Toward a potential total synthesis of gelsemine: A regioselective hydroboration directed by a remote olefin

Tetrahedron Letters

Volumn 39, Issue 8, 1998, Pages 767-770

  Ng, Fay ^a   Chiu, Pauline ^a   Danishefsky, Samuel J ^a,b  

^a Och Spine at New York Presbyterian Hospitals   (United States)

^b MEMORIAL SLOAN KETTERING CANCER CENTER   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

ALKENE; GELSEMINE; OXETANE DERIVATIVE; UNCLASSIFIED DRUG;

ARTICLE; CONTROLLED STUDY; DRUG SYNTHESIS; HYDROBORATION; NONHUMAN; UNITED STATES;

EID: 0032546077     PISSN: 00404039     EISSN: None     Source Type: Journal    
DOI: 10.1016/S0040-4039(97)10621-9     Document Type: Article

References (27)

1. 1. Isolation: Saxton, J. E. The Alkaloids, 1965, 8, 93. Structure elucidation of gelsemine: (a) Lovell, F. M.; Pepinsky, R.; Wilson, A. J. C. Tetrahedron Lett. 1959, 4, 1.
2. 1. Isolation: Saxton, J. E. The Alkaloids, 1965, 8, 93. Structure elucidation of gelsemine: (a) Lovell, F. M.; Pepinsky, R.; Wilson, A. J. C. Tetrahedron Lett. 1959, 4, 1.
3. (b) Conroy, H.; Chakrabarti, J. K. ibid 1959, 6.
4. 2. Total syntheses of gelsemine: (a) Fukuyama, T.; Liu, G. J. Am. Chem. Soc. 1996, 118, 7426;
5. (b) Kuzmich, D.; Wu, S. C.; Ha, D.-C.; Lee, C.-S.; Ramesh, S.; Atarashi, S.; Choi, J.-K.; Hart, D. J. ibid. 1994, 116, 6943;
6. (c) Newcombe, N. J.; Ya, F.; Vijn, R. J.; Hiemstra, H.; Speckamp, W. N. J. Chem. Soc., Chem. Commun. 1994, 767;
7. (d) Sheikh, Z.; Steel, R.; Tasker, A. S.; Johnson, A. P. ibid. 1994, 763.
8. 3. Electronic directing effects in hydroboration: Regioselection due to the inductive effect of C-3 substituents on cyclopentenes and cyclohexenes: Brown, H. C.; Knights, E. F. J. Am. Chem. Soc. 1968, 90, 4439 and Pasto, D. J.; Hickman, J. ibid. 1968, 90, 4445. Regioselectivity in endo- and exo- heterocyclic olefins: Brown, H. C.; Rangaishenvi, M. V. J. Heterocyclic Chem. 1990, 27, 13. Regiodirection by an acetal group on hydroboration and oxymercuration of cis-bicyclo[3.3.0]octenone derivatives: Carceller, E.; Castello, A.; Garcia, M. L.; Moyano, A.; Serrtosa, F. Chem. Lett. 1984, 775. Silicon as a regiodirecting group in allylsilane derivatives: Fleming, I.; Lawrence, N. J. J. Chem. Soc. Perkin Trans. 1 1992, 3309, and Akers, J. A.; Bryson, T. A. Tetrahedron Lett. 1989, 30, 2187, and references cited therein.
9. 3. Electronic directing effects in hydroboration: Regioselection due to the inductive effect of C-3 substituents on cyclopentenes and cyclohexenes: Brown, H. C.; Knights, E. F. J. Am. Chem. Soc. 1968, 90, 4439 and Pasto, D. J.; Hickman, J. ibid. 1968, 90, 4445. Regioselectivity in endo- and exo- heterocyclic olefins: Brown, H. C.; Rangaishenvi, M. V. J. Heterocyclic Chem. 1990, 27, 13. Regiodirection by an acetal group on hydroboration and oxymercuration of cis-bicyclo[3.3.0]octenone derivatives: Carceller, E.; Castello, A.; Garcia, M. L.; Moyano, A.; Serrtosa, F. Chem. Lett. 1984, 775. Silicon as a regiodirecting group in allylsilane derivatives: Fleming, I.; Lawrence, N. J. J. Chem. Soc. Perkin Trans. 1 1992, 3309, and Akers, J. A.; Bryson, T. A. Tetrahedron Lett. 1989, 30, 2187, and references cited therein.
10. 3. Electronic directing effects in hydroboration: Regioselection due to the inductive effect of C-3 substituents on cyclopentenes and cyclohexenes: Brown, H. C.; Knights, E. F. J. Am. Chem. Soc. 1968, 90, 4439 and Pasto, D. J.; Hickman, J. ibid. 1968, 90, 4445. Regioselectivity in endo- and exo- heterocyclic olefins: Brown, H. C.; Rangaishenvi, M. V. J. Heterocyclic Chem. 1990, 27, 13. Regiodirection by an acetal group on hydroboration and oxymercuration of cis-bicyclo[3.3.0]octenone derivatives: Carceller, E.; Castello, A.; Garcia, M. L.; Moyano, A.; Serrtosa, F. Chem. Lett. 1984, 775. Silicon as a regiodirecting group in allylsilane derivatives: Fleming, I.; Lawrence, N. J. J. Chem. Soc. Perkin Trans. 1 1992, 3309, and Akers, J. A.; Bryson, T. A. Tetrahedron Lett. 1989, 30, 2187, and references cited therein.
11. 3. Electronic directing effects in hydroboration: Regioselection due to the inductive effect of C-3 substituents on cyclopentenes and cyclohexenes: Brown, H. C.; Knights, E. F. J. Am. Chem. Soc. 1968, 90, 4439 and Pasto, D. J.; Hickman, J. ibid. 1968, 90, 4445. Regioselectivity in endo- and exo- heterocyclic olefins: Brown, H. C.; Rangaishenvi, M. V. J. Heterocyclic Chem. 1990, 27, 13. Regiodirection by an acetal group on hydroboration and oxymercuration of cis-bicyclo[3.3.0]octenone derivatives: Carceller, E.; Castello, A.; Garcia, M. L.; Moyano, A.; Serrtosa, F. Chem. Lett. 1984, 775. Silicon as a regiodirecting group in allylsilane derivatives: Fleming, I.; Lawrence, N. J. J. Chem. Soc. Perkin Trans. 1 1992, 3309, and Akers, J. A.; Bryson, T. A. Tetrahedron Lett. 1989, 30, 2187, and references cited therein.
12. 3. Electronic directing effects in hydroboration: Regioselection due to the inductive effect of C-3 substituents on cyclopentenes and cyclohexenes: Brown, H. C.; Knights, E. F. J. Am. Chem. Soc. 1968, 90, 4439 and Pasto, D. J.; Hickman, J. ibid. 1968, 90, 4445. Regioselectivity in endo- and exo- heterocyclic olefins: Brown, H. C.; Rangaishenvi, M. V. J. Heterocyclic Chem. 1990, 27, 13. Regiodirection by an acetal group on hydroboration and oxymercuration of cis-bicyclo[3.3.0]octenone derivatives: Carceller, E.; Castello, A.; Garcia, M. L.; Moyano, A.; Serrtosa, F. Chem. Lett. 1984, 775. Silicon as a regiodirecting group in allylsilane derivatives: Fleming, I.; Lawrence, N. J. J. Chem. Soc. Perkin Trans. 1 1992, 3309, and Akers, J. A.; Bryson, T. A. Tetrahedron Lett. 1989, 30, 2187, and references cited therein.
13. 3. Electronic directing effects in hydroboration: Regioselection due to the inductive effect of C-3 substituents on cyclopentenes and cyclohexenes: Brown, H. C.; Knights, E. F. J. Am. Chem. Soc. 1968, 90, 4439 and Pasto, D. J.; Hickman, J. ibid. 1968, 90, 4445. Regioselectivity in endo- and exo- heterocyclic olefins: Brown, H. C.; Rangaishenvi, M. V. J. Heterocyclic Chem. 1990, 27, 13. Regiodirection by an acetal group on hydroboration and oxymercuration of cis-bicyclo[3.3.0]octenone derivatives: Carceller, E.; Castello, A.; Garcia, M. L.; Moyano, A.; Serrtosa, F. Chem. Lett. 1984, 775. Silicon as a regiodirecting group in allylsilane derivatives: Fleming, I.; Lawrence, N. J. J. Chem. Soc. Perkin Trans. 1 1992, 3309, and Akers, J. A.; Bryson, T. A. Tetrahedron Lett. 1989, 30, 2187, and references cited therein.
14. 4. Cupas, C.; Watts, W. E.; Schleyer, P. von R. Tetrahedron Lett. 1964, 2503.
15. 5. Klumpp, G. W.; Barnick, J. W. F. K.; Veefkind, A. H.; Bickelhaupt, F. Recl. Trav. Chim. Pays-Bas 1969, 88, 766.
16. 6. Arbuzou product of o-nitrobenzylbromide: (a): LeCorne, M.; Hercouet, A.; LeStanc, Y.; LeBaron, H. Tetrahedron 1985, 41, 5313;
17. (b) Intermediate 5 was isolated and subjected to sealed tube thermalysis (150°C) in toluene to give compound 5. Intermediate 6 was not isolated and the 1,2-divinylcyclopropane rearrangement occurred at rt to give compound 6. For a review of 1,2-divinylcyclopropane rearrangement: Hudlicky, T.; Fan, R.; Reed, J. W.; Gadamasetti, K. G. Org. React. 1992, 41, 1.
18. 7. Sakai, M. Tetrahedron Lett. 1973, 347.
19. 8. Brown, H. C. in Hydroboration W. A. Benajamin, Inc., New York, 1962.
20. 9. Hydroboration of 3-methylcyclopentene, 3-methylcyclohexene, and 3,3-dimethylcyclohexene was non-regioselective: Brown, H. C.; Zweifel, G. J. Am. Chem. Soc. 1961, 83, 2544.
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24. 13. The structure of 11 was secured via a X-ray crystallographic analysis of an oxetane intermediate synthesized from 11, the synthesis of which will be reported in due course.
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27. 2 at -78° followed by silylation of the resultant alcohol with TBDPSCl, DMF, and imidazole.