Transannular Rearrangement of Activated Lactams: Stereoselective Synthesis of Substituted Pyrrolidine-2,4-diones from Diketopiperazines
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1 Transannular Rearrangement of Activated Lactams: Stereoselective Synthesis of Substituted Pyrrolidine-2,4-diones from Diketopiperazines Daniel Farran, Isabelle Parrot, Jean Martinez, Georges Dewynter Angew. Chem. Int. Ed. 2007, early view Current Literature Presentation Shuli Mao 09/15/07 Shuli Wipf Group 1 10/29/2007
2 Transannular Rearrangement of Activated Lactams (TRAL): A Serendipitous Finding Base * R 1 Base R 2 X * R 2 * * R 1 R 1 8 examples yield: 60-84% 95-99% ee 11 examples yield: 57-84% 67-99% de G. Dewynter, D. Farran, J. Martinez, Patent o , deposited March 21, Shuli Wipf Group 2 10/29/2007
3 utline Biological Activities and Synthesis of 2,5-DKPs Biological Activities and Synthesis of Pyrrolidine-2,4-diones Title Paper Summary and Future Directions Shuli Wipf Group 3 10/29/2007
4 Characteristics: 2,5-Diketopiperazines(DKPs) * R 1.The smallest cyclic peptide derived from the folding head-to-tail of a linear dipeptide 2.Structure is rigid and can be chiral molecule and can be functionalized Biological Activities: Inhibition of plasminogen activator inhibitor-1 (PAI-1), alteration of cardiovascular and blood-clotting functions, activity as antitumor, antiviral, antifungal, antibacterial agents etc. antitumor activity (IC 50 :4.3-18nM); being test in preclinical studies antibiotic Inhibition of glycogen phosphorylase Reviews:(a) Diketopiperazines: biological activity and synthesis Martins, M. B.; Carvalho, I. Tetrahydron 2007, 63, (b) Recent advances in the synthesis of diketopiperazines Dinsmore, C. J.; Beshore, D. C. Tetrahydron 2002, 58, (c) Diketopiperazines in peptide and combinatorial chemistry Fischer, P. M. J. Pept. Sci. 2003, 9, 9. Shuli Wipf Group 4 10/29/2007
5 Synthesis of 2,5-Diketopiperazines (a) Intramolecular formation of 1-C2 (1) Edmondson, S. D.; Danishefsky, S. J. Angew. Chem. Int. Ed. 1998, 37, (2) orton, D. A.; Bourne, G. T.; Smythe, M. L. Mol. Divers. 2000, 5, 289. Shuli Wipf Group 5 10/29/2007
6 Synthesis of 2,5-Diketopiperazines (b) Intramolecular formation of 1-C6 Marcaccini, S.; Pepino, R.; Pozo, M. A. Tetrahedron Lett. 2001, 42, Shuli Wipf Group 6 10/29/2007
7 Synthesis of 2,5-Diketopiperazines (c) Tandem formation of 1-C2/C3-4 (d) Tandem formation of 1-C2/4-C5 (1) Zawadzka, A.; Leniewski, A.; Maurin, J. K.; Wojtasiewicz, K.; Czarnocki, Z. rg. Lett. 2001, 3, 997. (2) Alcaraz, C.; errero, A.; Marco, J. L.; Fernández-Alvarez, E.; Bernabé, M. Tetrahedron Lett. 1992, 33, Shuli Wipf Group 7 10/29/2007
8 Synthesis of 2,5-Diketopiperazines (e) Tandem formation of C2-1-C6 Weigl, M.; Wünsch, B. rg. Lett. 2000, 2, Shuli Wipf Group 8 10/29/2007
9 Pyrrolidine-2,4-diones (Tetramic Acids) Electrophiles, Metallation ucleophiles Acylation 4 2 R 1 R 2 3-Acyl derivative of tetramic acid (common) 4--alkyl ether derivative of tetramic acid (less common) Spectrum of biological activity: antibiotic, antiviral, antiulcerative, cytotoxicity, mycotoxicity, tumor inhibition and fungicidal action α-cyclopiazonic acid Discodermide Dolastatin 15 very toxic (LD 50 :2-6 mgkg -1 ) potent inhibitor of calcium uptake and Ca 2+ ATP-ase activity antifungal and antitumor agent potent cytostatic agent against P388 leukemia cells Reviews: aturally occurring tetramic acids: structure, isolation and synthesis Royles, B. J. L. Chem. Rev. 1995, 95, Shuli Wipf Group 9 10/29/2007
10 Synthesis of Pyrrolidine-2,4-diones Solid-phase synthesis of tetramic acids via Claisen-type condensation: 4 2 R 1 R 2 Enantioselective Lacey-Dieckmann Cyclizations: Via urethane -carboxyanhydrides (UCAs or Leuchs anhydrides): (1) Kulkarni, B. A.; Ganesan, A. Tetrahedron Lett. 1998, 39, (2) Poncet, J.; Jouin, P.; Castro, B.; icolas, L.; Boutar, M.; Gaudemer, A. J. Chem. Soc., Perkin Trans , 611. (3) Pothion, C.; Fehrenta, J.-A.; Aumelas, A.; Loffet, A.; Martinez, J. Tetrahedron Lett. 1996, 37, Shuli Wipf Group 10 10/29/2007
11 riginal Plan: 6 Title Paper 1 5 enolate formation at 3 or 6 * 4 for the condensation reaction 2 3 R Farran, D.; Parrot, I.; Martinez, J.; Dewynter, G. Angew. Chem. Int. Ed. 2007, early view Reactions of -DKPs under basic condition: Example 1: Ph Example 2: 1 a Ph 90% no epimerization C Ph TMSI 60% Ph 2 C Ph tbuk, PhC + 84% 16% (1) Alcaraz, C.; errero, A.; Marco, J. L.; Fernández-Alvarez, E.; Bernabé, M. Tetrahedron Lett. 1992, 33, (2) ba, M.; Terauchi, T.; wari, Y.; Imai, Y.; motoyama, I.; ishiyama, K. J. Chem. Soc., Perkin Trans , Shuli Wipf Group 11 10/29/2007
12 Stereoselective Ring Contraction of Unsymmetrical DKPs into 3-Aminotetramates 1. tbuk, TF, RT * * R R 1 2 Shuli Wipf Group 12 10/29/2007
13 Stereoselective Ring Contraction of Symmetrical DKPs into Pyrrolidine-2,4-diones R R 1. tbuk, TF, RT R 1 3 R Shuli Wipf Group 13 10/29/2007
14 Tandem Rearrangement-alkylation of Symmetrical DKPs 1.LMDS ( 2eq) TF, -78 o C 2. RX (2eq) R 1a R 4a (R = allyl, 62%, de>95%) 4b (R = Bn, 57%, de>95%) Shuli Wipf Group 14 10/29/2007
15 Tandem Rearrangement-alkylation of Unsymmetrical DKPs * R LMDS, TF, -78 o C or a, TF, 0 o C 2. R 2 X R 2 * * R 1 5 Shuli Wipf Group 15 10/29/2007
16 Plausible Mechanism to Explain the Stereochemistry 1e Related reactions: Dieckmann and Gabriel-Colman reaction; Dakin-West reaction Shuli Wipf Group 16 10/29/2007
17 Scope Expansion: TRAL-Claisen Rearrangement K, allyl bromide DMS, 60% MWI, toluene/dms 170 o C, 30 min, 69% 2e 6 7 Stereochemistry controlled via chair-like TS What can you do with compound 7? steps 2 7 Statin derivatives Statin: constitutent of the naturally occuring peptide antibiotic Pepstatin, which functions as an unselective inhibitor of acid proteases such as renin, pepsin and cathepsin D. 7 Shuli Wipf Group 17 10/29/2007
18 Summary and Future Directions Pyrrolidine-2,4-diones was synthesized in a single step via ring contraction from DKPs; Reaction conditions are mild and the reaction is highly stereoselective; This methodology will be extended to make statine derivatives; Diversity can be introduced to these heterocyclic building blocks for library synthesis; Pyrrolidine-2,4-diones may have potential use as chiral auxillary; These new amino-acid derivatives can be used for the synthesis of pseudo-peptides or peptoids. Shuli Wipf Group 18 10/29/2007
19 Comments from the Audience (1) A similar acyclic version of this kind of rearrangement has been published from the Wipf group (rg. Lett. 2001, 3, 1261.) The mechanism of this rearrangement is not totally clear. (Radical may be involved?) (2) The stereochemistry of compounds 5(a-f) was not shown in Table 3, although in the supporting information they have this information. Shuli Wipf Group 19 10/29/2007
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