C 9 19 Et Few enantioselective domino reactions.!
37 37! Dominoʼs Future! Enantioselective! Multicomponent! rganometallic! "We need to set a time line, at which any natural products can be synthesized in less than 5 steps...! Cascade MacMillan, D. W. C.! rganic Reaction ne-pot Domino Tandem
38 38!
39 39! utline! 1. Brief Introduction! 2. ucleophilic Dominoes! 3. Electrophilic Dominoes! 4. Radical Dominoes! 5. Pericyclic Dominoes! 6. Transition-tal-Catalyzed Dominoes! 7. Summary and utlook! 8. Acknowledgement!
40 40! Acknowledgement! Prof. Yang, Prof. Chen, Prof. Tang! Mr. Lai Yang! Mr. an Yixin, Mr. You Lin, Mr. ao Puzhe! Everyone here!
41 41! Thank You! !
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