People, Travel, Seminars, Reading, the Classroom, and Curiosity-Sources of Research Inspiration
DOI:
https://doi.org/10.29356/jmcs.v54i2.956Keywords:
Electrohydrocyclization, redox, chemical synthesis, rearrangements, pseudopterosinAbstract
This manuscript is the outgrowth of a plenary lecture delivered by the author at the 44th Congreso Mexicano de Química that was held in Puebla, Mexico from 26-30 September of 2009. In formulating the presentation, consideration was given to thinking about the origins of the ideas that were integral to the formulation of the research to be described. The intent was to address the younger members of the audience – advanced undergraduate and graduate students, and those beginning the process of searching for a job. At a similar stage in my scientific career, I realized the need to formulate research plans in order to complete job applications where they were required. Where do these ideas come from? What factors stimulate one’s curiosity? What stimulates one to pursue a particular line of research? Topics discussed within the context of attempting to address these questions include electrohydrocyclization and electroreductive cyclization, and their application to the total synthesis of natural products, the use of nickel salen and triarylamines as mediators and redox catalysts, the regiospecific rearrangement of cation radicals derived from strained hydrocarbons and the application of the chemistry to the synthesis of a sesquiterpene, and finally, a discussion of the role redox chemistry may play in the expression of the bioactivity of the pseudopterosin class of marine natural products.
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1.The science described in this manuscript is the outgrowth of a plenary lecture delivered by the author at the 44th Congreso Mexicano de Química organized by the Sociedad Química de México that was held in Puebla, Mexico from 26-30 September of 2009.
2.Nobel Lecture, From Little Acorns to Tall Oaks – from Boranes through Organoboranes, H. C. Brown, 8 December, 1979.
3. (a) Anderson, J. D.; Baizer, M. M.; Petrovich, J. P. J. Org. Chem. 1965, 30, 1351-6. (b) Anderson, J. D.; Baizer, M. M.; Petrovich, J. P. J. Org. Chem. 1966, 31 (12), 3890-7. (c) Organic Electrochemistry, 4th ed.; Nielsen, M. F., Utley, J. H. P. In Organic Electrochemistry 4th etc. Lund, H., Hammerich, O., Eds.; Dekker: New York, 2001; pp 795-882 .
4. (a) Little, R. D; Moeller, K. D. Electrochem. Soc. Interface, 2002, 11(4), 36-42. (b) Schäfer, H. J. Angew. Chem. Int. Ed. Engl. 1981, 20, 911-934.
5. Interest in the area was first piqued while attending graduate school at the University of Wisconsin. Electrochemistry seemed to have many aspects in common with photochemistry, the study of which was the author’s major area of focus at the time.
6. Little, R. D.; Carroll, G. L. J. Org. Chem. 1979, 44, 4720-2.
7. Moëns, L.; Baizer, M. M.; Little, R. D. J. Org. Chem. 1986, 51, 4497-8.
8. The author expresses his appreciation to Professor Joseph W. Horton for being such an excellent and inspirational teacher.
9. Little, R. D.; Fox, D. P.; Van Hijfte, L.; Dannecker, R.; Sowell, G.; Wolin, R. L.; Moëns, L.; Baizer, M. M. J. Org. Chem. 1988, 53, 2287-94.
10. Sowell, C. G.; Wolin, R. L.; Little, R. D. Tetrahedron Lett. 1990, 31, 485-8.
11. (a) Cooper, K.; Pattenden, G. J. Chem. Soc., Perkin Trans. 1 1984, (4), 799-809. (b) Danishefsky, S.; Vaughan, K.; Gadwood, R.; Tsuzuki, K. J. Am. Chem. Soc. 1981, 103, 4136-41.
12. (a) Bode, H. E.; Sowell, C. G.; Little, R. D. Tetrahedron Lett. 1990, 31, 2525-8. (b) Amputch, M. A.; Little, R. D. Tetrahedron, 1991, 47, 383-402.
13. Fry, A. J.; Little, R. D; Leonetti, J. J. Org. Chem. 1994, 59, 501726.
14. European Research Conferences, Organic Electrochemistry: Interdisciplinary Approaches to Contemporary Problems in the Environment, San Feliu de Guixols, Spain; 19-23 April 1995.
15. Eru, E.; Hawkes, G. E.; Utley, J. H. P.; Wyatt, P. B. Tetrahedron 1995, 51, 3033-44.
16. The Dieckmann cyclization provides a good example. Thus, the initial acid-base reaction between a metal alkoxide and an ester clearly resides on the side of the starting materials. Nevertheless, the small amount of enolate that does form undergoes cyclization leading to the formation of a β-keto ester. The success of the process relies upon the fact that the proton residing between the carbonyl carbons in the product is the most acidic of all species present in the reaction mixture. Its removal irreversibly shifts the overall equilibrium to the product.
17. (a) Olivero, S.; Rolland, J.-P.; Dunach, E.; Labbe, E. Organometallics 2000, 19, 2798-2804. (b) The original inspiration stemmed from listening to Professor Dunach when she discussed the use of nickel salen and nickel cyclam to achieve selective transformations involving allyl aryl ethers. Her presentation was delivered to the 53rd Meeting of the International Society of Electrochemistry that was held in September of 2002 in Düsseldorf, Germany.
18. Miranda, J. A.; Wade, C. J.; Little, R. D. J. Org. Chem. 2005, 70, 8017-8026.
19. (a) Goken, D. M.; Ischay, M. A.; Peters, D. G.; Tomaszewski, J. W.; Karty, J. A.; Reilly, J. P.; Mubarak, M. S. J. Electrochem. Soc. 2006, 153, E71-E77. (b) Raess, P. W.; Mubarak, M. S.; Ischay, M. A.; Foley, M. P.; Jennermann, T. B.; Raghavachari, K.; Peters, D. G. J. Electroanal. Chem. 2007, 603, 124-134.
20. Calculations were carried out using Windows, Macintosh and Linux software supplied by Wavefunction, Inc. of Irvine, CA.
21. “Electron Transfer in Inorganic and Organic Chemistry”, a symposium held at the Westfälische Wilhelms-Universität in Münster, Germany in November of 2000.
22. Blancafort, L.; Adam, W.; Gonzalez, D.; Olivucci, M.; Vreven, T.; Robb, M. A. J. Am. Chem. Soc. 1999, 121, 10583-10590.
23. Gerken, J. B.; Wang, S. C.; Preciado, A. B.; Park, Y. S.; Nishiguchi, G.; Tantillo, D. J.; Little, R. D. J. Org. Chem. 2005, 70, 4598-4608.
24. Park, Y. S.; Wang, S. C.; Tantillo, D. J.; Little, R. D. J. Org. Chem. 2007, 72(12), 4351-4357.
25. Park, Y. S.; Little, R. D. J. Org. Chem. 2008, 73(17), 6807-6815.
26. Park, Y. S.; Little, R. D. Electrochimica Acta, 2009, 54, 50775082.
27. (a) Look, S. A.; Fenical, W.; Matsumoto, G. K.; Clardy, J. J. Org. Chem. 1986, 51, 5140–5145; (b) Roussis, V.; Wu, Z.; Fenical, W.; Strobel, S. A.; Van Duyne, G. D.; Clardy, J. J. Org. Chem. 1990, 55, 4916-4922;
28. Zhong, W.: Moya, C.; Jacobs, R. S.; Little, R. D. J. Org. Chem. 2008, 73, 7011-16.
29. The photo is from the web site: http://www.iquimica.unam.mx/ biblioteca.html
30. The phrase “child in a candy store” refers to the delight most children feel when they enter a candy store.
31. Corey, E. J.; Czakó, B.; Kürti, L. Molecules and Medicine; Wiley Interscience: New York, NY, 2007.
32. (a) Tanis, V. M.; Moya, C.; Jacobs, R. S.; Little, R. D. Tetrahedron, 2008, 64, 10649-10663. (b) Zhong, W.; Moya, C.; Jacobs, R. S.; Little, R. D. J. Org. Chem. 2008, 73, 7011-7016.
33. Hoarau, C.; Day, D.; Moya, C.; Wu, Guang; Hackim, A.; Jacobs, R. S.; Little, R. D. Tetrahedron Lett. 2008, 49, 4604-4606.
34. Zhong, W.; Little, R. D. Tetrahedron, 2009, 65, 10784-10790.
35. Unpublished results of Dr. Wei Zhong and Mr. Daniel Day, UCSB.
2.Nobel Lecture, From Little Acorns to Tall Oaks – from Boranes through Organoboranes, H. C. Brown, 8 December, 1979.
3. (a) Anderson, J. D.; Baizer, M. M.; Petrovich, J. P. J. Org. Chem. 1965, 30, 1351-6. (b) Anderson, J. D.; Baizer, M. M.; Petrovich, J. P. J. Org. Chem. 1966, 31 (12), 3890-7. (c) Organic Electrochemistry, 4th ed.; Nielsen, M. F., Utley, J. H. P. In Organic Electrochemistry 4th etc. Lund, H., Hammerich, O., Eds.; Dekker: New York, 2001; pp 795-882 .
4. (a) Little, R. D; Moeller, K. D. Electrochem. Soc. Interface, 2002, 11(4), 36-42. (b) Schäfer, H. J. Angew. Chem. Int. Ed. Engl. 1981, 20, 911-934.
5. Interest in the area was first piqued while attending graduate school at the University of Wisconsin. Electrochemistry seemed to have many aspects in common with photochemistry, the study of which was the author’s major area of focus at the time.
6. Little, R. D.; Carroll, G. L. J. Org. Chem. 1979, 44, 4720-2.
7. Moëns, L.; Baizer, M. M.; Little, R. D. J. Org. Chem. 1986, 51, 4497-8.
8. The author expresses his appreciation to Professor Joseph W. Horton for being such an excellent and inspirational teacher.
9. Little, R. D.; Fox, D. P.; Van Hijfte, L.; Dannecker, R.; Sowell, G.; Wolin, R. L.; Moëns, L.; Baizer, M. M. J. Org. Chem. 1988, 53, 2287-94.
10. Sowell, C. G.; Wolin, R. L.; Little, R. D. Tetrahedron Lett. 1990, 31, 485-8.
11. (a) Cooper, K.; Pattenden, G. J. Chem. Soc., Perkin Trans. 1 1984, (4), 799-809. (b) Danishefsky, S.; Vaughan, K.; Gadwood, R.; Tsuzuki, K. J. Am. Chem. Soc. 1981, 103, 4136-41.
12. (a) Bode, H. E.; Sowell, C. G.; Little, R. D. Tetrahedron Lett. 1990, 31, 2525-8. (b) Amputch, M. A.; Little, R. D. Tetrahedron, 1991, 47, 383-402.
13. Fry, A. J.; Little, R. D; Leonetti, J. J. Org. Chem. 1994, 59, 501726.
14. European Research Conferences, Organic Electrochemistry: Interdisciplinary Approaches to Contemporary Problems in the Environment, San Feliu de Guixols, Spain; 19-23 April 1995.
15. Eru, E.; Hawkes, G. E.; Utley, J. H. P.; Wyatt, P. B. Tetrahedron 1995, 51, 3033-44.
16. The Dieckmann cyclization provides a good example. Thus, the initial acid-base reaction between a metal alkoxide and an ester clearly resides on the side of the starting materials. Nevertheless, the small amount of enolate that does form undergoes cyclization leading to the formation of a β-keto ester. The success of the process relies upon the fact that the proton residing between the carbonyl carbons in the product is the most acidic of all species present in the reaction mixture. Its removal irreversibly shifts the overall equilibrium to the product.
17. (a) Olivero, S.; Rolland, J.-P.; Dunach, E.; Labbe, E. Organometallics 2000, 19, 2798-2804. (b) The original inspiration stemmed from listening to Professor Dunach when she discussed the use of nickel salen and nickel cyclam to achieve selective transformations involving allyl aryl ethers. Her presentation was delivered to the 53rd Meeting of the International Society of Electrochemistry that was held in September of 2002 in Düsseldorf, Germany.
18. Miranda, J. A.; Wade, C. J.; Little, R. D. J. Org. Chem. 2005, 70, 8017-8026.
19. (a) Goken, D. M.; Ischay, M. A.; Peters, D. G.; Tomaszewski, J. W.; Karty, J. A.; Reilly, J. P.; Mubarak, M. S. J. Electrochem. Soc. 2006, 153, E71-E77. (b) Raess, P. W.; Mubarak, M. S.; Ischay, M. A.; Foley, M. P.; Jennermann, T. B.; Raghavachari, K.; Peters, D. G. J. Electroanal. Chem. 2007, 603, 124-134.
20. Calculations were carried out using Windows, Macintosh and Linux software supplied by Wavefunction, Inc. of Irvine, CA.
21. “Electron Transfer in Inorganic and Organic Chemistry”, a symposium held at the Westfälische Wilhelms-Universität in Münster, Germany in November of 2000.
22. Blancafort, L.; Adam, W.; Gonzalez, D.; Olivucci, M.; Vreven, T.; Robb, M. A. J. Am. Chem. Soc. 1999, 121, 10583-10590.
23. Gerken, J. B.; Wang, S. C.; Preciado, A. B.; Park, Y. S.; Nishiguchi, G.; Tantillo, D. J.; Little, R. D. J. Org. Chem. 2005, 70, 4598-4608.
24. Park, Y. S.; Wang, S. C.; Tantillo, D. J.; Little, R. D. J. Org. Chem. 2007, 72(12), 4351-4357.
25. Park, Y. S.; Little, R. D. J. Org. Chem. 2008, 73(17), 6807-6815.
26. Park, Y. S.; Little, R. D. Electrochimica Acta, 2009, 54, 50775082.
27. (a) Look, S. A.; Fenical, W.; Matsumoto, G. K.; Clardy, J. J. Org. Chem. 1986, 51, 5140–5145; (b) Roussis, V.; Wu, Z.; Fenical, W.; Strobel, S. A.; Van Duyne, G. D.; Clardy, J. J. Org. Chem. 1990, 55, 4916-4922;
28. Zhong, W.: Moya, C.; Jacobs, R. S.; Little, R. D. J. Org. Chem. 2008, 73, 7011-16.
29. The photo is from the web site: http://www.iquimica.unam.mx/ biblioteca.html
30. The phrase “child in a candy store” refers to the delight most children feel when they enter a candy store.
31. Corey, E. J.; Czakó, B.; Kürti, L. Molecules and Medicine; Wiley Interscience: New York, NY, 2007.
32. (a) Tanis, V. M.; Moya, C.; Jacobs, R. S.; Little, R. D. Tetrahedron, 2008, 64, 10649-10663. (b) Zhong, W.; Moya, C.; Jacobs, R. S.; Little, R. D. J. Org. Chem. 2008, 73, 7011-7016.
33. Hoarau, C.; Day, D.; Moya, C.; Wu, Guang; Hackim, A.; Jacobs, R. S.; Little, R. D. Tetrahedron Lett. 2008, 49, 4604-4606.
34. Zhong, W.; Little, R. D. Tetrahedron, 2009, 65, 10784-10790.
35. Unpublished results of Dr. Wei Zhong and Mr. Daniel Day, UCSB.
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2019-06-17
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