Supporting Information. The synthesis of cardenolide and bufadienolide aglycones, and related steroids bearing a. heterocyclic subunit
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1 Electronic upplementary Material (EI) for Natural Product eports. This journal is The oyal ociety of Chemistry 2017 upporting Information The synthesis of cardenolide and bufadienolide aglycones, and related steroids bearing a heterocyclic subunit Michał Michalak, Karol Michalak and Jerzy Wicha Institute of rganic Chemistry, Polish Academy of ciences Kasprzaka 44/52, Warsaw, Poland jerzy.wicha@icho.edu.pl Table of contents Graphical presentation of preferred reagent approaches to C14 and C16 double bonds in steroid ring D...2 uzicka s synthesis of allo-uzarigenin...2 ondheimer s synthesis of digitoxigenin via the 14β-hydroxy etiocholanic acid derivative ondheimer s synthesis of resibufogenin and bufalin...3 Deghenghi s synthesis of periplogenin (19-desoxostrophanthidin)...4 Wiesner s synthesis of digitoxin...4 Daniewski et al. total synthesis of 9(11)-dehydrodigitoxygenin from Wieland-Miescher dione (384) applying vinyliodide 31 hydrogenation with diimide and tork s radical cyanation...5 tork s total synthesis of (+)-digitoxigenin. Part 1. The construction of tricyclic ABC intermediate applying intramolecular Diels-Alder reaction...6 tork s total synthesis of (+)-digitoxigenin. Part 2. Building up ring D and construction of the lactone moiety...6 verman s total-synthetic approach to C19-functionalized cardenolides. Part 1. etrosynthetic plan...7 verman s total-synthetic approach to cardenolides. Part 2. The synthesis of the ring A building block cheme 12. verman s synthetic approach to cardenolides. The synthesis of the CD building block 63 and the androstane derivative eferences...8 1
2 cheme 1. Graphical presentation of preferred reagent approaches to C14 and C16 double bonds in steroid ring D. C 3 peroxyacid C 3 C 3 peroxyacid C 3 C 3 C 3 C 3 TM 2 /cat. 2 /cat. 2 /cat. C 3 C 3 C 3 TM cheme 2. uzicka s synthesis of allo-uzarigenin. 1-3 Ac 4 Ac Ac 1. Zn, BrC 2 C 2 benzene/et 2, 15 min. 2. Ac 2, Py 73% 1. NB, Py, reflux, 0.5h 2. Py, 0.5h 3. Ac 2, Py 12% 35% 67% Pd/Ba 4 60% 1. Br 2, cat. Br Ac/CCl 4 2. Py, reflux 5 Ac Ac 6 Cl, Me, rt Ac monoperoxyphthalic a. CCl 3, rt allo-uzarigenin (7) 2
3 cheme 3. ondheimer s synthesis of digitoxigenin 4-5 via the 14β-hydroxy etiocholanic acid derivative steps C 2 Me 1. K 2 C 3, Me 2. Ac 2 2. MeLi, TF Li Et TF Ac ca. 45% Ac Et 1. 2% 2 4 Me 2. Ac 2, Py C 2 Et 1. e 2, benzene reflux 2. 5% Cl, Me % % digitoxigenin cheme 4. ondheimer s synthesis of resibufogenin and bufalin Li 2. 2N K 2 C 3 Me Et C 2 1.Li/N 3-70 to -50 C 2. C 2 N 2 3. Ac 2, Py C 2 Me 74% 95% Ac Ac 1.PCl 3 chrom. 2. K 2 C 3 Me 54% (Me) 2 C PCl 3 DMF 79% C 2 1. CDI 2. (t-bu) 3 Al t-bu 91% Me C Me 2. Ac 2, Py Ac Ac C 1. Na aq Et 2. BrC 2 C 2 Me Zn, DMF, 70 C 3. chrom. 15% 90% 1. Cl, aq Me and then p-tscl, Py 2. DMF, 80 C 3. Al Ac 2, Py 1. NB 2. Al 2 3 LiAl 4 Et 2-65 C Ac CDI - N,N'-carbonyldiimidazole 220 resibufogenin (19) bufalin (14) 3
4 cheme 5. Deghenghi s synthesis of periplogenin (19-desoxostrophanthidin). Ac Ac 1. LiAl 4 1. NB TF Ac aq dioxane 2. Ac 2 2. K Py Me anhyd Cu 4 acetone Ac LiAl 4 TF, reflux 2. Ac 2, Py N 2 4 Me 2. Ac 2, Py dioxane Ac 2 Cr 4 DMF Ac Ac Li Et Et 1N Cl benzene, Et 2 Me Ac Ac Periplogenin (21) cheme 6. Wiesner s synthesis of digitoxin steps Et 2 Li 1. Ac 2, Py 2. acetone aq. CaC 3, reflux 3. 2, Pd/CaC 3 Et 93% Bn m-cpba CCl 3, Ac AcNa 2. NaB 4 DCM-water MsCl, Py 1. NB aq acetone- Ac 2. a-ni DCM, Me AcK Ac 87% 85% 78% , Pd/C Etbenzene 93% digitoxigenin (27) stereoselective -glycosylation = tridigitoxoside unit digitoxin (1) 4
5 cheme 7. Daniewski et al total synthesis of 9(11)-dehydrodigitoxygenin from Wieland- Miescher dione (384) applying vinyliodide 31 hydrogenation with diimide and tork s radical cyanation steps 1. MeNa Me 2, Pd/C 2. 2, Pd/rC 3 Py % 29 87% 1. K-electride 2. N I 2, Et 3 N I N PrC 2 air I t-bu-nc Bu 3 ncl AIBN NaB 3 () t-bu 46% DP PPT 2. MeLi benzene 50% TP DP - dihydropyrane PPT - pyridinium p-toluenesulfonate MoP -oxodiperoxymolibdenum(pyridine) 34, = 35, = 1. LDA, TF 2. MoP MPA-TF 50% 86% Ph 3 P=C=C= Et 3 N, benzene 52% TP 36 82% 5
6 cheme 8. tork s 19 total synthesis of (+)-digitoxigenin. Part 1. The construction of tricyclic ABC intermediate applying intramolecular Diels-Alder reaction DCM-Me TM TMCl, Et 3 N 2. NaB 4, Me C DMF 3. NaI 4 C 54% Ph 2 P NaB(Ac) 3 benzene 67% C C 2 n-buli TF-MPA 2. wern ox. 42 Et 2 P n-buli, TF C 60% toluene 200 o C 75% in 2 steps Cl aq TF-acetone 2. NaB 4 -CeCl Et 64% DEAD, TFA Ph 3 P, BzNa TF 2. (Me 3 )BF 4 60% CF 3 C 2 46 DEAD - diethyl azodicarboxylate cheme 9. tork s total synthesis of (+)-digitoxigenin. Part 2. Building up ring D and construction of the lactone moiety EtNa, Et 2. TBCl im, DMF 78% 1. C 6 5 C 3 NaC 3 2. BF 3 Et 2-78 C to rt 63% TB TB TB 1. BrMg TF, rt 2. TBAF C 67% TM TB 1. N 2 Cl AcNa, Et 2. CDI, DCM, rt Bu 3 n AIBN, benzene then silica gel 40% 95% TB BnC 2 Li TF, -78 C 2. Pd/C, Et 85% TB 101, 17 :17 >4:1 102 digitoxigenin (27) 1. Ph 3 P=C=C= Et 3 N, benzene 2. Ts, Me 72% TB 1. LiNEt 2, TF, 0 C 2. BT 3. chromat % AIBN - 2,2'-azobis(2-methylpropionitrile) CDI - N,N'-carbonyldiimidazole BT - 2,6-di-tert-butyl-4-methylphenol 6
7 cheme 10. verman s total-synthetic approach to C19-functionalized cardenolides Part 1. etrosynthetic plan Tf 53 + I = C 2 P or, P = protective group cheme 11. verman s total-synthetic approach to cardenolides. Part 2. The synthesis of the ring A building block 55. Ph Ph N B 58 B 3 Me DCM, -25 C 98%, 93%ee Ac 2, Et 3 N DMAP 96% 57 Ac KMD TBDMCl MPA 2. KF, K 2 C 3 MeI, DMF I 2, PPh 3, im toluene 59 LiAl 4 C 2 Me % in 2 steps 55 I 7
8 cheme 12. verman s synthetic approach to cardenolides. The synthesis of the CD building block 63 and the androstane derivative NaB 4 2. Me 2 NN 2 Ac, Et 3. TM-im TM 1. Et 2 NLi TF, MPA, -78 C then Ac, AcNa aq TF 1. MsCl, py 2. K, 18-C-6 DM 85% N 337 NMe % NaB 4 CeCl mi 2, TF Me TM-im 2. V(acac) 2 t-bu 2 3. TPAP, NM 68% ad then 2 2. TBAF silica gel, CCl 3 8 KMD PhNTf 2-78 C, TF Tf Pd(dppb) AcK, DMA 75 C 90% Pd(dppb) - palladium bis(diphenylphosphino)butane eferences: 1. P. A. Plattner, L. uzicka,. eusser and E. Angliker, elv. Chim. Acta, 1947, 30, P. A. Plattner,. eusser and E. Angliker, elv. Chim. Acta, 1946, 29, P. A. Plattner, L. uzicka,. eusser and E. Angliker, elv. Chim. Acta, 1947, 30, N. Danieli, Y. Mazur and F. ondheimer, J. Am. Chem. oc., 1962, 84, F. ondheimer, Chem. Br., 1965, L. uzicka, P. A. Plattner,. eusser and J. Pataki, elv. Chim. Acta, 1946, 29, P. A. Plattner, L. uzicka,. eusser, J. Pataki and K. Meier, elv. Chim. Acta, 1946, 29, L. uzicka, P. A. Plattner,. eusser and K. Meier, elv. Chim. Acta, 1947, 30, F. ondheimer, W. McCrae and W. G. almond, J. Am. Chem. oc., 1969, 91, Deghenghi, A. Philipp and. Gaudry, Tetrahedron Lett., 1963, 4, Deghenghi, Pure Appl. Chem., 1970, 21, T. Y.. Tsai, A. Minta and K. Wiesner, eterocycles, 1979, 12, K. Wiesner and T. Tsai, Pure Appl. Chem., 1986, 58,
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