A Unified Strategy to ent-kauranoid Natural Products: Total Syntheses of ( )-Trichorabdal A and ( )-Longikaurin E
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1 A Unified Strategy to ent-kauranoid Natural Products: Total Syntheses of ( )-Trichorabdal A and ( )-Longikaurin E John T. S. Yeoman, Victor W. Mak, and Sarah E. Reisman. J. Am. Chem. Soc. 2013, 135, ( )-trichorabdal A Ac ( )-longikaurin E Kara George Rosenker Wipf Group - Current Literature 24 August 2013 Kara Wipf Group Page 1 of 15 8/24/2013
2 The ent-kaurenes (Diterpenoids) ent-kaurene Isodon species have a long tradi1on in Chinese folk medicine for their cura1ve proper1es ver 600 known Isodon diterpenoids (mainly ent- kaurenoids) Classified into 11 groups and 5 subgroups based on the different oxygena1on and cleavage paeerns Many of these compounds exhibit potent an1bacterial, an1- inflammatory, and an1cancer proper1es PP PP CPS KS geranylgeranyl diphosphate (GGDP) ( )-copalyl diphosphate ent-kaurene Sun,.-D.; uang, S.-X.; an, Q.-B. Nat. Prod. Rep. 2006, 23, 673. Dewick, P. M. dicinal Natural Products: A Biosynthetic Approach. 3rd ed.; Wiley: Great Britain, Kara Wipf Group Page 2 of 15 8/24/2013
3 The ent-kaurenes (Diterpenoids) ent-kaurene Isodon species have a long tradi1on in Chinese folk medicine for their cura1ve proper1es ver 600 known Isodon diterpenoids (mainly ent- kaurenoids) Classified into 11 groups and 5 subgroups based on the different oxygena1on and cleavage paeerns Many of these compounds exhibit potent an1bacterial, an1- inflammatory, and an1cancer proper1es R Sun,.-D.; uang, S.-X.; an, Q.-B. Nat. Prod. Rep. 2006, 23, 673. trichorabdal A (R = ) trichorabdal B (R= Ac) Ac maoecrystal Z Ac longikaurin E maoecrystal V shikodonin Kara Wipf Group Page 3 of 15 8/24/2013
4 The ent-kaurenoids: ( )-Trichorabdal A and ( )-Longikaurin E ent-kaurene ( )- Longikaurin E was isolated in 1981 from Rabdosia longituba - In vitro growth inhibi1on against 5 human cancer cells lines (IC50s < 10 µm; L- 60, SMMC- 7721, A- 549, MCF- 7, SW- 480) ( )- Trichorabdal A was isolated in 1981 from Rabdosia trichocarpa - Potent in vivo an1tumor ac1vity, IC50 = 548 nm (ela cells) - Modest an1bacterial ac1vity against. pylori R Ac ( )-longikaurin E R 7,20-epoxy-ent-kaurane ( )-trichorabdal A R ,7-seco-ent-kaurene Fujita, E.; Fuji, K.; Sai, M.; Node, M.; Watson, W..; Zabel,V. J. Chem. Soc. Chem. Commun. 1981, 899.; Fuji, K.; Node, M.; Sai, M.; Fujita, Takeda, S.; Unemi, N. Chem. Pharm. Bull. 1989, 37, 1472.; Kadota, S.; Basnet, P.; Ishii, E.; Tamura, T.; Namba, T. Zbl. Bakt. 1997, 286, 63. Fujita, T.; Takeda,Y.; Shingu, T. eterocycles 1981, 16, 227.Zhao, W.; Pu, J.-X.; Du, X.; Su, J.; Li, X.-N.;Yang, J.-.; Xue,Y.-B.; Li,Y.; Xiao, W.-L.; Sun,.-D. J. Nat. Prod. 2011, 74, Kara Wipf Group Page 4 of 15 8/24/2013
5 Synthesis of 6,7-seco-ent-Karanoids In 1986 Mander and co-workers reported a 33-step synthesis of 15-desoxyeffusin C 2 11 steps Et 2 C 3 steps MM 8 steps MM MM 10 steps 20 6 Ac 7,20-epoxy-ent-kaurane 7 5 I 6 Ac desoxyeffusin 6,7-seco-ent-kaurene Ac 15-desoxyeffusin Kenny, M. J.; Mander, L. N.; Sethi, S. P. Tetrahedron Letters 1986, 27, Kenny, M. J.; Mander, L. N.; Sethi, S. P. Tetrahedron Letters 1986, 27, Kara Wipf Group Page 5 of 15 8/24/2013
6 Synthesis of 6,7-seco-ent-Karanoids 12 years later this group completed a 29-step semisynthesis of longirabdolactone C C 2 gibberellic acid (commercial) C C K 86% C 20 3 steps 4 steps 2 C ,7-seco-ent-kaurene 7,20-epoxy-ent-kauranes longirabdolactone Adamson, G.; Mander, L. N. Aust. J. Chem. 2003, 56, 805. Kara Wipf Group Page 6 of 15 8/24/2013
7 Total Synthesis of ( )-Maoecrystal Z First total synthesis of maoecrystal Z was reported in 2011 by Reisman and coworkers 12 steps from ( )-γ-cyclogeraniol Ac ( )-maoecrystal Z Ti III -mediated reductive epoxide coupling Sm II -mediated reductive cascade cyclization TBS 2 steps from γ-cyclogeraniol C 2 C 2 CF 3 Cp 2 TiCl 2, Zn 0 2,4,6-collidine Cl TF, 23 C 74% C 2 CF 3 Ti IV single diastereomer SmI 2, LiBr t-bu TF, -78 C 54% Cha, J. Y.; Yeoman, J. R. S.; Reisman, S. E. J. Am. Chem. Soc. 2011, 133, Szostak, M.; Procter, D. J. Angew. Chem. Int. Ed. 2012, 51, Sm III 2 rings 4 stereogenic centers ( )-maoecrystal Z Kara Wipf Group Page 7 of 15 8/24/2013
8 A Unified Strategy to ent-kauranoid Natural Products TBS 2 steps from γ-cyclogeraniol R trichorabdal A (R = ) trichorabdal B (R= Ac) Ac maoecrystal Z Ac longikaurin E maoecrystal V shikodonin Cha, J. Y.; Yeoman, J. R. S.; Reisman, S. E. J. Am. Chem. Soc. 2011, 133, Yeoman, J. T. S.; Mak, V. W.; Reisman, S. E. J. Am. Chem. Soc. 2013, 135, Kara Wipf Group Page 8 of 15 8/24/2013
9 Title Paper: Retrosynthetic Design for Trichorabdal A and Longikaurin E ( )-trichorabdal A Ac Sm-mediated reductive cyclization R Pd-mediated oxidative cyclization R SiR' 3 ( )-longikaurin E Sm-mediated reductive cyclization intermediate in the synthesis of maoecrystal Z ( )- γ-cyclogeraniol Yeoman, J. T. S.; Mak, V. W.; Reisman, S. E. J. Am. Chem. Soc. 2013, 135, Kara Wipf Group Page 9 of 15 8/24/2013
10 Synthesis of Common Intermediate ( )- γ-cyclogeraniol 1. TBSCl, imidazole C 2 Cl 2 2. m-cpba, NaC 3 C 2 Cl 2 91% (2 steps) TBS 3:1 anti:syn C 2 C 2 CF 3 Cp 2 TiCl 2, Zn 0 2,4,6-collidine Cl TF, 23 C C 2 CF 3 Ti IV 74% single diastereomer A LMDS, 4:1 TF/MPA 0 to 23 C I 63% intermediate in the synthesis of maoecrystal Z PivCl, NEt 3 TF; then (R,R)-pseudoephedrine 82% Ph N I LDA, LiCl TF 92% TBS Ph N TBS 1. B 3 N 3 LDA, TF 2. I 2, PPh 3, im. C 2 Cl 2 85% (2 steps) A Cha, J. Y.; Yeoman, J. R. S.; Reisman, S. E. J. Am. Chem. Soc. 2011, 133, Yeoman, J. T. S.; Mak, V. W.; Reisman, S. E. J. Am. Chem. Soc. 2013, 135, Kara Wipf Group Page 10 of 15 8/24/2013
11 Synthesis of xidative Cyclization Substrate 1. n-bu 4 NS 4 p-ts, 0 C 2. DMP, DCM 77% (2 steps) SmI 2, LiBr t-bu TF, -78 C 57% Sm III Sm III single diastereomer MMCl n-bu 4 NI, DIPEA DMF, 45 C 91% MM KMDS TBSCl, DMPU TF, -78 C 85% MM TBS Yeoman, J. T. S.; Mak, V. W.; Reisman, S. E. J. Am. Chem. Soc. 2013, 135, Kara Wipf Group Page 11 of 15 8/24/2013
12 Reaction ptimization: Pd-diated xidative Cyclization MM TBS Pd II DMS, 45 C air MM entry Pd source addi/ve yield (%) 1 Pd(Ac) 2 (0.1) 7 2 Pd(Ac) 2 (1.0) 35 3 Pd(Ac) 2 (1.0) 28* 4 Pd(TFA) 2 (1.0) 19 5 PdCl 2 (1.0) AgBF 4 (2.0) 5 6 PdCl 2 (1.0) 0 7 Pd(Ac) 2 (1.0) 2 (5.0) 38 8 Pd(Ac) 2 (1.0) K 2 C 3 (5.0) 0 9 Pd(Ac) 2 (1.0) Ac (0.5) Pd(Ac) 2 (0.1) Ac (0.5) 7 11 Pd(Ac) 2 (1.0) Ac (1.0) Pd(Ac) 2 (1.0) p- Ts (0.5) Pd(Ac) 2 (1.0) Bz (0.5) Pd(Ac) 2 (1.0) Piv (0.5) 40 Little difference observed when the reaction was conducted under an air or oxygen atmosphere Entry 3 conducted in CN gives lower yield and increased side product formation All other solvents tested gave only trace quantities of product (toluene, glyme, dioxane, t-bu, DMF) First example of a Pd-mediated oxidative cyclization of a silyl ketene acetal to generate an all-carbon quaternary center Yeoman, J. T. S.; Mak, V. W.; Reisman, S. E. J. Am. Chem. Soc. 2013, 135, Kara Wipf Group Page 12 of 15 8/24/2013
13 Total Synthesis of ( )-Trichorabdal A MM 3, DCM -94 C; then PPh 3 69% MM 2 NC 2 N 2 Ac 2 DMF, 95 C 82% MM 1. 6 M aq. Cl dioxane, 45 C 2. TEMP, PhI(Ac) 2 DCM 73% (2 steps) ( )-trichorabdal A 15 steps from ( )-γ-cyclogeraniol Yeoman, J. T. S.; Mak, V. W.; Reisman, S. E. J. Am. Chem. Soc. 2013, 135, Kara Wipf Group Page 13 of 15 8/24/2013
14 Total Synthesis of ( )-Longikaurin E MM 6 M aq. Cl dioxane, 45 C 89% 1. TEMP PhI(Ac) 2 2. Ac 2 DMAP 58% (2 steps) Ac SmI , DCM, -94 C; then PPh 3 TF, 23 C 55% (75% BRSM) Ac 2. 2 NC 2 N 2 Ac 2, DMF, 95 C 44% (2 steps) Ac ( )-longikaurin E 17 steps from ( )-γ-cyclogeraniol Yeoman, J. T. S.; Mak, V. W.; Reisman, S. E. J. Am. Chem. Soc. 2013, 135, Kara Wipf Group Page 14 of 15 8/24/2013
15 Conclusions and utlook A unified synthetic strategy has been applied to the first total syntheses of ( )-trichorabdal A and ( )-lonikaurin E 15 and 17 steps, respectively from ( )-γ-cyclogeraniol Pd II -mediated oxidative cyclization reaction was employed to generate the an all-carbon quaternary center and build the bicyclo[3.2.1]octane core Three architecturally distinct ent-kauranoids were prepared from a common spirolactone intermediate ( )-trichorabdal A Ac ( )-maoecrystal Z Ac ( )-longikaurin E Kara Wipf Group Page 15 of 15 8/24/2013
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