A Divergent Approach to The Synthesis of The Yohimbinoid Alkaloids Venenatine and Alstovenine
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1 A Divergent Approach to The Synthesis of The Yohimbinoid Alkaloids Venenatine and Alstovenine T. P. Lebold, J. L. Wood, J. Deitch, M. W. Lodewyk, D. J. Tantillo, R. Sarpong! ature Chem. 2013, 5, ! DI: /CEM.1528!
2 Corynanthe Alkaloids Alstovenine/venenatine: isolated from the Bark of Alstonia Venenata (poison devil tree) along with various others alkaloids (reserpine, yohimbine ). Traditionally used in ayurvedic medicine. Alstonia venenata Me Me Me2C venenatine Me2C alstovenine Terpenoid indoles alkaloids Corynanthe type alkaloids found in many other plant species (e.g. reserpine in Rauwolfia serpentina) 1
3 General Biosynthetic Pathway C tryptamine + Glc secologanin tryptophan Glc deoxyloganin geraniol P. M. Dewick, Medicinal atural products, John Wiley & Sons, Chichester, 2002, p
4 Deoxyloganin Biosynthesis [x] C C ADP C geraniol C 10-oxogeranial Enz Enz [x] Glc C C C C C C iridodial iridotrial deoxyloganin P. M. Dewick, Medicinal atural products, John Wiley & Sons, Chichester, 2002, p
5 Secologanin Biosynthesis Glc deoxyloganin [x] Glc loganin CYP450 Enz-Fe V Glc Enz-Fe IV Glc EnzFe III Glc Glc secologanin P. M. Dewick, Medicinal atural products, John Wiley & Sons, Chichester, 2002, p
6 Geissoschizine Biosynthesis tryptamine 2 + Glc secologanin Pictet-Spengler 3 strictosidine Glc 2 Glc dehydrogeissoschizine P. M. Dewick, Medicinal atural products, John Wiley & Sons, Chichester, 2002, p
7 Related Alkaloids: Ajmaline dehydrogeissoschizine? C C 2 Me C Ac Ac vinorine Me ajmaline antiarrythmic agent S. E. Connor, J. J. Maresh, at. prod. Rep. 2006, 23,
8 Related Alkaloids: Strychnos geissoschizine [x] rad? C C 2Me formylstryctamine C C 2 Me preakuammicine strychnine S. E. Connor, J. J. Maresh, at. prod. Rep. 2006, 23, W. anssen, PhD thesis, University f British Columbia,
9 Related Alkaloids: Aspidosperma preakuammicine C 2 Me C 2 Me C 2 Me C 2 Me tabersonine Me vindoline Ac C 2 Me S. E. Connor, J. J. Maresh, at. prod. Rep. 2006, 23, W. anssen, PhD thesis, University f British Columbia,
10 Corynanthe Alkaloids Biosynthesis dehydrogeissoschizine Me [Red] Ajmalicine Me [Red] yohimbine-type alkaloids S. E. Connor, J. J. Maresh, at. prod. Rep. 2006, 23, P. M. Dewick, Medicinal atural products, John Wiley & Sons, Chichester, 2002, p
11 Yohimbine Type Alkaloids!-yohimbine yohimbine pseudoyohimbine alloyohimbine "-yohimbine 3-epi-!-yohimbine F.-E. Chen, J. uang, Chem. Rev. 2005, 105,
12 Pharmacological Activities Me Me alstovenine CS stimulant (1 mg kg 1 /mice) Monoamine xidase Inhibitor (MAI) venenatine CS depressant yohimbine Stimulant and aphrodisiac Treatment of male impotence Me Me (TMB = 3,4,5-trimethoxybenzoyl) reserpine CS depressant tranquiliser, antihypertensive TMB 11
13 General Synthetic Strategy Various approaches for the synthesis of corynanthe alkaloids Most of them relied on the preparation of the E-ring, followed by condensation with a tryptamine derivative then pictet-spengler reaction.) 2 + LG R R =, Cl A B C D E Some used a fused DE ring coupled with an ethylindole derivative finished then nucleophilc attack of the indole on a suitable iminium electrophile LG + R R =, Cl A B C D E F.-E. Chen, J. uang, Chem. Rev. 2005, 105,
14 Woodward s Synthesis C Me Ac + Me 2 ab 4 Me 81% Ac Me C 2 Me PCl 3 Me Ac Me ab 4 Me Ac Me 79% F.-E. Chen, J. uang, Chem. Rev. 2005, 105,
15 Woodward s Synthesis Me 1) K, Me 2) DCC, pyridine Me 67% Me Me t-buc 2 reflux Me 74% Me Me Me (TMB = 3,4,5-trimethoxybenzoyl) reserpine TMB F.-E. Chen, J. uang, Chem. Rev. 2005, 105,
16 Stork Synthesis C Ts Me + Me 2 MgS 4 KC, MeC Me C Me C 2 Me MeC reflux Me 65% (mainly!-epimer) Me 81% Cl TF, rt Me 90% " Me G. Stork, P. C. Tang, M. Casey, B. Goodman, M. Toyota, J. Am. Chem. Soc. 2005, 127,
17 Tight Ion Pair? Free iminium ion (TF, Cl). Kinetically favored axial attack chair-axial Tight ion pair (MeC, reflux). Chair-axial blocked boat-axial C desired!"epimer C chair-equatorial boat axial undesired!"epimer Sarpong: can this concept be extended to other Yohimbine alkaloids? G. Stork, P. C. Tang, M. Casey, B. Goodman, M. Toyota, J. Am. Chem. Soc. 2005, 127,
18 Sarpong Synthesis TBS Bn + PhMe 100 C Bn C 2 Me TBS 89% endo/exo > 10:1 1) Pd/C, 2 2) Cl/Me 3) BsCl, pyr. DMPA C 2 Me Bn Bs 82% Bs 1) TBSTf, Et 3 2) oxone, ac 3 3) Cl, Me Bn C 2 Me C 2 Allyl + Bs R Bn C 2 Me 85% 2 Pb(Ac) 4 MgS 4 KC, MeC 6 R 4 Bs Bn C 2 Me 82% C C 2 Allyl R = 90% R = 4-Me 81% Bn R = 6-Me 87% C 2 Allyl 17
19 Kinetic Cyclisation: Venenatine R C Bn C 2 Allyl Cl TF, rt R Allyl 2 C Bn C 2 Me R = 81% R = 4-Me 84% R = 6-Me 96% only!-epimer observed Me Allyl 2 C Bn C 2 Me Pd(Ac) 2, PPh 3 Et/ 2, 70 C Me 41% Bn Pd/C, 2 up to 1300 bars o cleavage BBr 3 C 2 Cl 2, 78 C Me venenatine 69% Bn 18
20 Thermal Cyclisation R C Bn C 2 Allyl MeC 160 C, MW R Allyl 2 C Allyl 2 C Bn! " R = 53%!/" = 1:3 R = 4-Me 72%!/" = 1:1.8 R = 6-Me 96%!/" = 1:8 Best ucleophile (6-Methoxyindole) gives the highest selectivity + Bn MeC Direct S 2? n the nitrile or on a solvent molecule? Various solvents: poor selectivity, difficult to rationalize. ucleophile additives (DMAP, imidazole, ai) Improved selectivity for the α-epimer 19
21 ai as an Additive R R C Bn C 2 Allyl MeC, ai 160 C, MW Allyl 2 C Bn yield! R = 53% R = 4-Me 72% "/! 1:10 R = 6-Me 96% 20
22 Alstovenine R C Bn C 2 Allyl MeC, ai 160 C, MW Me Allyl 2 C Bn C 2 Me!/" 1:10 " 72% Pd 2 (dba) 3, pyrrolidine MeC, 70 C Me Bn BBr 3 C 2 Cl 2, 78 C Me 65% alstovenine 69% 21
23 Conclusions Very much inspired by Stork! Interesting result with a difficult substrate using ai What s the role of the nucleophile? tight ion pair S 2-like reaction More details would be appreciable (wait for the full paper) 22
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