Strained Alkenes in Natural Product Synthesis. 15 October 2013 Denmark Group MeeAng Hyung Min Chi
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1 Strained Alkenes in Natural Product Synthesis 15 October 2013 Denmark Group MeeAng Hyung Min Chi
2 Overview Types of strains in alkene system PreparaAon of strained alkenes Strained alkenes used in natural product synthesis Strained Alkenes in [4+2] CycloaddiAons Rubrolone aglycon, Platensimycin, CorAstaAn A, Cycloclavine, Asteriscanolide, Pleocarpenone & Pleocarpenene, Vinigrol Sigmatropic Strain- Driven Siloxy- Cope Rearrangement Phomoidride B Metal- Catalyzed ReacAons Spirofungin A, RouAennocin, Pentalenene, Isoquinoline alkaloids Nucleophilic AddiAon Hyacinthacine A2
3 Types of Strains in alkene system Angle compression TwisAng PyramidalizaAon Distor'on energy: The deformaaon of the reactants required for an opamal transiaon- state geometry Interac'on energy: Stabilizing electrostaac, charge- transfer & repulsion interacaons between approaching reactants Houk and Bickelhaupt suggests that the lower acavaaon energy correlates most accurately with distoraon/interacaon energy Schoenebeck, F.; Ess, D. H.; Jones, G. O.; Houk, K. N., J. Am. Chem. Soc. 2009, 131, 8121 van Zeist, W. J.; Bickelhaupt, F. M., Org. Biomol. Chem. 2010, 8, 3118
4 AcAvaAon, DistorAon and InteracAon energies DistorAon/InteracAon model (acavaaon/strain model) Diene distoraon energy: green Dienophile distoraon energy: blue InteracAon energy: red AcAvaAon energy: black Paton, R. S.; Kim, S.; Ross, A. G.; Danishefsky, S. J.; Houk, K. N. Angew. Chem. Int. Ed. 2011, 50, 10366
5 PreparaAon of the strained alkenes Barton- Kellogg s olefinaaon Tying- back methods Carbene coupling methods Lenoir, D.; Wahenbach, C.; Liebman, J. F., Struct. Chem. 2006, 17, 419.
6 Strained alkenes First synthesis of cyclopropene (1922) Dem yanov & Doyarenko Strained alkenes used in synthesis D. L. Boger, C. E. Brotherton, Tetrahedron 1986, 42, 2777
7 Cyclopropene Ketals Boger, 1986 Accelerate both normal and inverse electron demand Diels- Alder reacaon Cyclopropene ketals show exclusive exo selecavity D. L. Boger, C. E. Brotherton, Tetrahedron 1986, 42, 2777
8 Cyclopropene Ketals Boger, 2000 Synthesis of rubrolone aglycon UAlizing cyclopropene ketal to access tropone moiety D. L. Boger, S. Ichikawa, H. Jiang, J. Am. Chem. Soc. 2000, 122,
![Boger, 2000 Cyclopropene Ketals [4+2] cycloaddiaon with](/docs-images/87/96383268/images/9-0.jpg "cyclopropene ketals show high exo selecavity nearly")
9 Boger, 2000 Cyclopropene Ketals [4+2] cycloaddiaon with cyclopropene ketals show high exo selecavity nearly quanataave yield of cycloadduct as a single exo diastereomer. D. L. Boger, S. Ichikawa, H. Jiang, J. Am. Chem. Soc. 2000, 122,
10 Tetrabromocyclopropene Oblak & Wright, 2011 near instantaneous exo- selecave [4+2] cycloaddiaon Synthesis of a Key Oxabicyclo[3.2.1]octadiene Intermediate E. Z. Oblak, D. L. Wright, Org. LeD. 2011, 13, 2263.
11 Intramolecular [4+2]: Cyclopropene Magnus and Lilch, 2009 corastaan A tandem nucleophilic addiaon/intramolecular cyclopropene Diels Alder reacaon P. Magnus, R. Lilch, Org. LeD. 2009, 11, 3938.
12 Intramolecular [4+2]: Cyclopropene De Clercq, 1979/1982 Failed with unstrained alkene system (De Clercq) Intramolecular Diels- Alder furan approach P. Magnus, R. Lilch, Org. LeD. 2009, 11, P. J. De Clercq, L. A. Van Royen, Synth. Commun. 1979, 9, 771. L. A. Van Royen, R. Mijngheer, P. J. De Clercq, Tetrahedron LeD. 1982, 23, 3283.
![Intramolecular [4+2]: Methylenecyclopropane Petronijevic & Wipf, 2011 ergot alkaloid cycloclavine simultaneous installaaon of the quaternary cyclopropane stereocenter and the trans-](/docs-images/87/96383268/images/13-0.jpg "hydroindole ring system The observed rate acceleraaon results from methylenecyclopropane ring strain (40 kcal/mol) single trans diastereomer F. R. Petronijevic, P. Wipf, J. Am. Chem. Soc.")
13 Intramolecular [4+2]: Methylenecyclopropane Petronijevic & Wipf, 2011 ergot alkaloid cycloclavine simultaneous installaaon of the quaternary cyclopropane stereocenter and the trans- hydroindole ring system The observed rate acceleraaon results from methylenecyclopropane ring strain (40 kcal/mol) single trans diastereomer F. R. Petronijevic, P. Wipf, J. Am. Chem. Soc. 2011, 133, 7704.
14 Intramolecular [4+2]: Methylenecyclopropane Parker and Iqbal, 1987 Diels Alder reacaons with unstrained dienophile 200 o C for 10 hours gave cycloadducts less than 20% yield and with poor cis/ trans selecavity F. R. Petronijevic, P. Wipf, J. Am. Chem. Soc. 2011, 133, K. A. Parker, T. Iqbal, J. Org. Chem. 1987, 52, 4369.
15 Intramolecular [4+2]: Cyclobutadiene Snapper, 2000 (+)- asteriscanolide [4+2] cycloaddiaon upon oxidaave decomplexaaon Cross- metathesis followed by in situ Cope rearrangement J. Limanto, M. L. Snapper, J. Am. Chem. Soc. 2000, 122, 8071.
16 Intramolecular [4+2]: Cyclobutadiene Snapper, 2007 Pleocarpenone and pleocarpenene M. J. Williams, H. L. Deak, M. L. Snapper, J. Am. Chem. Soc. 2007, 129, 486.
17 Intramolecular [4+2]: Bicyclo[2.2.2]octene Baran, 2009 Vinigrol intramolecular Diels Alder reacaon/grob fragmentaaon Diels Alder cycloaddiaon with acyclic alkadiene results in only 46% aper 90 hours at 162 o C. T. J. Maimone, A. F. Voica, P. S. Baran, Angew. Chem. Int. Ed. 2008, 47, 3054 T. J. Maimone, J. Shi, S. Ashida, P. S. Baran, J. Am. Chem. Soc. 2009, 131, Y. T. Lin, K. N. Houk, Tetrahedron LeD. 1985, 26, 2269.
18 Sigmatropic Strain- driven Siloxy- Cope Rearrangement Clive, 1997/1997 Phomoidride B Leighton, 2003 one- pot Pd- catalyzed carbonylaaon/siloxy- Cope rearrangement with enol triflate P.W. M. Sgarbi, D. L. J. Clive, Chem. Commun. 1997, 2157; D. L. J. Clive, S. Sun, X. He, J. Zhang, V. Gagliardini, Tetrahedron LeD. 1999, 40, M. M. Bio, J. L. Leighton, J. Am. Chem. Soc. 1999, 121, 890; M. M. Bio, J. L. Leighton, Org. LeD. 2000, 2, M. M. Bio, J. L. Leighton, J. Org. Chem. 2003, 68, 1693.
19 Cross- Metathesis: Cyclopropenone Ketal Marjanovic and Kozmin, 2007 spirofungin A J. Marjanovic, S. A. Kozmin, Angew. Chem. Int. Ed. 2007, 46, 8854.
20 Cross- Metathesis: Cyclopropenone Ketal Mazumoto and Kozmin, 2008 rouaennocin K. Matsumoto, S. A. Kozmin, Adv. Synth. Catal. 2008, 350, 557.
21 Intramolecular Pauson- Khand ReacAon Pallerla and Fox, 2007 mulacomponent formal [2+2+1] cycloaddiaon (- )- Pentalenene higher reacavity of strained alkenes in Pauson Khand reacaons results from greater back donaaon to the lower- lying LUMO of a strained alkene M. K. Pallerla, J. M. Fox, Org. LeD. 2007, 9, 5625.
22 AddiAon to Strained Azabicyclic Alkenes Lautens, 2008 Isoquinoline alkaloids [4+2] cycloaddiaon of benzyne intermediate, generated in situ from dibromobenzene H. A. McManus, M. J. Fleming, M. Lautens, Angew. Chem. Int. Ed. 2007, 46, 433; M. J. Fleming, H. A. McManus, A. Rudolph, W. H. Chan, J. Ruiz, C. Dockendorff, M. Lautens, Chem. Eur. J. 2008, 14, 2112.
23 Nucleophilic AddiAon: Intramolecular trans- Cyclooctene HydroaminaAon Fox, 2011 Hyacinthacine A2 The increased reacavity likely results from significant twisang of the alkene p- system HOMO of the alkene becomes significantly higher in energy, allowing the destabilizing NH lone pair to encounter the electron- rich olefin p- system M. Royzen, M. T. Taylor, A. DeAngelis, J. M. Fox, Chem. Sci. 2011, 2, 2162.
24 Conclusion Use of strained alkenes allow access to reacaons than typically require significant acavaaon. Strategic use of strained alkenes can promote complex transformaaons in natural product syntheses. CycloaddiAons, rearrangements, metal- catalyzed reacaons, and nucleophilic addiaons Development of syntheac methods has facilitated access to highly strained alkenes
25 References Wilson, R.; Taylor, R. E., Angew. Chem. Int. Ed. 2013, 52, Meijere, A. de.; Blechert, S., Strain and its implicakons in organic chemistry : organic stress and reackvity. Dordrecht ; Kluwer Academic Publishers, Liebman, J. F.; Greenberg, A., Chem. Rev. 1976, 76, 311. Shea, K. J., Tetrahedron, 1980, 36, 1683 Paquehe, L. A et al, J. Am. Chem. Soc. 1971, 93, Vazquez, S.; Camps, P. Tetrahedron 2005, 61, Schoenebeck, F.; Ess, D. H.; Jones, G. O.; Houk, K. N., J. Am. Chem. Soc. 2009, 131, 8121 van Zeist, W. J.; Bickelhaupt, F. M., Org. Biomol. Chem. 2010, 8, 3118 Paton, R. S.; Kim, S.; Ross, A. G.; Danishefsky, S. J.; Houk, K. N. Angew. Chem. Int. Ed. 2011, 50, Lenoir, D.; Wahenbach, C.; Liebman, J. F., Struct. Chem. 2006, 17, 419. D. L. Boger, S. Ichikawa, H. Jiang, J. Am. Chem. Soc. 2000, 122, E. Z. Oblak, D. L. Wright, Org. LeD. 2011, 13, P. Magnus, R. Lilch, Org. LeD. 2009, 11, P. J. De Clercq, L. A. Van Royen, Synth. Commun. 1979, 9, 771. L. A. Van Royen, R. Mijngheer, P. J. De Clercq, Tetrahedron LeD. 1982, 23, F. R. Petronijevic, P. Wipf, J. Am. Chem. Soc. 2011, 133, K. A. Parker, T. Iqbal, J. Org. Chem. 1987, 52, J. Limanto, M. L. Snapper, J. Am. Chem. Soc. 2000, 122, M. J. Williams, H. L. Deak, M. L. Snapper, J. Am. Chem. Soc. 2007, 129, 486. T. J. Maimone, A. F. Voica, P. S. Baran, Angew. Chem. Int. Ed. 2008, 47, 3054 T. J. Maimone, J. Shi, S. Ashida, P. S. Baran, J. Am. Chem. Soc. 2009, 131, Y. T. Lin, K. N. Houk, Tetrahedron LeD. 1985, 26, P.W. M. Sgarbi, D. L. J. Clive, Chem. Commun. 1997, 2157; D. L. J. Clive, S. Sun, X. He, J. Zhang, V. Gagliardini, Tetrahedron LeD. 1999, 40, M. M. Bio, J. L. Leighton, J. Org. Chem. 2003, 68, J. Marjanovic, S. A. Kozmin, Angew. Chem. Int. Ed. 2007, 46, K. Matsumoto, S. A. Kozmin, Adv. Synth. Catal. 2008, 350, 557. M. K. Pallerla, J. M. Fox, Org. LeD. 2007, 9, H. A. McManus, M. J. Fleming, M. Lautens, Angew. Chem. Int. Ed. 2007, 46, 433 M. J. Fleming, H. A. McManus, A. Rudolph, W. H. Chan, J. Ruiz, C. Dockendorff, M. Lautens, Chem. Eur. J. 2008, 14, M. Royzen, M. T. Taylor, A. DeAngelis, J. M. Fox, Chem. Sci. 2011, 2, 2162.
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