Stemona Alkaloids. tuberostemonol. OMe O O. neostemonine. OMe O O. protostemonine
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1 I. Introduction 9 9a The Stemonaceae plant family, which comprises over 0 species, produces a large class of structurally diverse alkaloids featuring a conserved pyrrolo [1,2-a] azepine = perhydroazaazulene = -azazaulene nucleus Their roots have been used for centuries in traditional chinese medicince for a variety of purposes including (but not limited to): treatment of bronchitis, tuberculosis, pertussis, as well as anti-parasitic agents ver 80 members have been discovered and many more are likely to be isolated (restriction is limited to only 8 species, mostly from the Stemona genus) I. Stenine Group stenine tuberostemonine ( = α) tuberostemonine A ( = β) tuberostemonol oxotuberostemonine neotuberostemonine II. Stemoamide Group stemoamide stemonine Me neostemonine didehydrotuberostemonine ( 11 = β, 12 = β, Et = β) bisdehydroneotuberostemonine ( 11 = α, 12 = α) Me bisdehydroneostemonine Me protostemonine Me protostemonine Me didehydroprotostemonin For excellent reviews see (and references therein): Pilli et al. at. Prod. Rep., 2000, 1, Seger et al. Chemistry & Biodiversity ,
2 II. Stemoamide Group (Con't) Me isoprotostemonine tuberstemoamide stemoninine Me stemodiol III. Tuberostemospironine Group tuberstemospironine Me Me R croomine (R = ) stemospironine (R = Me) Me Me stemotinine Me stemonidine isostemotinine didehydrocroomine IV. Stemonamine (maistemonine) Group stemonamine Me Me isostemonamine Me Me Me Me Me Me isostemonamide stemonamide maistemonine oxymaistemonine Pilli et al. at. Prod. Rep., 2000, 1,
3 V. Parvistemoline parvistemoline parvistemonine didehydroparvistemonine? Me VI. Miscellaneous Me R R stemofoline (R = ) oxystemofoline (R = ) methoxystemofoline (R = Me parvistemoninine (R = ) parvistemoninol (R = ) tuberostemonone tuberostemoninol parvistemoamide Pilli et al. at. Prod. Rep., 2000, 1,
4 II. Biosynthetic Considerations Consider the following carbocyclic skeletons where the C units of presumed terpene origin are drawn in bold: Me Me Stemofoline protostemonine tuberostemonine stemonine tuberstemonamide tuberostemospironine This leaves the following fragment unaccounted for: Thus the following biosynthetic picture emerges: Recall pyrrolizidine biosynthesis: 2 2 homospermidine mannich An analagous pathway could produce the stemona alkaloids 2 2 spermidine X X [] [] [] Me -C 2 Me stemofoline Seger et al. Chemistry & Biodiversity , 2-29.
5 III. Synthesis Croomine (D.R. Williams et al, 1989) J. Am. Chem. Soc. 1989, 111, MEM Bz MEM 8) Li, DMPU 110 C 1 MEM 1) n-buli, TF, ClC 2 C, -8 C (%) Bz MEM ) LiB, Me Et 2 2 MEM 2) MgBr C 2 C Bn CuBr DMS TMEDA, Et 2-8 C (9%) ) Swern, -8 C MEM MEM C 2 C Bn ) DIBAL, C 2 Cl 2, -8 C ) D-DIPT, t-bu, C 2 Cl 2-0 C (8%) Bn (9%) Bn % Rh/Al 2 2 ) BzCl, Et (0%) Bn then PPh =CC 2 C -8 C 2 C (89%) Bn 9) BF Et 2, C 10) Li, Me (9%) 11) Swern, then Bz 12) BF, Me then Li, Me: 2 C 2 C Ph P 1) Jones reagent Bz Bn 1) C 2 Bn 2 8 Bn (0-81%) 9 (8%) 10
6 Croomine (D.R. Williams et al, 1989) 10 C 2 C Bn 1) BCl, C 2 Cl 2, -8 C 1) swern (1%) C 2 C 11 1) PPh, 2 C then ab, Me (90%) 18) I 2, Et 2, C 2 Cl 2 2 C (2 C) mechanism? 12 C 2 C Stemonine (D.R. Williams et al, 200) rg. Lett. 200,, 1- A Similar iodination cascade was used here as well TBS TBS prepared in many steps C 1) EtPPh 2, Ph, 18h, 2 C, then ab, Me (0%) TBS TBS 1 Me 2) I 2, Et 2 :C 2 Cl 2, 8 h, 2 C 2% ) Jones Reagent (8%) 1 ) TBAF ) DMP (9%) TBS TBS C 1
7 Croomine (Martin et al, 1989) 1) TIPSTf, Et 0 C 2 C 2) s-buli, TMEDA TF, 0 C (99%) TIPS then TIPS 1 2 Br(C 2 ) Br (8%) Br Me C 2 Me ) % TIPS-Tf, 0 C (2%) J. Am. Chem. Soc. 199, 118, ) PCl, DMF (%) TIPS C 2 Br ) MM, DMF, Δ ) M Br, 0 C (%) Br C 2 Me ) TFA ) % Rh/C, 2 EtAc:Et (9%) Br C 2 Me 8 9) 10% Pd-C/ 2 10% Cl/Et (8%) Stemoamide (Jacobi et al, 2000) racemic synthesis: J. Am. Chem. Soc. 2000, 122, 29-0 Cl Cl 1) Methyl alaninate 2) P 2 (80%) Me Cl ) a, then succinimide (9%) 1 2 Me
8 Stemoamide (Jacobi et al, 2000) Me ) ab, Me, + (2%) Me Me ) BF Et 2 (92%) Sn(Bu) Me ) Diethylbenzene reflux (%) % ab icl 2 + Me 8 an enantioselective route was also developed using L-pyroglutamic acid 2 C R rationalize the following by-products formed in the IMDA cascade Me 2 C 8
9 Me Me stemonamide isostemonamide (Kende et al.) rg. Lett , ) Bn(C 2 ) MgBr Et 2, reflux 2) PPTS, Me Me (90%) Bn 1 2 ) 2, % Pd/C ) BF Et 2 (82%) TMS Me Me 8 10) MgBr Me 8) TBDMSTf, collidine, 0 C 9) Pd(Ac) 2 2, DMS, 80 C (9% of ) (89% of 8) Me Me ) swern ) DBU, 2 C ) swern (0%) 1:1 mixture of : Me % CuBr DMS TMSCl, MPA -8 C Me TMS Me 9 (%) 10 (%) 11 (2%) Me 11) K, Me 2 =C 2 + CF C 2 - (for ketones) or Me 2 =C 2 + CF C 2 - (for enol ether) Me Me 12 (%) 1 (90) 9
10 Me Me Me Me 12) CA, 2 /MeC 1) RhCl, Et, 2 Me Me stemonamide (Kende et al.) isostemonamide (%) 1 1) MsCl, DMAP pyr. (2%) Me Me 1) a Me Me Ms Ms 1 1 Stenine (art et al.) 1) Et 2 AlCl, CCl 8 C (%) 2) 2 2 Me (8%) Ac ) C I, K 2 C ) AcCl (Me) 2 J. rg. Chem ,
11 Stenine (David art et al.) I 11 1) 12 Ac C2 Me C2 Me (Me) 2 1) I 2, TF, 2 Sn(n-Bu) AIB, Ph (8%) (%) 18) LDA, MeI (8%) ) Mesitiylene, Δ ) Me (9%) Me 2 1 Ac SiMe 2 t-bu 10 C2 Me C 2 Me C 2 Me 19) swern 20) Ph P=CC 2 Et (91%) ) 9-BB/aB 8) MsCl, Et 9) MeLi, TF (89%) 1) t-bume 2 SiCl, Et 1) MeC(Me) 2 Me 2, xylene, Δ (9%) Et 2 C 1 9 C2 Me C2 Me C2 Me 21) Red-Al, CuBr (8%) 10) Jones reag. acetone (8%) 1) ab, Me t--bu (100%) 2 C 11) I 2, TF, 2 12) DBU (91%) Et 2 C 1 8 C2 Me C2 Me C 2 Me 11
12 Stenine (David art et al.) Et 2 C C2 Me 22) TMSI, then PhMe, Δ (8%) 1 1 2) s (cat) ai 2) S S Si 2 /SCl 2 S S 1 2) Lawesson's reagent (8%) for a similar synthesis with an asymmetric Diels-Alder see Morimoto et al. Angew. Chem. Int. Ed. Engl. 199,, ) Raney i Et (%) S S 18 S Stenine (Peter Wipf et al.) C 2 Cbz 1) PhI(Ac) 2, ac Me, 21 0 C (%) Cbz C 2 Me 2) Bz 2 ) ab, CeCl (89%) 1 2 Bz Cbz C 2 Me J. Am. Chem. Soc. 199, 11,
13 Bz C 2 Me Cbz 2 ) Pd 2 (dba) CCl Bu P, C 2, Et (8%) Cbz C 2 Me ) TPAP, M ) KMDSA, Tf (%) Cbz C 2 Me Stenine (Peter Wipf et al.) ) ab, CeCl 8) CC(Me) 2 Me 2, 10 C (%) TIPS 8 Cbz (Me) 2 1) I 2, p. 1) Allyl-SnBu, AIB 1) LDA, MPA, MeI 18) s, ai 19) ab, -0 C 20)o-( 2 )PhSeC, Bu P, 2 2 (%) TIPS Cbz 12) Li, 2 /TF 1) PhPCl 2, Et, PhSe 1) Bu Sn, AIB, 10 (0%) TIPS (Me) 2 Cbz C 2 Me 9) AD-mix β, ai 10) ab 11) TIPS-Cl, DMAP (%) (Me) 2 C 2 Me Cbz 9 TIPS Cbz 21) F, MeC 2) Pd() 2, 2 22) DMP, acl 2 2) FDPP (1%) Cbz 10 2) Lawesson's 2) Raney-i (%) 1
14 Stenine Padwa et al. TMS 1) LDA, then (MeS) 2 CC, then Ac 2 (80%) MeS Ac SMe 1 2) Cl C 2 Me MeS C 2 Me Ac SMe 2 ) DMTSF Et (80%) MeS C 2 Me rg. Lett. 2002,, I 8) Li, 2 9) I 2, MeC (0%) Me 2 C ) Crabtree's Cat, 2 ) MsCl, Et, DBU (%) Me 2 C ) Raney-i ) ab, CeCl (1%) Me 2 C MeS 10) allyl-sn(bu), AIB 11) s, ai (8%) 8 12) ethane dithiol 1) lawesson's 1) Raney-i 1) LDA, MPA, MeI (%) 1
15 P Me Me 1) a/ TF (92%) 1 2) TMSTf (9%) TMS ) SnCl (0% :1 dr) Stenine Aubé et al. J. Am. Chem. Soc. 200, 12, ) LMDS, then BrC 2 C 2 Me (%) Me 2 C 8 Steps 19% Yield o PG's ) Lawesson's 8) Raney i (8%) ) ab ) LMDS, MeI (1%) Tuberstemonine Wipf et al 2)Et Si, Pd(Ac) 2, Et C 2 Me ) cinnamyl bromide Cbz ) TBAF 1 (80%) 2 from the oxidative tyrosine cyclization 1) TBDMS-Cl, imidazole DMAP C 2 Me Ph ) TPAP, M ) KMDS, allyl iodide (8%) C 2 Me Ph 1
16 Tuberstemonine (Wipf et al.) 8 C 2 Me ) Grubbs (92%) Ph 1) L-selectride, -8 C 1) Ts, Me TBDMS (%) C 2 Me Br 8) PhS, Et 9) (PPh ) RhCl, 2 10) DBU (81%) 1) (Me)(Me) Cl Me 2 AlCl 1) LiDBB 11) ab, CeCl 12) TBDMS-Cl, imid. DMAP (%) TBDMS C 2 Me C 2 Me (89%) PhSe 9 1) MeC(Me) 2 Me 2, xylene, Δ 18) PhSeCl, MeC/ 2 (2%) 19) allyl-snph 20) LDA, MPA, MeI 21) allyltritylamine, DIEA, toluene, 110 C (%) 10 22) Grubbs, Ts, ethylene 2) Pd/C, 2 1
17 Me Ac Me 1 1) aq. acl, Ac 2) MMCl, Et(i-Pr) 2 (0%) 2 MM ) KEt (80%) Me2 MM Isostemofoline (Kende et al.) J. Am. Chem. Soc , 1-2 ) a 2 S 2, Et, 2, 90 C ) BC 2, DMAP MM 10) a, Me (90%) MM ) Bu F 8) 2, Pd/C, Me, 9) 2, DMS, 10 C (2%) Me 2 C TBS MM ) (2%) (90%) TBS 2 C 2 Me Rhodium octanoate dimer MM MM 8 11) LMDS, DMPU allyl iodide (91%) 12) K 2 s, ai, 2 1) Zn(B ) 2, TF, -10 C 1) TIPSCl, imid., DMF (8%) Ts TIPS 1) MeLi (2.2 eq.) TIPS DMPU, Et 2 1) Bu F, TF -0 C (8%) 1) TsCl, pyr, MM MM CCl MM (81%)
18 Ts Ts Me Me MM 11 18), DMS (%) 2 C MM 12 Isostemofoline (Kende et al.) 19) i-buccl, MM 20) ab, Me 21) DMP Ts Ts 22) Me Ts Me MM 1 Li 2) DMP, C 2 Cl 2 (1%) (%) Me MM 1 MM 1 2) CF C 2 then ac (%) Me 1 2) Tf 2 Me (12%) (1%)? 18
19 Me Didehydrostemofoline (Asparagamine A) (verman et al.) Me J. Am. Chem. Soc , Me 1) LDA, IC 2 C 2 Et 1) DBU, PhMe, 10 C Isodidehydrostemofoline 12) TBAF 1) S Py, Et, DMS 1) Julia olefination (0%) Me 1 Me TIPS 1) 2 2) 2, Pd/C (%) C 2 Et 11) (C 2 )n, PhMe/ MeC, (9%) 2 Et 2 C 2 Me I Me TIPS ) DBU, then 2, Pd/C ) TIPSTf, 2,-lutidine ) DIBAL, PhMe, -8 C 9) VinylMgBr, CeCl 10) TMSI (8%) ) DMP ) TIPSTf, Et 8), DMS (%) Me TIPS Me TIPS 22) Me Me 2 C 1) BBr ; aq. a Me 2 C TMS 18) TMS-imid., 10 C Me (%) ) DIBAL, -8 C 20) DMP 21) Si 2 (epim.) % C TMS 11 Li then aq. Cl Me 12 Didehydrostemofoline + 2) P(Me) Isodidehydrostemofoline (%) S Me. : 1 S Me Me 2) CSCl 2 DMAP 1 2) IBX, DMS 0 C 19
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