A practical and efficient synthetic route to dihydropipercide and pipercide

Journal of Organic Chemistry

Volumn 63, Issue 19, 1998, Pages 6667-6672

  Rotherham, Lloyd W ^a,b   Edward Semple, J ^a,b,c  

^a SHELL GLOBAL SOLUTIONS INTERNATIONAL B V   (United States)

^b DUPONT COMPANY   (United States)

^c Dendreon   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

DIHYDROPIPERCIDE; INSECTICIDE; PIPERCIDE; UNCLASSIFIED DRUG;

ARTICLE; DRUG ISOLATION; DRUG SYNTHESIS; HYDROLYSIS; HYDROPHOBICITY; ISOMERISM; NONHUMAN; POTASSIUM TRANSPORT; TANDEM REPEAT;

EID: 7344223255     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo981039d     Document Type: Article

References (59)

1. Dedicated with genuine respect and admiration to Professor Victor A. Snieckus, Department of Chemistry, Guelph-Waterloo Centre for Graduate Work in Chemistry, Ontario, Canada, on the occasion of his 60th birthday.
2. Crombie, L.; Fisher, D. Tetrahedron Lett. 1985, 26, (a) 2477, (b) 2481. (c) Miyakado, M.; Nakayama, I.; Ohno, N. In Insecticides of Plant Origin, Arnason, J. T., Philogene, B. J. R., Morand, P., Eds.; ACS Symposium Series 387; American Chemical Society: Washington, DC, 1989.
3. Crombie, L.; Fisher, D. Tetrahedron Lett. 1985, 26, (a) 2477, (b) 2481. (c) Miyakado, M.; Nakayama, I.; Ohno, N. In Insecticides of Plant Origin, Arnason, J. T., Philogene, B. J. R., Morand, P., Eds.; ACS Symposium Series 387; American Chemical Society: Washington, DC, 1989.
4. Crombie, L.; Fisher, D. Tetrahedron Lett. 1985, 26, (a) 2477, (b) 2481. (c) Miyakado, M.; Nakayama, I.; Ohno, N. In Insecticides of Plant Origin, Arnason, J. T., Philogene, B. J. R., Morand, P., Eds.; ACS Symposium Series 387; American Chemical Society: Washington, DC, 1989.
5. Seminal contributions: Crombie, L. J. Chem. Soc. 1955, (a) 1007, (b) 999. (c) Jacobson, M. J. Am. Chem. Soc. 1949, 71, 366.
6. Seminal contributions: Crombie, L. J. Chem. Soc. 1955, (a) 1007, (b) 999. (c) Jacobson, M. J. Am. Chem. Soc. 1949, 71, 366.
7. Seminal contributions: Crombie, L. J. Chem. Soc. 1955, (a) 1007, (b) 999. (c) Jacobson, M. J. Am. Chem. Soc. 1949, 71, 366.
8. (a) Authoritative reviews: Jacobson, M. In Naturally Occurring Insecticides, Ch. 4; Jacobson, M., Crosby, D. G., Eds.; John Wiley: New York, 1971.
9. (b) Hsu, H. C. F. In Comprehensive Insect Physiology, Biochemistry, and Pharmacology, Vol. 12, Ch. 9; Kerkut, G. A., Gilbert, L. I., Eds.; Pergamon Press: New York, 1985.
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11. Miyakado, M.; Nakayama, I.; Yoshioka, H.; Nakatani, N. Agric. Biol. Chem. 1979, 43, 1609.
12. Dihydropipercide and Pipercide total synthesis: (a) Strunz, G. M.; Finlay, H. Tetrahedron 1994, 50, 11113. (b) Sabharwal, A.; Dogra, V.; Sharma, S.; Kaira, R.; Vig, O. P.; Kad, G. L. J. Indian Chem. Soc. 1990, 67, 318. (c) Bloch, R.; Hassan-Gonzales, D. Tetrahedron 1986, 42, 4975. (d) Crombie, L. Denman, R. Tetrahedron Lett. 1984, 25, 4267. (e) Miyakado, M.; Yoshioka, H. Agric. Biol. Chem. 1979, 43, 2413.
13. Dihydropipercide and Pipercide total synthesis: (a) Strunz, G. M.; Finlay, H. Tetrahedron 1994, 50, 11113. (b) Sabharwal, A.; Dogra, V.; Sharma, S.; Kaira, R.; Vig, O. P.; Kad, G. L. J. Indian Chem. Soc. 1990, 67, 318. (c) Bloch, R.; Hassan-Gonzales, D. Tetrahedron 1986, 42, 4975. (d) Crombie, L. Denman, R. Tetrahedron Lett. 1984, 25, 4267. (e) Miyakado, M.; Yoshioka, H. Agric. Biol. Chem. 1979, 43, 2413.
14. Dihydropipercide and Pipercide total synthesis: (a) Strunz, G. M.; Finlay, H. Tetrahedron 1994, 50, 11113. (b) Sabharwal, A.; Dogra, V.; Sharma, S.; Kaira, R.; Vig, O. P.; Kad, G. L. J. Indian Chem. Soc. 1990, 67, 318. (c) Bloch, R.; Hassan-Gonzales, D. Tetrahedron 1986, 42, 4975. (d) Crombie, L. Denman, R. Tetrahedron Lett. 1984, 25, 4267. (e) Miyakado, M.; Yoshioka, H. Agric. Biol. Chem. 1979, 43, 2413.
15. Dihydropipercide and Pipercide total synthesis: (a) Strunz, G. M.; Finlay, H. Tetrahedron 1994, 50, 11113. (b) Sabharwal, A.; Dogra, V.; Sharma, S.; Kaira, R.; Vig, O. P.; Kad, G. L. J. Indian Chem. Soc. 1990, 67, 318. (c) Bloch, R.; Hassan-Gonzales, D. Tetrahedron 1986, 42, 4975. (d) Crombie, L. Denman, R. Tetrahedron Lett. 1984, 25, 4267. (e) Miyakado, M.; Yoshioka, H. Agric. Biol. Chem. 1979, 43, 2413.
16. Dihydropipercide and Pipercide total synthesis: (a) Strunz, G. M.; Finlay, H. Tetrahedron 1994, 50, 11113. (b) Sabharwal, A.; Dogra, V.; Sharma, S.; Kaira, R.; Vig, O. P.; Kad, G. L. J. Indian Chem. Soc. 1990, 67, 318. (c) Bloch, R.; Hassan-Gonzales, D. Tetrahedron 1986, 42, 4975. (d) Crombie, L. Denman, R. Tetrahedron Lett. 1984, 25, 4267. (e) Miyakado, M.; Yoshioka, H. Agric. Biol. Chem. 1979, 43, 2413.
17. Pellitorine synthesis: (a) Jacobson, M. J. Am. Chem. Soc. 1953, 75, 2584. Most recent approaches: (b) Abarbri, M.; Parrain, J. L.; Duchene, A. Synth. Commun. 1998, 28, 239. (c) Semple, J. E. Org. Prep. Proc. Intl. 1995, 27, 582.
18. Pellitorine synthesis: (a) Jacobson, M. J. Am. Chem. Soc. 1953, 75, 2584. Most recent approaches: (b) Abarbri, M.; Parrain, J. L.; Duchene, A. Synth. Commun. 1998, 28, 239. (c) Semple, J. E. Org. Prep. Proc. Intl. 1995, 27, 582.
19. Pellitorine synthesis: (a) Jacobson, M. J. Am. Chem. Soc. 1953, 75, 2584. Most recent approaches: (b) Abarbri, M.; Parrain, J. L.; Duchene, A. Synth. Commun. 1998, 28, 239. (c) Semple, J. E. Org. Prep. Proc. Intl. 1995, 27, 582.
20. The reported neurological, synergism, and mode of action results were confirmed by independent studies at Shell. Personal communication from Dr. M. E. Schroeder, Shell Development BSRC.
21. (a) Mukerjee, S. K.; Walia, S.; Saxena, V. S.; Tomar, S. S. Agric. Biol. Chem. 1982, 46, 1277.
22. (b) Tomar, S. S.; Dutta, S. Indian J. Ent. 1980, 42, 802.
23. (c) Tomar, S. S.; Saxena, V. S., ref 10b, 713.
24. (d) Su, H. C. F. J. Econ. Entomol. 1977, 70, 18.
25. (e) Gordon, H. T.; Jao, L. T. J. Econ. Entomol. 1971, 64, 546.
26. Johnson orthoacetate Claisen rearrangement: (a) Johnson, W. S.; Werthemann, L.; Bartlett, W. R.; Brocksom, T. J.; Li, T. T.; Faulkner, D. J.; Petersen, M. R. J. Am. Chem. Soc. 1970, 92, 741. (b) Brenna, E.; Caraccia, N.; Fuganti, C.; Fuganti, D.; Grasselli, P. Tetrahedron: Asymmetry 1997, 8, 3801. (c) Basavaiah, D.; Pandiaraju, S.; Krishnamacharyulu, M. Synlett 1996, 747. (d) Guthrie, A. E.; Semple, J. E.; Joullie, M. M. J. Org. Chem. 1982, 47, 2369.
27. Johnson orthoacetate Claisen rearrangement: (a) Johnson, W. S.; Werthemann, L.; Bartlett, W. R.; Brocksom, T. J.; Li, T. T.; Faulkner, D. J.; Petersen, M. R. J. Am. Chem. Soc. 1970, 92, 741. (b) Brenna, E.; Caraccia, N.; Fuganti, C.; Fuganti, D.; Grasselli, P. Tetrahedron: Asymmetry 1997, 8, 3801. (c) Basavaiah, D.; Pandiaraju, S.; Krishnamacharyulu, M. Synlett 1996, 747. (d) Guthrie, A. E.; Semple, J. E.; Joullie, M. M. J. Org. Chem. 1982, 47, 2369.
28. Johnson orthoacetate Claisen rearrangement: (a) Johnson, W. S.; Werthemann, L.; Bartlett, W. R.; Brocksom, T. J.; Li, T. T.; Faulkner, D. J.; Petersen, M. R. J. Am. Chem. Soc. 1970, 92, 741. (b) Brenna, E.; Caraccia, N.; Fuganti, C.; Fuganti, D.; Grasselli, P. Tetrahedron: Asymmetry 1997, 8, 3801. (c) Basavaiah, D.; Pandiaraju, S.; Krishnamacharyulu, M. Synlett 1996, 747. (d) Guthrie, A. E.; Semple, J. E.; Joullie, M. M. J. Org. Chem. 1982, 47, 2369.
29. Johnson orthoacetate Claisen rearrangement: (a) Johnson, W. S.; Werthemann, L.; Bartlett, W. R.; Brocksom, T. J.; Li, T. T.; Faulkner, D. J.; Petersen, M. R. J. Am. Chem. Soc. 1970, 92, 741. (b) Brenna, E.; Caraccia, N.; Fuganti, C.; Fuganti, D.; Grasselli, P. Tetrahedron: Asymmetry 1997, 8, 3801. (c) Basavaiah, D.; Pandiaraju, S.; Krishnamacharyulu, M. Synlett 1996, 747. (d) Guthrie, A. E.; Semple, J. E.; Joullie, M. M. J. Org. Chem. 1982, 47, 2369.
30. Wittig olefination reaction: (a) Wittig, G.; Geissler, G. Liebigs Ann. Chem. 1953, 580, 44. (b) Wittig, G. Science 1980, 210, 600. (c) Vedejs, E.; Peterson, M. J. Adv. Carbanion Chem. 1996, 2, 1. (d) Walker, B. J. Organophosphorus Chem. 1996, 27, 264. (e) Ager, D. J. Org. React. 1990, 38, 1. (f) Maryanoff, B. E.; Reitz, A. B. Chem. Rev. 1989, 89, 3. (g) Maercker, A. Org. React. 1965, 14, 270.
31. Wittig olefination reaction: (a) Wittig, G.; Geissler, G. Liebigs Ann. Chem. 1953, 580, 44. (b) Wittig, G. Science 1980, 210, 600. (c) Vedejs, E.; Peterson, M. J. Adv. Carbanion Chem. 1996, 2, 1. (d) Walker, B. J. Organophosphorus Chem. 1996, 27, 264. (e) Ager, D. J. Org. React. 1990, 38, 1. (f) Maryanoff, B. E.; Reitz, A. B. Chem. Rev. 1989, 89, 3. (g) Maercker, A. Org. React. 1965, 14, 270.
32. Wittig olefination reaction: (a) Wittig, G.; Geissler, G. Liebigs Ann. Chem. 1953, 580, 44. (b) Wittig, G. Science 1980, 210, 600. (c) Vedejs, E.; Peterson, M. J. Adv. Carbanion Chem. 1996, 2, 1. (d) Walker, B. J. Organophosphorus Chem. 1996, 27, 264. (e) Ager, D. J. Org. React. 1990, 38, 1. (f) Maryanoff, B. E.; Reitz, A. B. Chem. Rev. 1989, 89, 3. (g) Maercker, A. Org. React. 1965, 14, 270.
33. Wittig olefination reaction: (a) Wittig, G.; Geissler, G. Liebigs Ann. Chem. 1953, 580, 44. (b) Wittig, G. Science 1980, 210, 600. (c) Vedejs, E.; Peterson, M. J. Adv. Carbanion Chem. 1996, 2, 1. (d) Walker, B. J. Organophosphorus Chem. 1996, 27, 264. (e) Ager, D. J. Org. React. 1990, 38, 1. (f) Maryanoff, B. E.; Reitz, A. B. Chem. Rev. 1989, 89, 3. (g) Maercker, A. Org. React. 1965, 14, 270.
34. Wittig olefination reaction: (a) Wittig, G.; Geissler, G. Liebigs Ann. Chem. 1953, 580, 44. (b) Wittig, G. Science 1980, 210, 600. (c) Vedejs, E.; Peterson, M. J. Adv. Carbanion Chem. 1996, 2, 1. (d) Walker, B. J. Organophosphorus Chem. 1996, 27, 264. (e) Ager, D. J. Org. React. 1990, 38, 1. (f) Maryanoff, B. E.; Reitz, A. B. Chem. Rev. 1989, 89, 3. (g) Maercker, A. Org. React. 1965, 14, 270.
35. Wittig olefination reaction: (a) Wittig, G.; Geissler, G. Liebigs Ann. Chem. 1953, 580, 44. (b) Wittig, G. Science 1980, 210, 600. (c) Vedejs, E.; Peterson, M. J. Adv. Carbanion Chem. 1996, 2, 1. (d) Walker, B. J. Organophosphorus Chem. 1996, 27, 264. (e) Ager, D. J. Org. React. 1990, 38, 1. (f) Maryanoff, B. E.; Reitz, A. B. Chem. Rev. 1989, 89, 3. (g) Maercker, A. Org. React. 1965, 14, 270.
36. Wittig olefination reaction: (a) Wittig, G.; Geissler, G. Liebigs Ann. Chem. 1953, 580, 44. (b) Wittig, G. Science 1980, 210, 600. (c) Vedejs, E.; Peterson, M. J. Adv. Carbanion Chem. 1996, 2, 1. (d) Walker, B. J. Organophosphorus Chem. 1996, 27, 264. (e) Ager, D. J. Org. React. 1990, 38, 1. (f) Maryanoff, B. E.; Reitz, A. B. Chem. Rev. 1989, 89, 3. (g) Maercker, A. Org. React. 1965, 14, 270.
37. For a useful compilation of olefin isomerization protocols, see: Larock, R. C. Comprehensive Organic Transformations, 109; VCH Publishers: New York, 1989.
38. Thiophenyl radical olefin isomerization: (a) Henrick, C. A.; Willy, W. E.; Baum, J. W.; Baer, T. A.; Garcia, B. A.; Mastre, T. A.; Chang, S. M. J. Org. Chem. 1975, 40, 1. (b) We wish to thank our colleague Mr. Thomas L. Brown of Shell BSRC for bringing this excellent procedure to our attention.
39. Thiophenyl radical olefin isomerization: (a) Henrick, C. A.; Willy, W. E.; Baum, J. W.; Baer, T. A.; Garcia, B. A.; Mastre, T. A.; Chang, S. M. J. Org. Chem. 1975, 40, 1. (b) We wish to thank our colleague Mr. Thomas L. Brown of Shell BSRC for bringing this excellent procedure to our attention.
40. Horner-Wadsworth-Emmons reaction: (a) Mulzer, J.; Berger, M. Tetrahedron Lett. 1998, 39, 803. (b) Coleman, R. S.; Carpenter, A. J. Tetrahedron 1997, 53, 16313. (c) Nicolaou, K. C.; Harter, M. W.; Gunzner, J. L.; Nadin, A. Liebigs Ann./Recl. 1997, Issue 7, 1283. (d) Lawrence, N. J. Prep. Alkenes; Williams, J. M. J., Ed.; Oxford University Press: Oxford, U.K., 1996; p 19. (e) Kelly, S. E. Compr. Org. Synth. 1991, 1, 755. (f) Wadsworth, W. S. Org. React. 1977, 25, 73. (g) Boutagy, J.; Thomas, R. Chem. Rev. 1974, 74, 87.
41. Horner-Wadsworth-Emmons reaction: (a) Mulzer, J.; Berger, M. Tetrahedron Lett. 1998, 39, 803. (b) Coleman, R. S.; Carpenter, A. J. Tetrahedron 1997, 53, 16313. (c) Nicolaou, K. C.; Harter, M. W.; Gunzner, J. L.; Nadin, A. Liebigs Ann./Recl. 1997, Issue 7, 1283. (d) Lawrence, N. J. Prep. Alkenes; Williams, J. M. J., Ed.; Oxford University Press: Oxford, U.K., 1996; p 19. (e) Kelly, S. E. Compr. Org. Synth. 1991, 1, 755. (f) Wadsworth, W. S. Org. React. 1977, 25, 73. (g) Boutagy, J.; Thomas, R. Chem. Rev. 1974, 74, 87.
42. Horner-Wadsworth-Emmons reaction: (a) Mulzer, J.; Berger, M. Tetrahedron Lett. 1998, 39, 803. (b) Coleman, R. S.; Carpenter, A. J. Tetrahedron 1997, 53, 16313. (c) Nicolaou, K. C.; Harter, M. W.; Gunzner, J. L.; Nadin, A. Liebigs Ann./Recl. 1997, Issue 7, 1283. (d) Lawrence, N. J. Prep. Alkenes; Williams, J. M. J., Ed.; Oxford University Press: Oxford, U.K., 1996; p 19. (e) Kelly, S. E. Compr. Org. Synth. 1991, 1, 755. (f) Wadsworth, W. S. Org. React. 1977, 25, 73. (g) Boutagy, J.; Thomas, R. Chem. Rev. 1974, 74, 87.
43. Horner-Wadsworth-Emmons reaction: (a) Mulzer, J.; Berger, M. Tetrahedron Lett. 1998, 39, 803. (b) Coleman, R. S.; Carpenter, A. J. Tetrahedron 1997, 53, 16313. (c) Nicolaou, K. C.; Harter, M. W.; Gunzner, J. L.; Nadin, A. Liebigs Ann./Recl. 1997, Issue 7, 1283. (d) Lawrence, N. J. Prep. Alkenes; Williams, J. M. J., Ed.; Oxford University Press: Oxford, U.K., 1996; p 19. (e) Kelly, S. E. Compr. Org. Synth. 1991, 1, 755. (f) Wadsworth, W. S. Org. React. 1977, 25, 73. (g) Boutagy, J.; Thomas, R. Chem. Rev. 1974, 74, 87.
44. Horner-Wadsworth-Emmons reaction: (a) Mulzer, J.; Berger, M. Tetrahedron Lett. 1998, 39, 803. (b) Coleman, R. S.; Carpenter, A. J. Tetrahedron 1997, 53, 16313. (c) Nicolaou, K. C.; Harter, M. W.; Gunzner, J. L.; Nadin, A. Liebigs Ann./Recl. 1997, Issue 7, 1283. (d) Lawrence, N. J. Prep. Alkenes; Williams, J. M. J., Ed.; Oxford University Press: Oxford, U.K., 1996; p 19. (e) Kelly, S. E. Compr. Org. Synth. 1991, 1, 755. (f) Wadsworth, W. S. Org. React. 1977, 25, 73. (g) Boutagy, J.; Thomas, R. Chem. Rev. 1974, 74, 87.
45. Horner-Wadsworth-Emmons reaction: (a) Mulzer, J.; Berger, M. Tetrahedron Lett. 1998, 39, 803. (b) Coleman, R. S.; Carpenter, A. J. Tetrahedron 1997, 53, 16313. (c) Nicolaou, K. C.; Harter, M. W.; Gunzner, J. L.; Nadin, A. Liebigs Ann./Recl. 1997, Issue 7, 1283. (d) Lawrence, N. J. Prep. Alkenes; Williams, J. M. J., Ed.; Oxford University Press: Oxford, U.K., 1996; p 19. (e) Kelly, S. E. Compr. Org. Synth. 1991, 1, 755. (f) Wadsworth, W. S. Org. React. 1977, 25, 73. (g) Boutagy, J.; Thomas, R. Chem. Rev. 1974, 74, 87.
46. Horner-Wadsworth-Emmons reaction: (a) Mulzer, J.; Berger, M. Tetrahedron Lett. 1998, 39, 803. (b) Coleman, R. S.; Carpenter, A. J. Tetrahedron 1997, 53, 16313. (c) Nicolaou, K. C.; Harter, M. W.; Gunzner, J. L.; Nadin, A. Liebigs Ann./Recl. 1997, Issue 7, 1283. (d) Lawrence, N. J. Prep. Alkenes; Williams, J. M. J., Ed.; Oxford University Press: Oxford, U.K., 1996; p 19. (e) Kelly, S. E. Compr. Org. Synth. 1991, 1, 755. (f) Wadsworth, W. S. Org. React. 1977, 25, 73. (g) Boutagy, J.; Thomas, R. Chem. Rev. 1974, 74, 87.
47. Bedoukian, P. Z. J. Am. Chem. Soc. 1945, 67, 1430.
48. Interestingly, a GAS Sci-Finder search (May, 1998) on the synthesis of Me 6-oxohexanoate 9 revealed many (ca. 77 hits) literature and patent citations. We believe the method disclosed herein is very practical and in our hands has consistently provided good yields of pure material. Following is a listing of protocols which are complimentary to ours and would appear most suitable for laboratory scale preparation of this useful intermediate: (a) Hon, Y. S.; Yan, J. L. Tetrahedron 1997, 53, 5217. (b) Floresca, R.; Kurihara, M.; Watt, D. S.; Demir, A. J. Org. Chem. 1993, 58, 2196. (d) Claus, R. E.; Schreiber, S. L. Org. Synth. 1986, 64, 150. (e) Bosone, E.; Farina, P.; Guazzi, G.; Innocenti, S.; Marotta, V. Synthesis 1983, 942. (f) Schreiber, S. L.; Claus, R. E.; Reagan, J. Tetrahedron Lett. 1982, 23, 3867. (g) Buchi, G.; Wuest, H. Helv. Chim. Acta 1979, 62, 2661.
49. Interestingly, a GAS Sci-Finder search (May, 1998) on the synthesis of Me 6-oxohexanoate 9 revealed many (ca. 77 hits) literature and patent citations. We believe the method disclosed herein is very practical and in our hands has consistently provided good yields of pure material. Following is a listing of protocols which are complimentary to ours and would appear most suitable for laboratory scale preparation of this useful intermediate: (a) Hon, Y. S.; Yan, J. L. Tetrahedron 1997, 53, 5217. (b) Floresca, R.; Kurihara, M.; Watt, D. S.; Demir, A. J. Org. Chem. 1993, 58, 2196. (d) Claus, R. E.; Schreiber, S. L. Org. Synth. 1986, 64, 150. (e) Bosone, E.; Farina, P.; Guazzi, G.; Innocenti, S.; Marotta, V. Synthesis 1983, 942. (f) Schreiber, S. L.; Claus, R. E.; Reagan, J. Tetrahedron Lett. 1982, 23, 3867. (g) Buchi, G.; Wuest, H. Helv. Chim. Acta 1979, 62, 2661.
50. Interestingly, a GAS Sci-Finder search (May, 1998) on the synthesis of Me 6-oxohexanoate 9 revealed many (ca. 77 hits) literature and patent citations. We believe the method disclosed herein is very practical and in our hands has consistently provided good yields of pure material. Following is a listing of protocols which are complimentary to ours and would appear most suitable for laboratory scale preparation of this useful intermediate: (a) Hon, Y. S.; Yan, J. L. Tetrahedron 1997, 53, 5217. (b) Floresca, R.; Kurihara, M.; Watt, D. S.; Demir, A. J. Org. Chem. 1993, 58, 2196. (d) Claus, R. E.; Schreiber, S. L. Org. Synth. 1986, 64, 150. (e) Bosone, E.; Farina, P.; Guazzi, G.; Innocenti, S.; Marotta, V. Synthesis 1983, 942. (f) Schreiber, S. L.; Claus, R. E.; Reagan, J. Tetrahedron Lett. 1982, 23, 3867. (g) Buchi, G.; Wuest, H. Helv. Chim. Acta 1979, 62, 2661.
51. Interestingly, a GAS Sci-Finder search (May, 1998) on the synthesis of Me 6-oxohexanoate 9 revealed many (ca. 77 hits) literature and patent citations. We believe the method disclosed herein is very practical and in our hands has consistently provided good yields of pure material. Following is a listing of protocols which are complimentary to ours and would appear most suitable for laboratory scale preparation of this useful intermediate: (a) Hon, Y. S.; Yan, J. L. Tetrahedron 1997, 53, 5217. (b) Floresca, R.; Kurihara, M.; Watt, D. S.; Demir, A. J. Org. Chem. 1993, 58, 2196. (d) Claus, R. E.; Schreiber, S. L. Org. Synth. 1986, 64, 150. (e) Bosone, E.; Farina, P.; Guazzi, G.; Innocenti, S.; Marotta, V. Synthesis 1983, 942. (f) Schreiber, S. L.; Claus, R. E.; Reagan, J. Tetrahedron Lett. 1982, 23, 3867. (g) Buchi, G.; Wuest, H. Helv. Chim. Acta 1979, 62, 2661.
52. Interestingly, a GAS Sci-Finder search (May, 1998) on the synthesis of Me 6-oxohexanoate 9 revealed many (ca. 77 hits) literature and patent citations. We believe the method disclosed herein is very practical and in our hands has consistently provided good yields of pure material. Following is a listing of protocols which are complimentary to ours and would appear most suitable for laboratory scale preparation of this useful intermediate: (a) Hon, Y. S.; Yan, J. L. Tetrahedron 1997, 53, 5217. (b) Floresca, R.; Kurihara, M.; Watt, D. S.; Demir, A. J. Org. Chem. 1993, 58, 2196. (d) Claus, R. E.; Schreiber, S. L. Org. Synth. 1986, 64, 150. (e) Bosone, E.; Farina, P.; Guazzi, G.; Innocenti, S.; Marotta, V. Synthesis 1983, 942. (f) Schreiber, S. L.; Claus, R. E.; Reagan, J. Tetrahedron Lett. 1982, 23, 3867. (g) Buchi, G.; Wuest, H. Helv. Chim. Acta 1979, 62, 2661.
53. Interestingly, a GAS Sci-Finder search (May, 1998) on the synthesis of Me 6-oxohexanoate 9 revealed many (ca. 77 hits) literature and patent citations. We believe the method disclosed herein is very practical and in our hands has consistently provided good yields of pure material. Following is a listing of protocols which are complimentary to ours and would appear most suitable for laboratory scale preparation of this useful intermediate: (a) Hon, Y. S.; Yan, J. L. Tetrahedron 1997, 53, 5217. (b) Floresca, R.; Kurihara, M.; Watt, D. S.; Demir, A. J. Org. Chem. 1993, 58, 2196. (d) Claus, R. E.; Schreiber, S. L. Org. Synth. 1986, 64, 150. (e) Bosone, E.; Farina, P.; Guazzi, G.; Innocenti, S.; Marotta, V. Synthesis 1983, 942. (f) Schreiber, S. L.; Claus, R. E.; Reagan, J. Tetrahedron Lett. 1982, 23, 3867. (g) Buchi, G.; Wuest, H. Helv. Chim. Acta 1979, 62, 2661.
54. House, H. O.; Jones, V. K.; Frank, J. J. Org. Chem. 1964, 29, 3327.
55. (a) Mancuso, A. J.; Swern, D. Synthesis 1981, 165.
56. (b) Tidwell, T. T. Org. React. 1990, 39, 297.
57. Tidwell, T. T. Synthesis 1990, 857.
58. Miyakado, M.; Nakayama, I.; Inoue, A.; Hatakoshi, M.; Ohno, N. J. Pesticide Sci. Jpn. 1983, 10, (a) 11, (b) 25.
59. Miyakado, M.; Nakayama, I.; Inoue, A.; Hatakoshi, M.; Ohno, N. J. Pesticide Sci. Jpn. 1983, 10, (a) 11, (b) 25.