Concise Total Synthesis of Variocolortides A and B through an Unusual Hetero-Diels- Alder Reaction!
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1 Concise Total Synthesis of Variocolortides A and B through an Unusual etero-diels- Alder Reaction! Christian A. Kuttruff, endrik Zipse, and Dirk Trauner! ACIE Early View, DI: /anie ! Marija Manojlović!! Wipf Group Current Literature eting! !
2 Variecolortides A and B! 2 R variecolortide A variecolortide B R = Exiguamine A R = Exiguamine B Isolated in 2007 from black mold, Aspergillus variecolor! Modest cytotoxic and oxygen scavenging activity (μm range)! Structural features: unprecedent anthraquinone methide moiety, diketopiperazine, spirocyclic,acetal! Black mold, Aspergillus variecolor! Zhu et al. Chem. Biodiversity 2007, 4, 2913.
3 Biomimetic Synthesis of Exiguamines A and B! Bn 1. a, 3 C 2 2. o-xylene, 160 C 2 C 47% Br emetsberger indole synthesis Bn Br Bn Br Stille coupling Bn 1. Pd black C 2 4, 94% 2. Salcomine, 2 C 3. 1% C 2 in 2 77%, 2 steps : Exiguamine B LiMDS, TF -78 to -40 C 60% 2 2 Ag (20 equiv), 2% C 2 47% 2 1. BBr % C 2, 43% Ag (10 equiv), 2% C 2 46% 2 Exiguamine A Trauner et al. at. Chem. Biol. 2008, 4, 535.
4 Biosynthetic Analysis of Variecolortides Is Diels- Alderase involved?! type II polyketide pathway hydroxyviocristin from Aspergillus cristatus R R = prenyl isoechinulin B R = neoechinulin B from Aspergillus ruber etero- Diels-Alder variocolortide A PP 2 2 Shikimic acid pathway SR PP terpenoid pathway 1989 Monoclonal antibodies that catalyze Diels-Alder (DA) reaction! 1999 RA (ribozymes) can catalyze DA reaction! potential Diels-Alderases isolated from fungi: lovastatin nonaketide synthase, solanapyrone synthase, and macrophomate synthase! 2005 Theoretical study of macrophomate synthase stepwise process (Michael then aldol reaction) has more probable energetic profile then concerted process! 2008 Macrophomate synthase is a very efficient aldolase! Existence of real Diels-Alderases still elusive! ACIE 2003, 42, BC 2008, 6, JACS 2005, 130, C&E ews, May 4, 2005.
5 etero Diels-Alder Reactions of 1-oxa-1,3- butadiene! TBS K 2 C 3, 110 C, 48 h 68% TBS 2 C 2 C (-)-Reveromycin B Rizzacasa et al. JC 2001, 66, C 2 Et 1. DDQ, Ac (cat.) dioxane 2. Et 3 Si, BF 3 Et 2 C % Camptothecin Yao et al. L 2008, 10, C 2 Yb(FD) 3 Et C 2 Et C 2 Et Quassin and other quassinoids Spino et al. JC 1994, 59, 5596.
6 etero Diels-Alder Reactions of 1-oxa-1,3- butadiene! Cbz C EDDA sonication Cbz Bz Cbz Et Et Bz 86% Cbz Et Bz 18,19-Dihydroantirhine Tietze, et al. Liebigs Ann. 1997, 881. Ph C Et 3 Et! Ph Ph Ph Leporin A Snider and Lu, JC 1996, 61, 2839.
7 Title Paper Synthesis of Precursors! B - a, TF 52% B Al 3 /a, 180 C 75% hydroxyviocristin B -
8 Title Paper Synthesis of Precursors! Br Cbz 3 - SnBu 3 Pd 2, PPh 3 90% 1. EDCI, Bt DIPEA, 77% 2. 2, Pd/C (cat.), 87% 3. S 2, then 3 (aq), 57% B 1. isoprene, Grubbs II, 79% 2. CS, 73% 3. 9-prenyl-BB, 96% A, piperidine 110 C 39% P % A 1. CS, 91% 2. 9-prenyl-BB, 74% 93% P 2 2 isoechinulin B B, piperidine 110 C 36% neoechinulin B
9 Computational Studies on Model System! ,5 shift (0.0) (16.7) TS[42] (133.7) TS[42] (74.2) o-dcb, air 180 C, 1.5 h 73% 1,5 shift (55.1) labile bond (-49.8) []
10 Title Paper End Game! hydroxyviocristin isoechinulin B o-dcb, air 180 C, 0.5 h 48% variecolortide A o-dcb, air 180 C, 1 h 32% neoechinulin B variecolortide B There is no reaction under more biological conditions (aqueous phosphate buffer at room temperature) => catalyst is needed in nature, possibly Diels-Alderase!
11 Conclusions! Variecolortides A and B were synthesized in concise manner (7 and 5 steps, respectively)! Synthesis is mostly protecting group free (except for amide coupling reaction to form dipeptide)! Unprecedented hetero-diels-alder reaction is used in a key step, and the concerted mechanism is strongly supported by DFT calculations! The question of whether similar reaction occurs in nature is yet to be answered! Further biological exploration of these natural product is ongoing.!
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