Total Synthesis of (+/-)-Goniomitine via a Formal Nitrile/Donor-Acceptor Cyclopropane [3 + 2] Cyclization
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1 Total Synthesis of (+/-)-Goniomitine via a Formal itrile/donor-acceptor Cyclopropane [3 + 2] Cyclization (-)-Goniomitine Christian L. Morales and Brian Pagenkopf* rganic Letters, ASAP Current Literature Jennifer Davoren January 5, 2008 Jennifer Wipf Group 1 2/17/2008
2 Background Isolated in 1987 from the root bark of Gonioma malagasy Molecular formula determined by RMS λ max (Et) 228 and 291 nm were consistent with an indolinic chromophore and groups present were determined by IR 3200 and 3450 cm -1 respectively Remainder of the structure was elucidated by MR and partial synthesis Absolute stereochemistry was unknown, but tentatively assigned based on analogy with similar natural products within the class o known biological activity, but some analogs have demonstrated weak cytotoxicity toward L1210 leukemia cells (-)-Goniomitine Isolation paper: usson,.p; Tetrahedron Lett, 1987, Jennifer Wipf Group 2 2/17/2008
3 First Total Synthesis of (-)-Goniomitine Kinetically resolved from dicyclopentadiene by lipase 1. Zn, Ac/Et, 92% 2. EtI, Bu t K, TF o-dichlorobenzene, reflux 3. Allyl bromide, Bu t K, TF 58% (2 Steps) 24h LiAl 4, CuI, MPA-TF propane-1,3-diyldithiotosylate, 91% (2 Steps) ButK, 80% S S 1. K, Bu t K 2. C 2 2, Et 2 75% (2 Steps) S S Me 1. MeI, CaC 3, 10% aq. MeC 2. PPh 3, CBr 4, Et 3 3. LDA, TF, 82% (3 Steps) I C 2 Me Me C 2 Et PdCl(PPh 3 ) 2, CuI, Et 3 81% C 2 Et Takano, S.; J. Chem. Soc., Chem. Comm, 1991, Jennifer Wipf Group 3 2/17/2008
4 First Total Synthesis of (-)-Goniomitine C 2 Et C 2 Me aet, Et 3, Et (70% + 11%) Me Minor product from indole formation was also transformed to the lactam in 44% overall yield via sequential hydroboration-oxidation, Mitsonubu reaction and deacylation Major Minor dicyclohexylborane, then a and pthalimide, PPh 3, DIAD , 2 /Et 65% (3 Steps) 2 C reflux 1. Me 2 + =C 2 (Cl - ), C 2 Cl 2 2. MeI, Me 3. ac, DMF 78% (3 Steps) Takano, S.; J. Chem. Soc., Chem. Comm, 1991, Jennifer Wipf Group 4 2/17/2008
5 First Total Synthesis of (-)-Goniomitine C C C C PCl 3, toluene, reflux then ab 4, Me 84% 1. DIBAL 2. aq. 2 S 4 3. ab 4 49% (3 Steps) Cl Cl addition-elimination presumed reduction at the sterically less hindered top face Cl Spectral data did not match that of the natural product! rigin of the discrepancy was unknown. Stereochemistry was originally unknown Cl/Me, (1:10), reflux, 30 min 100%, single diastereomer Takano, S.; J. Chem. Soc., Chem. Comm, 1991, Jennifer Wipf Group 5 2/17/2008
6 First Total Synthesis of (-)-Goniomitine Et + Et Et (-)-goniomitine Takano, S.; J. Chem. Soc., Chem. Comm, 1991, Jennifer Wipf Group 6 2/17/2008
7 Pagenkopf s Total Synthesis of (+/-)-Goniomitine C 2 Et Bn (+/-)-goniomitine Synthetic Intermediate Common to Takano's Synthesis Formal Cycloaddition reaction C itrile Bn Me C 2 Et Donor-Acceptor Cyclopropane R R' Bond Cleavage C 2 R'' Me 3 SiTf R R' C 2 R'' C Y R R' Y C 2 R'' t Bu 2 Si TMSTf, PhC C 2 Cl 2, rt, 81% t Bu 2 Si Ph Pagenkopf, B. L; rg. Lett, ASAP For seminal publication see: Pagenkopf, B. L.; J. Am. Chem. Soc. 2003, 125, Jennifer Wipf Group 7 2/17/
8 Formal [3 + 2] Cycloadditions of Donor-Acceptor Cyclopropanes and itriles For seminal publication see: Pagenkopf, B. L.; J. Am. Chem. Soc. 2003, 125, Jennifer Wipf Group 8 2/17/2008
9 Formal [3 + 2] Cycloadditions to Form Pyrroles Synthesis of substituted Pyrroles from DA cyclopropanes via a domino cycloaddition, dehydration, and tautomerization strategy n Bu TMSTf R C 2 Et RC C 2 Et R R 2 R 3 C 2 Et TMSTf, Me 2 R 1 R R 3 R 2 R 1 C 2 Et -R R 3 R 1 R 2 C 2 Et Pagenkopf, B. L.; rg. Lett. 2003, 5, Jennifer Wipf Group 9 2/17/2008
10 Formal [3 + 2] Cycloadditions to Form Pyrroles: Scope Pagenkopf, B. L.; rg. Lett. 2003, 5, Jennifer Wipf Group 10 2/17/2008
11 Formal [3 + 2] Cycloaddition Methodology Successfully revealing the dipolar nature of the cyclopropane is highly dependent upon the LA and solvent used Ideal conditions are DA cyclopropane (1 eq), TMSTf (1 eq), RC (5-10 eq), Me 2 or C 2 Cl 2 (solvent) t Bu 2 Si uc TiCl 4, nucleophile ucleophile = allyltrimethylsilane alcohols Thiols t Bu 2 Si TMSTf, allyltrimethylsilane BF. 3 Et 2 t Bu 2 Si instead: t Bu 2 Si F Me 2 must be used as solvent when forming pyrroles R R 2 R 3 C 2 Et TMSTf, Toluene or C 2 Cl 2 R 1 R 3 R 1 R 2 C 2 Et instead: R 3 R 2 C 2 Et Jennifer Wipf Group 11 2/17/2008
12 Pagenkopf s Total Synthesis of (+/-)-Goniomitine 2 eq. n-buli, EtI then BnBr, 83% Bn 1. LDA, BrC 2 C 2 TP 2. cat. p-ts, Me 74% (2 Steps) Bn 1. MsCl, Et 3, C 2 Cl 2 2. ac, MeC 70% (2 Steps) Bn Me C 2 Et TMSTf, Et 2 74% C 2 Et Bn 1. Pd/C, mesitylene, 98% 2. a, Et/ 2 (1:1) 150 o C, µw, 75% 3. a, 3, 97% Formal syntheis 8 Steps, 20% yield (+/-)-Goniomitine Pagenkopf, B. L; rg. Lett, ASAP Jennifer Wipf Group 12 2/17/2008
13 Conclusions (-)-Goniomitine Pagenkopf s Synthesis: - 17 Linear Steps, 5% overall yield - Racemic - First practical application of his formal [3 +2] nitrile/donor-acceptor cyclopropane cyclization Takano s Synthesis: - 24 Linear Steps, 2.8% (1.4) overall yield - Asymmetric Jennifer Wipf Group 13 2/17/2008
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