Exploiting the palladium[0]-catalysed Ullmann cross-coupling reaction in natural products chemistry: Application to a total synthesis of the alkaloid (±)-aspidospermidine

Organic and Biomolecular Chemistry

Volumn 3, Issue 2, 2005, Pages 213-215

  Banwell, Martin G ^a   Lupton, David W ^a  

^a AUSTRALIAN NATIONAL UNIVERSITY   (Australia)

Author keywords

[No Author keywords available]

Indexed keywords

ALCOHOLS; CATALYSIS; HYDROLYSIS; MIXTURES; REDUCTION; SYNTHESIS (CHEMICAL);

ALLYLIC ALCOHOLS; CROSS-COUPLING REACTIONS; HYDROCHLORIDE SALTS;

AROMATIC COMPOUNDS;

EID: 12844255830     PISSN: 14770520     EISSN: None     Source Type: Journal    
DOI: 10.1039/b415977b     Document Type: Article

References (42)

1. M. G. Banwell, B. D. Kelly, O. J. Kokas and D. W. Lupton, Org. Lett., 2003, 5, 2497.
2. Analogous protocols utilising β-halo-enones or -enals have been applied to the preparation of quinolincs; M. G. Banwell, D. W. Lupton, X. Ma, J. Renner and M. O. Sydnes, Org. Lett., 2004, 6, 2741.
3. Antitumor Bisindole Alkaloids from Catharanthus roseus (L.), The Alkaloids, Vol. 37, ed. A. Brossi and M. Suffness, Academic Press, San Diego, CA, 1990.
4. (a) S. Yokoshima, T. Ueda, S. Kobayashi, A. Sato, T. Kuboyama, H. Tokuyama and T. Fukuyama, J. Am. Chem. Soc., 2002, 124, 2137; for useful reviews see;
5. (b) S. Yokoshima, T. Ueda, S. Kobayashi, A. Sato, T. Kuboyama, H. Tokuyama and T. Fukuyama, Pure Appl. Chem., 2003, 75, 29; (c) C. Schneider, Angew. Chem., Int. Ed., 2002, 41, 4217.
6. (b) S. Yokoshima, T. Ueda, S. Kobayashi, A. Sato, T. Kuboyama, H. Tokuyama and T. Fukuyama, Pure Appl. Chem., 2003, 75, 29; (c) C. Schneider, Angew. Chem., Int. Ed., 2002, 41, 4217.
7. M. G. Banwell, A. J. Edwards, D. W. Lupton and G. Whited, Aust. J. Chem., in press.
8. For previously reported total syntheses of aspidospermidine see; (a) G. Stork and J. E. Dolfini, J. Am. Chem. Soc., 1963, 85, 2872; (b) A. Camerman, N. Camerman, J. P. Kutney, E. Piers and J. Trotter, Tetrahedron Lett., 1965, 637; (c) J. Harley-Mason and M. Kaplan, J. Chem. Soc., Chem. Commun., 1967, 915; (d)J.-Y. Laronze, J. Laronze-Fontaine, J. Lévy and J. Le Men, Tetrahedron Lett., 1974, 491; (e) Y. Ban, K. Yoshida, J. Goto and T. Oishi, J. Am. Chem. Soc., 1981, 103, 6990; (f) T. Gallagher, P. Magnus and J. Huffman, J. Am. Chem. Soc., 1982, 104, 1140; (g) E. Wenkert and T. Hudlicky, J. Org. Chem., 1988, 53, 1953; (h) S. B. Mandal, Y S. Giri, M. S. Sabeena and S. C. Pakrashi, J. Org. Chem., 1988, 53, 4236; (i) A. I. Myers and D. Berney, J. Org. Chem., 1989, 54, 4673; (j) M. Node, H. Nagasawa and K. Fuji, J. Org. Chem., 1990, 55, 517; (k) P. Le Menez, N. Kunesch, S. Liu and E. Wenkert, J. Org. Chem., 1991, 56, 2915; (l) D. Desmaële and J. d'Angelo, J. Org. Chem., 1994, 59, 2292; (m) E. Wenkert and S. Liu, J. Org. Chem., 1994, 59, 7677; (n) P. Forns, A. Diez and M. Rubiralta, J. Org. Chem., 1996, 61, 7882; (o) A. G. Schultz and L. Pettus, J. Org. Chem., 1997, 62, 6855; (p) O. Callaghan, C. Lampard, A. R. Kennedy and J. A. Murphy, J. Chem. Soc., Perkin Trans. 1, 1999, 995; (q) R. Iyengar, K. Schildknegt and J. Aubé, Org. Lett., 2000, 2, 1625; (r) M. A. Toczko and C. H. Heathcock, J. Org. Chem., 2000, 65, 2642; (s) B. Patro and J. A. Murphy, Org. Lett., 2000, 2, 3599; (t) S. A. Kozmin, T. Iwama, Y. Huang and V H. Rawal, J. Am. Chem. Soc., 2002, 124, 4628; (u) M. G. Banwell and J. A. Smith, J. Chem. Sac., Perkin Trans. 1, 2002, 2613; (v) J. P. Marino, M. B. Rubio, G. Cao and A. de Dios, J. Am. Chem. Soc., 2002, 124, 13398; (w) D. Gnecco, E. Vázquez, A. Galindo, J. L. Terán, L. Orea, S. Bernès and R. G. Enríquez, ARKIVOC, 2003, xi, 185; (x) H. Tanino, K. Fukuishi, M. Ushiyama and K. Okada, Tetrahedron, 2004, 60, 3273.
9. For previously reported total syntheses of aspidospermidine see; (a) G. Stork and J. E. Dolfini, J. Am. Chem. Soc., 1963, 85, 2872; (b) A. Camerman, N. Camerman, J. P. Kutney, E. Piers and J. Trotter, Tetrahedron Lett., 1965, 637; (c) J. Harley-Mason and M. Kaplan, J. Chem. Soc., Chem. Commun., 1967, 915; (d)J.-Y. Laronze, J. Laronze-Fontaine, J. Lévy and J. Le Men, Tetrahedron Lett., 1974, 491; (e) Y. Ban, K. Yoshida, J. Goto and T. Oishi, J. Am. Chem. Soc., 1981, 103, 6990; (f) T. Gallagher, P. Magnus and J. Huffman, J. Am. Chem. Soc., 1982, 104, 1140; (g) E. Wenkert and T. Hudlicky, J. Org. Chem., 1988, 53, 1953; (h) S. B. Mandal, Y S. Giri, M. S. Sabeena and S. C. Pakrashi, J. Org. Chem., 1988, 53, 4236; (i) A. I. Myers and D. Berney, J. Org. Chem., 1989, 54, 4673; (j) M. Node, H. Nagasawa and K. Fuji, J. Org. Chem., 1990, 55, 517; (k) P. Le Menez, N. Kunesch, S. Liu and E. Wenkert, J. Org. Chem., 1991, 56, 2915; (l) D. Desmaële and J. d'Angelo, J. Org. Chem., 1994, 59, 2292; (m) E. Wenkert and S. Liu, J. Org. Chem., 1994, 59, 7677; (n) P. Forns, A. Diez and M. Rubiralta, J. Org. Chem., 1996, 61, 7882; (o) A. G. Schultz and L. Pettus, J. Org. Chem., 1997, 62, 6855; (p) O. Callaghan, C. Lampard, A. R. Kennedy and J. A. Murphy, J. Chem. Soc., Perkin Trans. 1, 1999, 995; (q) R. Iyengar, K. Schildknegt and J. Aubé, Org. Lett., 2000, 2, 1625; (r) M. A. Toczko and C. H. Heathcock, J. Org. Chem., 2000, 65, 2642; (s) B. Patro and J. A. Murphy, Org. Lett., 2000, 2, 3599; (t) S. A. Kozmin, T. Iwama, Y. Huang and V H. Rawal, J. Am. Chem. Soc., 2002, 124, 4628; (u) M. G. Banwell and J. A. Smith, J. Chem. Sac., Perkin Trans. 1, 2002, 2613; (v) J. P. Marino, M. B. Rubio, G. Cao and A. de Dios, J. Am. Chem. Soc., 2002, 124, 13398; (w) D. Gnecco, E. Vázquez, A. Galindo, J. L. Terán, L. Orea, S. Bernès and R. G. Enríquez, ARKIVOC, 2003, xi, 185; (x) H. Tanino, K. Fukuishi, M. Ushiyama and K. Okada, Tetrahedron, 2004, 60, 3273.
10. For previously reported total syntheses of aspidospermidine see; (a) G. Stork and J. E. Dolfini, J. Am. Chem. Soc., 1963, 85, 2872; (b) A. Camerman, N. Camerman, J. P. Kutney, E. Piers and J. Trotter, Tetrahedron Lett., 1965, 637; (c) J. Harley-Mason and M. Kaplan, J. Chem. Soc., Chem. Commun., 1967, 915; (d)J.-Y. Laronze, J. Laronze-Fontaine, J. Lévy and J. Le Men, Tetrahedron Lett., 1974, 491; (e) Y. Ban, K. Yoshida, J. Goto and T. Oishi, J. Am. Chem. Soc., 1981, 103, 6990; (f) T. Gallagher, P. Magnus and J. Huffman, J. Am. Chem. Soc., 1982, 104, 1140; (g) E. Wenkert and T. Hudlicky, J. Org. Chem., 1988, 53, 1953; (h) S. B. Mandal, Y S. Giri, M. S. Sabeena and S. C. Pakrashi, J. Org. Chem., 1988, 53, 4236; (i) A. I. Myers and D. Berney, J. Org. Chem., 1989, 54, 4673; (j) M. Node, H. Nagasawa and K. Fuji, J. Org. Chem., 1990, 55, 517; (k) P. Le Menez, N. Kunesch, S. Liu and E. Wenkert, J. Org. Chem., 1991, 56, 2915; (l) D. Desmaële and J. d'Angelo, J. Org. Chem., 1994, 59, 2292; (m) E. Wenkert and S. Liu, J. Org. Chem., 1994, 59, 7677; (n) P. Forns, A. Diez and M. Rubiralta, J. Org. Chem., 1996, 61, 7882; (o) A. G. Schultz and L. Pettus, J. Org. Chem., 1997, 62, 6855; (p) O. Callaghan, C. Lampard, A. R. Kennedy and J. A. Murphy, J. Chem. Soc., Perkin Trans. 1, 1999, 995; (q) R. Iyengar, K. Schildknegt and J. Aubé, Org. Lett., 2000, 2, 1625; (r) M. A. Toczko and C. H. Heathcock, J. Org. Chem., 2000, 65, 2642; (s) B. Patro and J. A. Murphy, Org. Lett., 2000, 2, 3599; (t) S. A. Kozmin, T. Iwama, Y. Huang and V H. Rawal, J. Am. Chem. Soc., 2002, 124, 4628; (u) M. G. Banwell and J. A. Smith, J. Chem. Sac., Perkin Trans. 1, 2002, 2613; (v) J. P. Marino, M. B. Rubio, G. Cao and A. de Dios, J. Am. Chem. Soc., 2002, 124, 13398; (w) D. Gnecco, E. Vázquez, A. Galindo, J. L. Terán, L. Orea, S. Bernès and R. G. Enríquez, ARKIVOC, 2003, xi, 185; (x) H. Tanino, K. Fukuishi, M. Ushiyama and K. Okada, Tetrahedron, 2004, 60, 3273.
11. For previously reported total syntheses of aspidospermidine see; (a) G. Stork and J. E. Dolfini, J. Am. Chem. Soc., 1963, 85, 2872; (b) A. Camerman, N. Camerman, J. P. Kutney, E. Piers and J. Trotter, Tetrahedron Lett., 1965, 637; (c) J. Harley-Mason and M. Kaplan, J. Chem. Soc., Chem. Commun., 1967, 915; (d)J.-Y. Laronze, J. Laronze-Fontaine, J. Lévy and J. Le Men, Tetrahedron Lett., 1974, 491; (e) Y. Ban, K. Yoshida, J. Goto and T. Oishi, J. Am. Chem. Soc., 1981, 103, 6990; (f) T. Gallagher, P. Magnus and J. Huffman, J. Am. Chem. Soc., 1982, 104, 1140; (g) E. Wenkert and T. Hudlicky, J. Org. Chem., 1988, 53, 1953; (h) S. B. Mandal, Y S. Giri, M. S. Sabeena and S. C. Pakrashi, J. Org. Chem., 1988, 53, 4236; (i) A. I. Myers and D. Berney, J. Org. Chem., 1989, 54, 4673; (j) M. Node, H. Nagasawa and K. Fuji, J. Org. Chem., 1990, 55, 517; (k) P. Le Menez, N. Kunesch, S. Liu and E. Wenkert, J. Org. Chem., 1991, 56, 2915; (l) D. Desmaële and J. d'Angelo, J. Org. Chem., 1994, 59, 2292; (m) E. Wenkert and S. Liu, J. Org. Chem., 1994, 59, 7677; (n) P. Forns, A. Diez and M. Rubiralta, J. Org. Chem., 1996, 61, 7882; (o) A. G. Schultz and L. Pettus, J. Org. Chem., 1997, 62, 6855; (p) O. Callaghan, C. Lampard, A. R. Kennedy and J. A. Murphy, J. Chem. Soc., Perkin Trans. 1, 1999, 995; (q) R. Iyengar, K. Schildknegt and J. Aubé, Org. Lett., 2000, 2, 1625; (r) M. A. Toczko and C. H. Heathcock, J. Org. Chem., 2000, 65, 2642; (s) B. Patro and J. A. Murphy, Org. Lett., 2000, 2, 3599; (t) S. A. Kozmin, T. Iwama, Y. Huang and V H. Rawal, J. Am. Chem. Soc., 2002, 124, 4628; (u) M. G. Banwell and J. A. Smith, J. Chem. Sac., Perkin Trans. 1, 2002, 2613; (v) J. P. Marino, M. B. Rubio, G. Cao and A. de Dios, J. Am. Chem. Soc., 2002, 124, 13398; (w) D. Gnecco, E. Vázquez, A. Galindo, J. L. Terán, L. Orea, S. Bernès and R. G. Enríquez, ARKIVOC, 2003, xi, 185; (x) H. Tanino, K. Fukuishi, M. Ushiyama and K. Okada, Tetrahedron, 2004, 60, 3273.
12. For previously reported total syntheses of aspidospermidine see; (a) G. Stork and J. E. Dolfini, J. Am. Chem. Soc., 1963, 85, 2872; (b) A. Camerman, N. Camerman, J. P. Kutney, E. Piers and J. Trotter, Tetrahedron Lett., 1965, 637; (c) J. Harley-Mason and M. Kaplan, J. Chem. Soc., Chem. Commun., 1967, 915; (d)J.-Y. Laronze, J. Laronze-Fontaine, J. Lévy and J. Le Men, Tetrahedron Lett., 1974, 491; (e) Y. Ban, K. Yoshida, J. Goto and T. Oishi, J. Am. Chem. Soc., 1981, 103, 6990; (f) T. Gallagher, P. Magnus and J. Huffman, J. Am. Chem. Soc., 1982, 104, 1140; (g) E. Wenkert and T. Hudlicky, J. Org. Chem., 1988, 53, 1953; (h) S. B. Mandal, Y S. Giri, M. S. Sabeena and S. C. Pakrashi, J. Org. Chem., 1988, 53, 4236; (i) A. I. Myers and D. Berney, J. Org. Chem., 1989, 54, 4673; (j) M. Node, H. Nagasawa and K. Fuji, J. Org. Chem., 1990, 55, 517; (k) P. Le Menez, N. Kunesch, S. Liu and E. Wenkert, J. Org. Chem., 1991, 56, 2915; (l) D. Desmaële and J. d'Angelo, J. Org. Chem., 1994, 59, 2292; (m) E. Wenkert and S. Liu, J. Org. Chem., 1994, 59, 7677; (n) P. Forns, A. Diez and M. Rubiralta, J. Org. Chem., 1996, 61, 7882; (o) A. G. Schultz and L. Pettus, J. Org. Chem., 1997, 62, 6855; (p) O. Callaghan, C. Lampard, A. R. Kennedy and J. A. Murphy, J. Chem. Soc., Perkin Trans. 1, 1999, 995; (q) R. Iyengar, K. Schildknegt and J. Aubé, Org. Lett., 2000, 2, 1625; (r) M. A. Toczko and C. H. Heathcock, J. Org. Chem., 2000, 65, 2642; (s) B. Patro and J. A. Murphy, Org. Lett., 2000, 2, 3599; (t) S. A. Kozmin, T. Iwama, Y. Huang and V H. Rawal, J. Am. Chem. Soc., 2002, 124, 4628; (u) M. G. Banwell and J. A. Smith, J. Chem. Sac., Perkin Trans. 1, 2002, 2613; (v) J. P. Marino, M. B. Rubio, G. Cao and A. de Dios, J. Am. Chem. Soc., 2002, 124, 13398; (w) D. Gnecco, E. Vázquez, A. Galindo, J. L. Terán, L. Orea, S. Bernès and R. G. Enríquez, ARKIVOC, 2003, xi, 185; (x) H. Tanino, K. Fukuishi, M. Ushiyama and K. Okada, Tetrahedron, 2004, 60, 3273.
13. For previously reported total syntheses of aspidospermidine see; (a) G. Stork and J. E. Dolfini, J. Am. Chem. Soc., 1963, 85, 2872; (b) A. Camerman, N. Camerman, J. P. Kutney, E. Piers and J. Trotter, Tetrahedron Lett., 1965, 637; (c) J. Harley-Mason and M. Kaplan, J. Chem. Soc., Chem. Commun., 1967, 915; (d)J.-Y. Laronze, J. Laronze-Fontaine, J. Lévy and J. Le Men, Tetrahedron Lett., 1974, 491; (e) Y. Ban, K. Yoshida, J. Goto and T. Oishi, J. Am. Chem. Soc., 1981, 103, 6990; (f) T. Gallagher, P. Magnus and J. Huffman, J. Am. Chem. Soc., 1982, 104, 1140; (g) E. Wenkert and T. Hudlicky, J. Org. Chem., 1988, 53, 1953; (h) S. B. Mandal, Y S. Giri, M. S. Sabeena and S. C. Pakrashi, J. Org. Chem., 1988, 53, 4236; (i) A. I. Myers and D. Berney, J. Org. Chem., 1989, 54, 4673; (j) M. Node, H. Nagasawa and K. Fuji, J. Org. Chem., 1990, 55, 517; (k) P. Le Menez, N. Kunesch, S. Liu and E. Wenkert, J. Org. Chem., 1991, 56, 2915; (l) D. Desmaële and J. d'Angelo, J. Org. Chem., 1994, 59, 2292; (m) E. Wenkert and S. Liu, J. Org. Chem., 1994, 59, 7677; (n) P. Forns, A. Diez and M. Rubiralta, J. Org. Chem., 1996, 61, 7882; (o) A. G. Schultz and L. Pettus, J. Org. Chem., 1997, 62, 6855; (p) O. Callaghan, C. Lampard, A. R. Kennedy and J. A. Murphy, J. Chem. Soc., Perkin Trans. 1, 1999, 995; (q) R. Iyengar, K. Schildknegt and J. Aubé, Org. Lett., 2000, 2, 1625; (r) M. A. Toczko and C. H. Heathcock, J. Org. Chem., 2000, 65, 2642; (s) B. Patro and J. A. Murphy, Org. Lett., 2000, 2, 3599; (t) S. A. Kozmin, T. Iwama, Y. Huang and V H. Rawal, J. Am. Chem. Soc., 2002, 124, 4628; (u) M. G. Banwell and J. A. Smith, J. Chem. Sac., Perkin Trans. 1, 2002, 2613; (v) J. P. Marino, M. B. Rubio, G. Cao and A. de Dios, J. Am. Chem. Soc., 2002, 124, 13398; (w) D. Gnecco, E. Vázquez, A. Galindo, J. L. Terán, L. Orea, S. Bernès and R. G. Enríquez, ARKIVOC, 2003, xi, 185; (x) H. Tanino, K. Fukuishi, M. Ushiyama and K. Okada, Tetrahedron, 2004, 60, 3273.
14. For previously reported total syntheses of aspidospermidine see; (a) G. Stork and J. E. Dolfini, J. Am. Chem. Soc., 1963, 85, 2872; (b) A. Camerman, N. Camerman, J. P. Kutney, E. Piers and J. Trotter, Tetrahedron Lett., 1965, 637; (c) J. Harley-Mason and M. Kaplan, J. Chem. Soc., Chem. Commun., 1967, 915; (d)J.-Y. Laronze, J. Laronze-Fontaine, J. Lévy and J. Le Men, Tetrahedron Lett., 1974, 491; (e) Y. Ban, K. Yoshida, J. Goto and T. Oishi, J. Am. Chem. Soc., 1981, 103, 6990; (f) T. Gallagher, P. Magnus and J. Huffman, J. Am. Chem. Soc., 1982, 104, 1140; (g) E. Wenkert and T. Hudlicky, J. Org. Chem., 1988, 53, 1953; (h) S. B. Mandal, Y S. Giri, M. S. Sabeena and S. C. Pakrashi, J. Org. Chem., 1988, 53, 4236; (i) A. I. Myers and D. Berney, J. Org. Chem., 1989, 54, 4673; (j) M. Node, H. Nagasawa and K. Fuji, J. Org. Chem., 1990, 55, 517; (k) P. Le Menez, N. Kunesch, S. Liu and E. Wenkert, J. Org. Chem., 1991, 56, 2915; (l) D. Desmaële and J. d'Angelo, J. Org. Chem., 1994, 59, 2292; (m) E. Wenkert and S. Liu, J. Org. Chem., 1994, 59, 7677; (n) P. Forns, A. Diez and M. Rubiralta, J. Org. Chem., 1996, 61, 7882; (o) A. G. Schultz and L. Pettus, J. Org. Chem., 1997, 62, 6855; (p) O. Callaghan, C. Lampard, A. R. Kennedy and J. A. Murphy, J. Chem. Soc., Perkin Trans. 1, 1999, 995; (q) R. Iyengar, K. Schildknegt and J. Aubé, Org. Lett., 2000, 2, 1625; (r) M. A. Toczko and C. H. Heathcock, J. Org. Chem., 2000, 65, 2642; (s) B. Patro and J. A. Murphy, Org. Lett., 2000, 2, 3599; (t) S. A. Kozmin, T. Iwama, Y. Huang and V H. Rawal, J. Am. Chem. Soc., 2002, 124, 4628; (u) M. G. Banwell and J. A. Smith, J. Chem. Sac., Perkin Trans. 1, 2002, 2613; (v) J. P. Marino, M. B. Rubio, G. Cao and A. de Dios, J. Am. Chem. Soc., 2002, 124, 13398; (w) D. Gnecco, E. Vázquez, A. Galindo, J. L. Terán, L. Orea, S. Bernès and R. G. Enríquez, ARKIVOC, 2003, xi, 185; (x) H. Tanino, K. Fukuishi, M. Ushiyama and K. Okada, Tetrahedron, 2004, 60, 3273.
15. For previously reported total syntheses of aspidospermidine see; (a) G. Stork and J. E. Dolfini, J. Am. Chem. Soc., 1963, 85, 2872; (b) A. Camerman, N. Camerman, J. P. Kutney, E. Piers and J. Trotter, Tetrahedron Lett., 1965, 637; (c) J. Harley-Mason and M. Kaplan, J. Chem. Soc., Chem. Commun., 1967, 915; (d)J.-Y. Laronze, J. Laronze-Fontaine, J. Lévy and J. Le Men, Tetrahedron Lett., 1974, 491; (e) Y. Ban, K. Yoshida, J. Goto and T. Oishi, J. Am. Chem. Soc., 1981, 103, 6990; (f) T. Gallagher, P. Magnus and J. Huffman, J. Am. Chem. Soc., 1982, 104, 1140; (g) E. Wenkert and T. Hudlicky, J. Org. Chem., 1988, 53, 1953; (h) S. B. Mandal, Y S. Giri, M. S. Sabeena and S. C. Pakrashi, J. Org. Chem., 1988, 53, 4236; (i) A. I. Myers and D. Berney, J. Org. Chem., 1989, 54, 4673; (j) M. Node, H. Nagasawa and K. Fuji, J. Org. Chem., 1990, 55, 517; (k) P. Le Menez, N. Kunesch, S. Liu and E. Wenkert, J. Org. Chem., 1991, 56, 2915; (l) D. Desmaële and J. d'Angelo, J. Org. Chem., 1994, 59, 2292; (m) E. Wenkert and S. Liu, J. Org. Chem., 1994, 59, 7677; (n) P. Forns, A. Diez and M. Rubiralta, J. Org. Chem., 1996, 61, 7882; (o) A. G. Schultz and L. Pettus, J. Org. Chem., 1997, 62, 6855; (p) O. Callaghan, C. Lampard, A. R. Kennedy and J. A. Murphy, J. Chem. Soc., Perkin Trans. 1, 1999, 995; (q) R. Iyengar, K. Schildknegt and J. Aubé, Org. Lett., 2000, 2, 1625; (r) M. A. Toczko and C. H. Heathcock, J. Org. Chem., 2000, 65, 2642; (s) B. Patro and J. A. Murphy, Org. Lett., 2000, 2, 3599; (t) S. A. Kozmin, T. Iwama, Y. Huang and V H. Rawal, J. Am. Chem. Soc., 2002, 124, 4628; (u) M. G. Banwell and J. A. Smith, J. Chem. Sac., Perkin Trans. 1, 2002, 2613; (v) J. P. Marino, M. B. Rubio, G. Cao and A. de Dios, J. Am. Chem. Soc., 2002, 124, 13398; (w) D. Gnecco, E. Vázquez, A. Galindo, J. L. Terán, L. Orea, S. Bernès and R. G. Enríquez, ARKIVOC, 2003, xi, 185; (x) H. Tanino, K. Fukuishi, M. Ushiyama and K. Okada, Tetrahedron, 2004, 60, 3273.
16. For previously reported total syntheses of aspidospermidine see; (a) G. Stork and J. E. Dolfini, J. Am. Chem. Soc., 1963, 85, 2872; (b) A. Camerman, N. Camerman, J. P. Kutney, E. Piers and J. Trotter, Tetrahedron Lett., 1965, 637; (c) J. Harley-Mason and M. Kaplan, J. Chem. Soc., Chem. Commun., 1967, 915; (d)J.-Y. Laronze, J. Laronze-Fontaine, J. Lévy and J. Le Men, Tetrahedron Lett., 1974, 491; (e) Y. Ban, K. Yoshida, J. Goto and T. Oishi, J. Am. Chem. Soc., 1981, 103, 6990; (f) T. Gallagher, P. Magnus and J. Huffman, J. Am. Chem. Soc., 1982, 104, 1140; (g) E. Wenkert and T. Hudlicky, J. Org. Chem., 1988, 53, 1953; (h) S. B. Mandal, Y S. Giri, M. S. Sabeena and S. C. Pakrashi, J. Org. Chem., 1988, 53, 4236; (i) A. I. Myers and D. Berney, J. Org. Chem., 1989, 54, 4673; (j) M. Node, H. Nagasawa and K. Fuji, J. Org. Chem., 1990, 55, 517; (k) P. Le Menez, N. Kunesch, S. Liu and E. Wenkert, J. Org. Chem., 1991, 56, 2915; (l) D. Desmaële and J. d'Angelo, J. Org. Chem., 1994, 59, 2292; (m) E. Wenkert and S. Liu, J. Org. Chem., 1994, 59, 7677; (n) P. Forns, A. Diez and M. Rubiralta, J. Org. Chem., 1996, 61, 7882; (o) A. G. Schultz and L. Pettus, J. Org. Chem., 1997, 62, 6855; (p) O. Callaghan, C. Lampard, A. R. Kennedy and J. A. Murphy, J. Chem. Soc., Perkin Trans. 1, 1999, 995; (q) R. Iyengar, K. Schildknegt and J. Aubé, Org. Lett., 2000, 2, 1625; (r) M. A. Toczko and C. H. Heathcock, J. Org. Chem., 2000, 65, 2642; (s) B. Patro and J. A. Murphy, Org. Lett., 2000, 2, 3599; (t) S. A. Kozmin, T. Iwama, Y. Huang and V H. Rawal, J. Am. Chem. Soc., 2002, 124, 4628; (u) M. G. Banwell and J. A. Smith, J. Chem. Sac., Perkin Trans. 1, 2002, 2613; (v) J. P. Marino, M. B. Rubio, G. Cao and A. de Dios, J. Am. Chem. Soc., 2002, 124, 13398; (w) D. Gnecco, E. Vázquez, A. Galindo, J. L. Terán, L. Orea, S. Bernès and R. G. Enríquez, ARKIVOC, 2003, xi, 185; (x) H. Tanino, K. Fukuishi, M. Ushiyama and K. Okada, Tetrahedron, 2004, 60, 3273.
17. For previously reported total syntheses of aspidospermidine see; (a) G. Stork and J. E. Dolfini, J. Am. Chem. Soc., 1963, 85, 2872; (b) A. Camerman, N. Camerman, J. P. Kutney, E. Piers and J. Trotter, Tetrahedron Lett., 1965, 637; (c) J. Harley-Mason and M. Kaplan, J. Chem. Soc., Chem. Commun., 1967, 915; (d)J.-Y. Laronze, J. Laronze-Fontaine, J. Lévy and J. Le Men, Tetrahedron Lett., 1974, 491; (e) Y. Ban, K. Yoshida, J. Goto and T. Oishi, J. Am. Chem. Soc., 1981, 103, 6990; (f) T. Gallagher, P. Magnus and J. Huffman, J. Am. Chem. Soc., 1982, 104, 1140; (g) E. Wenkert and T. Hudlicky, J. Org. Chem., 1988, 53, 1953; (h) S. B. Mandal, Y S. Giri, M. S. Sabeena and S. C. Pakrashi, J. Org. Chem., 1988, 53, 4236; (i) A. I. Myers and D. Berney, J. Org. Chem., 1989, 54, 4673; (j) M. Node, H. Nagasawa and K. Fuji, J. Org. Chem., 1990, 55, 517; (k) P. Le Menez, N. Kunesch, S. Liu and E. Wenkert, J. Org. Chem., 1991, 56, 2915; (l) D. Desmaële and J. d'Angelo, J. Org. Chem., 1994, 59, 2292; (m) E. Wenkert and S. Liu, J. Org. Chem., 1994, 59, 7677; (n) P. Forns, A. Diez and M. Rubiralta, J. Org. Chem., 1996, 61, 7882; (o) A. G. Schultz and L. Pettus, J. Org. Chem., 1997, 62, 6855; (p) O. Callaghan, C. Lampard, A. R. Kennedy and J. A. Murphy, J. Chem. Soc., Perkin Trans. 1, 1999, 995; (q) R. Iyengar, K. Schildknegt and J. Aubé, Org. Lett., 2000, 2, 1625; (r) M. A. Toczko and C. H. Heathcock, J. Org. Chem., 2000, 65, 2642; (s) B. Patro and J. A. Murphy, Org. Lett., 2000, 2, 3599; (t) S. A. Kozmin, T. Iwama, Y. Huang and V H. Rawal, J. Am. Chem. Soc., 2002, 124, 4628; (u) M. G. Banwell and J. A. Smith, J. Chem. Sac., Perkin Trans. 1, 2002, 2613; (v) J. P. Marino, M. B. Rubio, G. Cao and A. de Dios, J. Am. Chem. Soc., 2002, 124, 13398; (w) D. Gnecco, E. Vázquez, A. Galindo, J. L. Terán, L. Orea, S. Bernès and R. G. Enríquez, ARKIVOC, 2003, xi, 185; (x) H. Tanino, K. Fukuishi, M. Ushiyama and K. Okada, Tetrahedron, 2004, 60, 3273.
18. For previously reported total syntheses of aspidospermidine see; (a) G. Stork and J. E. Dolfini, J. Am. Chem. Soc., 1963, 85, 2872; (b) A. Camerman, N. Camerman, J. P. Kutney, E. Piers and J. Trotter, Tetrahedron Lett., 1965, 637; (c) J. Harley-Mason and M. Kaplan, J. Chem. Soc., Chem. Commun., 1967, 915; (d)J.-Y. Laronze, J. Laronze-Fontaine, J. Lévy and J. Le Men, Tetrahedron Lett., 1974, 491; (e) Y. Ban, K. Yoshida, J. Goto and T. Oishi, J. Am. Chem. Soc., 1981, 103, 6990; (f) T. Gallagher, P. Magnus and J. Huffman, J. Am. Chem. Soc., 1982, 104, 1140; (g) E. Wenkert and T. Hudlicky, J. Org. Chem., 1988, 53, 1953; (h) S. B. Mandal, Y S. Giri, M. S. Sabeena and S. C. Pakrashi, J. Org. Chem., 1988, 53, 4236; (i) A. I. Myers and D. Berney, J. Org. Chem., 1989, 54, 4673; (j) M. Node, H. Nagasawa and K. Fuji, J. Org. Chem., 1990, 55, 517; (k) P. Le Menez, N. Kunesch, S. Liu and E. Wenkert, J. Org. Chem., 1991, 56, 2915; (l) D. Desmaële and J. d'Angelo, J. Org. Chem., 1994, 59, 2292; (m) E. Wenkert and S. Liu, J. Org. Chem., 1994, 59, 7677; (n) P. Forns, A. Diez and M. Rubiralta, J. Org. Chem., 1996, 61, 7882; (o) A. G. Schultz and L. Pettus, J. Org. Chem., 1997, 62, 6855; (p) O. Callaghan, C. Lampard, A. R. Kennedy and J. A. Murphy, J. Chem. Soc., Perkin Trans. 1, 1999, 995; (q) R. Iyengar, K. Schildknegt and J. Aubé, Org. Lett., 2000, 2, 1625; (r) M. A. Toczko and C. H. Heathcock, J. Org. Chem., 2000, 65, 2642; (s) B. Patro and J. A. Murphy, Org. Lett., 2000, 2, 3599; (t) S. A. Kozmin, T. Iwama, Y. Huang and V H. Rawal, J. Am. Chem. Soc., 2002, 124, 4628; (u) M. G. Banwell and J. A. Smith, J. Chem. Sac., Perkin Trans. 1, 2002, 2613; (v) J. P. Marino, M. B. Rubio, G. Cao and A. de Dios, J. Am. Chem. Soc., 2002, 124, 13398; (w) D. Gnecco, E. Vázquez, A. Galindo, J. L. Terán, L. Orea, S. Bernès and R. G. Enríquez, ARKIVOC, 2003, xi, 185; (x) H. Tanino, K. Fukuishi, M. Ushiyama and K. Okada, Tetrahedron, 2004, 60, 3273.
19. For previously reported total syntheses of aspidospermidine see; (a) G. Stork and J. E. Dolfini, J. Am. Chem. Soc., 1963, 85, 2872; (b) A. Camerman, N. Camerman, J. P. Kutney, E. Piers and J. Trotter, Tetrahedron Lett., 1965, 637; (c) J. Harley-Mason and M. Kaplan, J. Chem. Soc., Chem. Commun., 1967, 915; (d)J.-Y. Laronze, J. Laronze-Fontaine, J. Lévy and J. Le Men, Tetrahedron Lett., 1974, 491; (e) Y. Ban, K. Yoshida, J. Goto and T. Oishi, J. Am. Chem. Soc., 1981, 103, 6990; (f) T. Gallagher, P. Magnus and J. Huffman, J. Am. Chem. Soc., 1982, 104, 1140; (g) E. Wenkert and T. Hudlicky, J. Org. Chem., 1988, 53, 1953; (h) S. B. Mandal, Y S. Giri, M. S. Sabeena and S. C. Pakrashi, J. Org. Chem., 1988, 53, 4236; (i) A. I. Myers and D. Berney, J. Org. Chem., 1989, 54, 4673; (j) M. Node, H. Nagasawa and K. Fuji, J. Org. Chem., 1990, 55, 517; (k) P. Le Menez, N. Kunesch, S. Liu and E. Wenkert, J. Org. Chem., 1991, 56, 2915; (l) D. Desmaële and J. d'Angelo, J. Org. Chem., 1994, 59, 2292; (m) E. Wenkert and S. Liu, J. Org. Chem., 1994, 59, 7677; (n) P. Forns, A. Diez and M. Rubiralta, J. Org. Chem., 1996, 61, 7882; (o) A. G. Schultz and L. Pettus, J. Org. Chem., 1997, 62, 6855; (p) O. Callaghan, C. Lampard, A. R. Kennedy and J. A. Murphy, J. Chem. Soc., Perkin Trans. 1, 1999, 995; (q) R. Iyengar, K. Schildknegt and J. Aubé, Org. Lett., 2000, 2, 1625; (r) M. A. Toczko and C. H. Heathcock, J. Org. Chem., 2000, 65, 2642; (s) B. Patro and J. A. Murphy, Org. Lett., 2000, 2, 3599; (t) S. A. Kozmin, T. Iwama, Y. Huang and V H. Rawal, J. Am. Chem. Soc., 2002, 124, 4628; (u) M. G. Banwell and J. A. Smith, J. Chem. Sac., Perkin Trans. 1, 2002, 2613; (v) J. P. Marino, M. B. Rubio, G. Cao and A. de Dios, J. Am. Chem. Soc., 2002, 124, 13398; (w) D. Gnecco, E. Vázquez, A. Galindo, J. L. Terán, L. Orea, S. Bernès and R. G. Enríquez, ARKIVOC, 2003, xi, 185; (x) H. Tanino, K. Fukuishi, M. Ushiyama and K. Okada, Tetrahedron, 2004, 60, 3273.
20. For previously reported total syntheses of aspidospermidine see; (a) G. Stork and J. E. Dolfini, J. Am. Chem. Soc., 1963, 85, 2872; (b) A. Camerman, N. Camerman, J. P. Kutney, E. Piers and J. Trotter, Tetrahedron Lett., 1965, 637; (c) J. Harley-Mason and M. Kaplan, J. Chem. Soc., Chem. Commun., 1967, 915; (d)J.-Y. Laronze, J. Laronze-Fontaine, J. Lévy and J. Le Men, Tetrahedron Lett., 1974, 491; (e) Y. Ban, K. Yoshida, J. Goto and T. Oishi, J. Am. Chem. Soc., 1981, 103, 6990; (f) T. Gallagher, P. Magnus and J. Huffman, J. Am. Chem. Soc., 1982, 104, 1140; (g) E. Wenkert and T. Hudlicky, J. Org. Chem., 1988, 53, 1953; (h) S. B. Mandal, Y S. Giri, M. S. Sabeena and S. C. Pakrashi, J. Org. Chem., 1988, 53, 4236; (i) A. I. Myers and D. Berney, J. Org. Chem., 1989, 54, 4673; (j) M. Node, H. Nagasawa and K. Fuji, J. Org. Chem., 1990, 55, 517; (k) P. Le Menez, N. Kunesch, S. Liu and E. Wenkert, J. Org. Chem., 1991, 56, 2915; (l) D. Desmaële and J. d'Angelo, J. Org. Chem., 1994, 59, 2292; (m) E. Wenkert and S. Liu, J. Org. Chem., 1994, 59, 7677; (n) P. Forns, A. Diez and M. Rubiralta, J. Org. Chem., 1996, 61, 7882; (o) A. G. Schultz and L. Pettus, J. Org. Chem., 1997, 62, 6855; (p) O. Callaghan, C. Lampard, A. R. Kennedy and J. A. Murphy, J. Chem. Soc., Perkin Trans. 1, 1999, 995; (q) R. Iyengar, K. Schildknegt and J. Aubé, Org. Lett., 2000, 2, 1625; (r) M. A. Toczko and C. H. Heathcock, J. Org. Chem., 2000, 65, 2642; (s) B. Patro and J. A. Murphy, Org. Lett., 2000, 2, 3599; (t) S. A. Kozmin, T. Iwama, Y. Huang and V H. Rawal, J. Am. Chem. Soc., 2002, 124, 4628; (u) M. G. Banwell and J. A. Smith, J. Chem. Sac., Perkin Trans. 1, 2002, 2613; (v) J. P. Marino, M. B. Rubio, G. Cao and A. de Dios, J. Am. Chem. Soc., 2002, 124, 13398; (w) D. Gnecco, E. Vázquez, A. Galindo, J. L. Terán, L. Orea, S. Bernès and R. G. Enríquez, ARKIVOC, 2003, xi, 185; (x) H. Tanino, K. Fukuishi, M. Ushiyama and K. Okada, Tetrahedron, 2004, 60, 3273.
21. For previously reported total syntheses of aspidospermidine see; (a) G. Stork and J. E. Dolfini, J. Am. Chem. Soc., 1963, 85, 2872; (b) A. Camerman, N. Camerman, J. P. Kutney, E. Piers and J. Trotter, Tetrahedron Lett., 1965, 637; (c) J. Harley-Mason and M. Kaplan, J. Chem. Soc., Chem. Commun., 1967, 915; (d)J.-Y. Laronze, J. Laronze-Fontaine, J. Lévy and J. Le Men, Tetrahedron Lett., 1974, 491; (e) Y. Ban, K. Yoshida, J. Goto and T. Oishi, J. Am. Chem. Soc., 1981, 103, 6990; (f) T. Gallagher, P. Magnus and J. Huffman, J. Am. Chem. Soc., 1982, 104, 1140; (g) E. Wenkert and T. Hudlicky, J. Org. Chem., 1988, 53, 1953; (h) S. B. Mandal, Y S. Giri, M. S. Sabeena and S. C. Pakrashi, J. Org. Chem., 1988, 53, 4236; (i) A. I. Myers and D. Berney, J. Org. Chem., 1989, 54, 4673; (j) M. Node, H. Nagasawa and K. Fuji, J. Org. Chem., 1990, 55, 517; (k) P. Le Menez, N. Kunesch, S. Liu and E. Wenkert, J. Org. Chem., 1991, 56, 2915; (l) D. Desmaële and J. d'Angelo, J. Org. Chem., 1994, 59, 2292; (m) E. Wenkert and S. Liu, J. Org. Chem., 1994, 59, 7677; (n) P. Forns, A. Diez and M. Rubiralta, J. Org. Chem., 1996, 61, 7882; (o) A. G. Schultz and L. Pettus, J. Org. Chem., 1997, 62, 6855; (p) O. Callaghan, C. Lampard, A. R. Kennedy and J. A. Murphy, J. Chem. Soc., Perkin Trans. 1, 1999, 995; (q) R. Iyengar, K. Schildknegt and J. Aubé, Org. Lett., 2000, 2, 1625; (r) M. A. Toczko and C. H. Heathcock, J. Org. Chem., 2000, 65, 2642; (s) B. Patro and J. A. Murphy, Org. Lett., 2000, 2, 3599; (t) S. A. Kozmin, T. Iwama, Y. Huang and V H. Rawal, J. Am. Chem. Soc., 2002, 124, 4628; (u) M. G. Banwell and J. A. Smith, J. Chem. Sac., Perkin Trans. 1, 2002, 2613; (v) J. P. Marino, M. B. Rubio, G. Cao and A. de Dios, J. Am. Chem. Soc., 2002, 124, 13398; (w) D. Gnecco, E. Vázquez, A. Galindo, J. L. Terán, L. Orea, S. Bernès and R. G. Enríquez, ARKIVOC, 2003, xi, 185; (x) H. Tanino, K. Fukuishi, M. Ushiyama and K. Okada, Tetrahedron, 2004, 60, 3273.
22. For previously reported total syntheses of aspidospermidine see; (a) G. Stork and J. E. Dolfini, J. Am. Chem. Soc., 1963, 85, 2872; (b) A. Camerman, N. Camerman, J. P. Kutney, E. Piers and J. Trotter, Tetrahedron Lett., 1965, 637; (c) J. Harley-Mason and M. Kaplan, J. Chem. Soc., Chem. Commun., 1967, 915; (d)J.-Y. Laronze, J. Laronze-Fontaine, J. Lévy and J. Le Men, Tetrahedron Lett., 1974, 491; (e) Y. Ban, K. Yoshida, J. Goto and T. Oishi, J. Am. Chem. Soc., 1981, 103, 6990; (f) T. Gallagher, P. Magnus and J. Huffman, J. Am. Chem. Soc., 1982, 104, 1140; (g) E. Wenkert and T. Hudlicky, J. Org. Chem., 1988, 53, 1953; (h) S. B. Mandal, Y S. Giri, M. S. Sabeena and S. C. Pakrashi, J. Org. Chem., 1988, 53, 4236; (i) A. I. Myers and D. Berney, J. Org. Chem., 1989, 54, 4673; (j) M. Node, H. Nagasawa and K. Fuji, J. Org. Chem., 1990, 55, 517; (k) P. Le Menez, N. Kunesch, S. Liu and E. Wenkert, J. Org. Chem., 1991, 56, 2915; (l) D. Desmaële and J. d'Angelo, J. Org. Chem., 1994, 59, 2292; (m) E. Wenkert and S. Liu, J. Org. Chem., 1994, 59, 7677; (n) P. Forns, A. Diez and M. Rubiralta, J. Org. Chem., 1996, 61, 7882; (o) A. G. Schultz and L. Pettus, J. Org. Chem., 1997, 62, 6855; (p) O. Callaghan, C. Lampard, A. R. Kennedy and J. A. Murphy, J. Chem. Soc., Perkin Trans. 1, 1999, 995; (q) R. Iyengar, K. Schildknegt and J. Aubé, Org. Lett., 2000, 2, 1625; (r) M. A. Toczko and C. H. Heathcock, J. Org. Chem., 2000, 65, 2642; (s) B. Patro and J. A. Murphy, Org. Lett., 2000, 2, 3599; (t) S. A. Kozmin, T. Iwama, Y. Huang and V H. Rawal, J. Am. Chem. Soc., 2002, 124, 4628; (u) M. G. Banwell and J. A. Smith, J. Chem. Sac., Perkin Trans. 1, 2002, 2613; (v) J. P. Marino, M. B. Rubio, G. Cao and A. de Dios, J. Am. Chem. Soc., 2002, 124, 13398; (w) D. Gnecco, E. Vázquez, A. Galindo, J. L. Terán, L. Orea, S. Bernès and R. G. Enríquez, ARKIVOC, 2003, xi, 185; (x) H. Tanino, K. Fukuishi, M. Ushiyama and K. Okada, Tetrahedron, 2004, 60, 3273.
23. For previously reported total syntheses of aspidospermidine see; (a) G. Stork and J. E. Dolfini, J. Am. Chem. Soc., 1963, 85, 2872; (b) A. Camerman, N. Camerman, J. P. Kutney, E. Piers and J. Trotter, Tetrahedron Lett., 1965, 637; (c) J. Harley-Mason and M. Kaplan, J. Chem. Soc., Chem. Commun., 1967, 915; (d)J.-Y. Laronze, J. Laronze-Fontaine, J. Lévy and J. Le Men, Tetrahedron Lett., 1974, 491; (e) Y. Ban, K. Yoshida, J. Goto and T. Oishi, J. Am. Chem. Soc., 1981, 103, 6990; (f) T. Gallagher, P. Magnus and J. Huffman, J. Am. Chem. Soc., 1982, 104, 1140; (g) E. Wenkert and T. Hudlicky, J. Org. Chem., 1988, 53, 1953; (h) S. B. Mandal, Y S. Giri, M. S. Sabeena and S. C. Pakrashi, J. Org. Chem., 1988, 53, 4236; (i) A. I. Myers and D. Berney, J. Org. Chem., 1989, 54, 4673; (j) M. Node, H. Nagasawa and K. Fuji, J. Org. Chem., 1990, 55, 517; (k) P. Le Menez, N. Kunesch, S. Liu and E. Wenkert, J. Org. Chem., 1991, 56, 2915; (l) D. Desmaële and J. d'Angelo, J. Org. Chem., 1994, 59, 2292; (m) E. Wenkert and S. Liu, J. Org. Chem., 1994, 59, 7677; (n) P. Forns, A. Diez and M. Rubiralta, J. Org. Chem., 1996, 61, 7882; (o) A. G. Schultz and L. Pettus, J. Org. Chem., 1997, 62, 6855; (p) O. Callaghan, C. Lampard, A. R. Kennedy and J. A. Murphy, J. Chem. Soc., Perkin Trans. 1, 1999, 995; (q) R. Iyengar, K. Schildknegt and J. Aubé, Org. Lett., 2000, 2, 1625; (r) M. A. Toczko and C. H. Heathcock, J. Org. Chem., 2000, 65, 2642; (s) B. Patro and J. A. Murphy, Org. Lett., 2000, 2, 3599; (t) S. A. Kozmin, T. Iwama, Y. Huang and V H. Rawal, J. Am. Chem. Soc., 2002, 124, 4628; (u) M. G. Banwell and J. A. Smith, J. Chem. Sac., Perkin Trans. 1, 2002, 2613; (v) J. P. Marino, M. B. Rubio, G. Cao and A. de Dios, J. Am. Chem. Soc., 2002, 124, 13398; (w) D. Gnecco, E. Vázquez, A. Galindo, J. L. Terán, L. Orea, S. Bernès and R. G. Enríquez, ARKIVOC, 2003, xi, 185; (x) H. Tanino, K. Fukuishi, M. Ushiyama and K. Okada, Tetrahedron, 2004, 60, 3273.
24. For previously reported total syntheses of aspidospermidine see; (a) G. Stork and J. E. Dolfini, J. Am. Chem. Soc., 1963, 85, 2872; (b) A. Camerman, N. Camerman, J. P. Kutney, E. Piers and J. Trotter, Tetrahedron Lett., 1965, 637; (c) J. Harley-Mason and M. Kaplan, J. Chem. Soc., Chem. Commun., 1967, 915; (d)J.-Y. Laronze, J. Laronze-Fontaine, J. Lévy and J. Le Men, Tetrahedron Lett., 1974, 491; (e) Y. Ban, K. Yoshida, J. Goto and T. Oishi, J. Am. Chem. Soc., 1981, 103, 6990; (f) T. Gallagher, P. Magnus and J. Huffman, J. Am. Chem. Soc., 1982, 104, 1140; (g) E. Wenkert and T. Hudlicky, J. Org. Chem., 1988, 53, 1953; (h) S. B. Mandal, Y S. Giri, M. S. Sabeena and S. C. Pakrashi, J. Org. Chem., 1988, 53, 4236; (i) A. I. Myers and D. Berney, J. Org. Chem., 1989, 54, 4673; (j) M. Node, H. Nagasawa and K. Fuji, J. Org. Chem., 1990, 55, 517; (k) P. Le Menez, N. Kunesch, S. Liu and E. Wenkert, J. Org. Chem., 1991, 56, 2915; (l) D. Desmaële and J. d'Angelo, J. Org. Chem., 1994, 59, 2292; (m) E. Wenkert and S. Liu, J. Org. Chem., 1994, 59, 7677; (n) P. Forns, A. Diez and M. Rubiralta, J. Org. Chem., 1996, 61, 7882; (o) A. G. Schultz and L. Pettus, J. Org. Chem., 1997, 62, 6855; (p) O. Callaghan, C. Lampard, A. R. Kennedy and J. A. Murphy, J. Chem. Soc., Perkin Trans. 1, 1999, 995; (q) R. Iyengar, K. Schildknegt and J. Aubé, Org. Lett., 2000, 2, 1625; (r) M. A. Toczko and C. H. Heathcock, J. Org. Chem., 2000, 65, 2642; (s) B. Patro and J. A. Murphy, Org. Lett., 2000, 2, 3599; (t) S. A. Kozmin, T. Iwama, Y. Huang and V H. Rawal, J. Am. Chem. Soc., 2002, 124, 4628; (u) M. G. Banwell and J. A. Smith, J. Chem. Sac., Perkin Trans. 1, 2002, 2613; (v) J. P. Marino, M. B. Rubio, G. Cao and A. de Dios, J. Am. Chem. Soc., 2002, 124, 13398; (w) D. Gnecco, E. Vázquez, A. Galindo, J. L. Terán, L. Orea, S. Bernès and R. G. Enríquez, ARKIVOC, 2003, xi, 185; (x) H. Tanino, K. Fukuishi, M. Ushiyama and K. Okada, Tetrahedron, 2004, 60, 3273.
25. For previously reported total syntheses of aspidospermidine see; (a) G. Stork and J. E. Dolfini, J. Am. Chem. Soc., 1963, 85, 2872; (b) A. Camerman, N. Camerman, J. P. Kutney, E. Piers and J. Trotter, Tetrahedron Lett., 1965, 637; (c) J. Harley-Mason and M. Kaplan, J. Chem. Soc., Chem. Commun., 1967, 915; (d)J.-Y. Laronze, J. Laronze-Fontaine, J. Lévy and J. Le Men, Tetrahedron Lett., 1974, 491; (e) Y. Ban, K. Yoshida, J. Goto and T. Oishi, J. Am. Chem. Soc., 1981, 103, 6990; (f) T. Gallagher, P. Magnus and J. Huffman, J. Am. Chem. Soc., 1982, 104, 1140; (g) E. Wenkert and T. Hudlicky, J. Org. Chem., 1988, 53, 1953; (h) S. B. Mandal, Y S. Giri, M. S. Sabeena and S. C. Pakrashi, J. Org. Chem., 1988, 53, 4236; (i) A. I. Myers and D. Berney, J. Org. Chem., 1989, 54, 4673; (j) M. Node, H. Nagasawa and K. Fuji, J. Org. Chem., 1990, 55, 517; (k) P. Le Menez, N. Kunesch, S. Liu and E. Wenkert, J. Org. Chem., 1991, 56, 2915; (l) D. Desmaële and J. d'Angelo, J. Org. Chem., 1994, 59, 2292; (m) E. Wenkert and S. Liu, J. Org. Chem., 1994, 59, 7677; (n) P. Forns, A. Diez and M. Rubiralta, J. Org. Chem., 1996, 61, 7882; (o) A. G. Schultz and L. Pettus, J. Org. Chem., 1997, 62, 6855; (p) O. Callaghan, C. Lampard, A. R. Kennedy and J. A. Murphy, J. Chem. Soc., Perkin Trans. 1, 1999, 995; (q) R. Iyengar, K. Schildknegt and J. Aubé, Org. Lett., 2000, 2, 1625; (r) M. A. Toczko and C. H. Heathcock, J. Org. Chem., 2000, 65, 2642; (s) B. Patro and J. A. Murphy, Org. Lett., 2000, 2, 3599; (t) S. A. Kozmin, T. Iwama, Y. Huang and V H. Rawal, J. Am. Chem. Soc., 2002, 124, 4628; (u) M. G. Banwell and J. A. Smith, J. Chem. Sac., Perkin Trans. 1, 2002, 2613; (v) J. P. Marino, M. B. Rubio, G. Cao and A. de Dios, J. Am. Chem. Soc., 2002, 124, 13398; (w) D. Gnecco, E. Vázquez, A. Galindo, J. L. Terán, L. Orea, S. Bernès and R. G. Enríquez, ARKIVOC, 2003, xi, 185; (x) H. Tanino, K. Fukuishi, M. Ushiyama and K. Okada, Tetrahedron, 2004, 60, 3273.
26. For previously reported total syntheses of aspidospermidine see; (a) G. Stork and J. E. Dolfini, J. Am. Chem. Soc., 1963, 85, 2872; (b) A. Camerman, N. Camerman, J. P. Kutney, E. Piers and J. Trotter, Tetrahedron Lett., 1965, 637; (c) J. Harley-Mason and M. Kaplan, J. Chem. Soc., Chem. Commun., 1967, 915; (d)J.-Y. Laronze, J. Laronze-Fontaine, J. Lévy and J. Le Men, Tetrahedron Lett., 1974, 491; (e) Y. Ban, K. Yoshida, J. Goto and T. Oishi, J. Am. Chem. Soc., 1981, 103, 6990; (f) T. Gallagher, P. Magnus and J. Huffman, J. Am. Chem. Soc., 1982, 104, 1140; (g) E. Wenkert and T. Hudlicky, J. Org. Chem., 1988, 53, 1953; (h) S. B. Mandal, Y S. Giri, M. S. Sabeena and S. C. Pakrashi, J. Org. Chem., 1988, 53, 4236; (i) A. I. Myers and D. Berney, J. Org. Chem., 1989, 54, 4673; (j) M. Node, H. Nagasawa and K. Fuji, J. Org. Chem., 1990, 55, 517; (k) P. Le Menez, N. Kunesch, S. Liu and E. Wenkert, J. Org. Chem., 1991, 56, 2915; (l) D. Desmaële and J. d'Angelo, J. Org. Chem., 1994, 59, 2292; (m) E. Wenkert and S. Liu, J. Org. Chem., 1994, 59, 7677; (n) P. Forns, A. Diez and M. Rubiralta, J. Org. Chem., 1996, 61, 7882; (o) A. G. Schultz and L. Pettus, J. Org. Chem., 1997, 62, 6855; (p) O. Callaghan, C. Lampard, A. R. Kennedy and J. A. Murphy, J. Chem. Soc., Perkin Trans. 1, 1999, 995; (q) R. Iyengar, K. Schildknegt and J. Aubé, Org. Lett., 2000, 2, 1625; (r) M. A. Toczko and C. H. Heathcock, J. Org. Chem., 2000, 65, 2642; (s) B. Patro and J. A. Murphy, Org. Lett., 2000, 2, 3599; (t) S. A. Kozmin, T. Iwama, Y. Huang and V H. Rawal, J. Am. Chem. Soc., 2002, 124, 4628; (u) M. G. Banwell and J. A. Smith, J. Chem. Sac., Perkin Trans. 1, 2002, 2613; (v) J. P. Marino, M. B. Rubio, G. Cao and A. de Dios, J. Am. Chem. Soc., 2002, 124, 13398; (w) D. Gnecco, E. Vázquez, A. Galindo, J. L. Terán, L. Orea, S. Bernès and R. G. Enríquez, ARKIVOC, 2003, xi, 185; (x) H. Tanino, K. Fukuishi, M. Ushiyama and K. Okada, Tetrahedron, 2004, 60, 3273.
27. For previously reported total syntheses of aspidospermidine see; (a) G. Stork and J. E. Dolfini, J. Am. Chem. Soc., 1963, 85, 2872; (b) A. Camerman, N. Camerman, J. P. Kutney, E. Piers and J. Trotter, Tetrahedron Lett., 1965, 637; (c) J. Harley-Mason and M. Kaplan, J. Chem. Soc., Chem. Commun., 1967, 915; (d)J.-Y. Laronze, J. Laronze-Fontaine, J. Lévy and J. Le Men, Tetrahedron Lett., 1974, 491; (e) Y. Ban, K. Yoshida, J. Goto and T. Oishi, J. Am. Chem. Soc., 1981, 103, 6990; (f) T. Gallagher, P. Magnus and J. Huffman, J. Am. Chem. Soc., 1982, 104, 1140; (g) E. Wenkert and T. Hudlicky, J. Org. Chem., 1988, 53, 1953; (h) S. B. Mandal, Y S. Giri, M. S. Sabeena and S. C. Pakrashi, J. Org. Chem., 1988, 53, 4236; (i) A. I. Myers and D. Berney, J. Org. Chem., 1989, 54, 4673; (j) M. Node, H. Nagasawa and K. Fuji, J. Org. Chem., 1990, 55, 517; (k) P. Le Menez, N. Kunesch, S. Liu and E. Wenkert, J. Org. Chem., 1991, 56, 2915; (l) D. Desmaële and J. d'Angelo, J. Org. Chem., 1994, 59, 2292; (m) E. Wenkert and S. Liu, J. Org. Chem., 1994, 59, 7677; (n) P. Forns, A. Diez and M. Rubiralta, J. Org. Chem., 1996, 61, 7882; (o) A. G. Schultz and L. Pettus, J. Org. Chem., 1997, 62, 6855; (p) O. Callaghan, C. Lampard, A. R. Kennedy and J. A. Murphy, J. Chem. Soc., Perkin Trans. 1, 1999, 995; (q) R. Iyengar, K. Schildknegt and J. Aubé, Org. Lett., 2000, 2, 1625; (r) M. A. Toczko and C. H. Heathcock, J. Org. Chem., 2000, 65, 2642; (s) B. Patro and J. A. Murphy, Org. Lett., 2000, 2, 3599; (t) S. A. Kozmin, T. Iwama, Y. Huang and V H. Rawal, J. Am. Chem. Soc., 2002, 124, 4628; (u) M. G. Banwell and J. A. Smith, J. Chem. Sac., Perkin Trans. 1, 2002, 2613; (v) J. P. Marino, M. B. Rubio, G. Cao and A. de Dios, J. Am. Chem. Soc., 2002, 124, 13398; (w) D. Gnecco, E. Vázquez, A. Galindo, J. L. Terán, L. Orea, S. Bernès and R. G. Enríquez, ARKIVOC, 2003, xi, 185; (x) H. Tanino, K. Fukuishi, M. Ushiyama and K. Okada, Tetrahedron, 2004, 60, 3273.
28. For previously reported total syntheses of aspidospermidine see; (a) G. Stork and J. E. Dolfini, J. Am. Chem. Soc., 1963, 85, 2872; (b) A. Camerman, N. Camerman, J. P. Kutney, E. Piers and J. Trotter, Tetrahedron Lett., 1965, 637; (c) J. Harley-Mason and M. Kaplan, J. Chem. Soc., Chem. Commun., 1967, 915; (d)J.-Y. Laronze, J. Laronze-Fontaine, J. Lévy and J. Le Men, Tetrahedron Lett., 1974, 491; (e) Y. Ban, K. Yoshida, J. Goto and T. Oishi, J. Am. Chem. Soc., 1981, 103, 6990; (f) T. Gallagher, P. Magnus and J. Huffman, J. Am. Chem. Soc., 1982, 104, 1140; (g) E. Wenkert and T. Hudlicky, J. Org. Chem., 1988, 53, 1953; (h) S. B. Mandal, Y S. Giri, M. S. Sabeena and S. C. Pakrashi, J. Org. Chem., 1988, 53, 4236; (i) A. I. Myers and D. Berney, J. Org. Chem., 1989, 54, 4673; (j) M. Node, H. Nagasawa and K. Fuji, J. Org. Chem., 1990, 55, 517; (k) P. Le Menez, N. Kunesch, S. Liu and E. Wenkert, J. Org. Chem., 1991, 56, 2915; (l) D. Desmaële and J. d'Angelo, J. Org. Chem., 1994, 59, 2292; (m) E. Wenkert and S. Liu, J. Org. Chem., 1994, 59, 7677; (n) P. Forns, A. Diez and M. Rubiralta, J. Org. Chem., 1996, 61, 7882; (o) A. G. Schultz and L. Pettus, J. Org. Chem., 1997, 62, 6855; (p) O. Callaghan, C. Lampard, A. R. Kennedy and J. A. Murphy, J. Chem. Soc., Perkin Trans. 1, 1999, 995; (q) R. Iyengar, K. Schildknegt and J. Aubé, Org. Lett., 2000, 2, 1625; (r) M. A. Toczko and C. H. Heathcock, J. Org. Chem., 2000, 65, 2642; (s) B. Patro and J. A. Murphy, Org. Lett., 2000, 2, 3599; (t) S. A. Kozmin, T. Iwama, Y. Huang and V H. Rawal, J. Am. Chem. Soc., 2002, 124, 4628; (u) M. G. Banwell and J. A. Smith, J. Chem. Sac., Perkin Trans. 1, 2002, 2613; (v) J. P. Marino, M. B. Rubio, G. Cao and A. de Dios, J. Am. Chem. Soc., 2002, 124, 13398; (w) D. Gnecco, E. Vázquez, A. Galindo, J. L. Terán, L. Orea, S. Bernès and R. G. Enríquez, ARKIVOC, 2003, xi, 185; (x) H. Tanino, K. Fukuishi, M. Ushiyama and K. Okada, Tetrahedron, 2004, 60, 3273.
29. For previously reported total syntheses of aspidospermidine see; (a) G. Stork and J. E. Dolfini, J. Am. Chem. Soc., 1963, 85, 2872; (b) A. Camerman, N. Camerman, J. P. Kutney, E. Piers and J. Trotter, Tetrahedron Lett., 1965, 637; (c) J. Harley-Mason and M. Kaplan, J. Chem. Soc., Chem. Commun., 1967, 915; (d)J.-Y. Laronze, J. Laronze-Fontaine, J. Lévy and J. Le Men, Tetrahedron Lett., 1974, 491; (e) Y. Ban, K. Yoshida, J. Goto and T. Oishi, J. Am. Chem. Soc., 1981, 103, 6990; (f) T. Gallagher, P. Magnus and J. Huffman, J. Am. Chem. Soc., 1982, 104, 1140; (g) E. Wenkert and T. Hudlicky, J. Org. Chem., 1988, 53, 1953; (h) S. B. Mandal, Y S. Giri, M. S. Sabeena and S. C. Pakrashi, J. Org. Chem., 1988, 53, 4236; (i) A. I. Myers and D. Berney, J. Org. Chem., 1989, 54, 4673; (j) M. Node, H. Nagasawa and K. Fuji, J. Org. Chem., 1990, 55, 517; (k) P. Le Menez, N. Kunesch, S. Liu and E. Wenkert, J. Org. Chem., 1991, 56, 2915; (l) D. Desmaële and J. d'Angelo, J. Org. Chem., 1994, 59, 2292; (m) E. Wenkert and S. Liu, J. Org. Chem., 1994, 59, 7677; (n) P. Forns, A. Diez and M. Rubiralta, J. Org. Chem., 1996, 61, 7882; (o) A. G. Schultz and L. Pettus, J. Org. Chem., 1997, 62, 6855; (p) O. Callaghan, C. Lampard, A. R. Kennedy and J. A. Murphy, J. Chem. Soc., Perkin Trans. 1, 1999, 995; (q) R. Iyengar, K. Schildknegt and J. Aubé, Org. Lett., 2000, 2, 1625; (r) M. A. Toczko and C. H. Heathcock, J. Org. Chem., 2000, 65, 2642; (s) B. Patro and J. A. Murphy, Org. Lett., 2000, 2, 3599; (t) S. A. Kozmin, T. Iwama, Y. Huang and V H. Rawal, J. Am. Chem. Soc., 2002, 124, 4628; (u) M. G. Banwell and J. A. Smith, J. Chem. Sac., Perkin Trans. 1, 2002, 2613; (v) J. P. Marino, M. B. Rubio, G. Cao and A. de Dios, J. Am. Chem. Soc., 2002, 124, 13398; (w) D. Gnecco, E. Vázquez, A. Galindo, J. L. Terán, L. Orea, S. Bernès and R. G. Enríquez, ARKIVOC, 2003, xi, 185; (x) H. Tanino, K. Fukuishi, M. Ushiyama and K. Okada, Tetrahedron, 2004, 60, 3273.
30. For previously reported total syntheses of aspidospermidine see; (a) G. Stork and J. E. Dolfini, J. Am. Chem. Soc., 1963, 85, 2872; (b) A. Camerman, N. Camerman, J. P. Kutney, E. Piers and J. Trotter, Tetrahedron Lett., 1965, 637; (c) J. Harley-Mason and M. Kaplan, J. Chem. Soc., Chem. Commun., 1967, 915; (d)J.-Y. Laronze, J. Laronze-Fontaine, J. Lévy and J. Le Men, Tetrahedron Lett., 1974, 491; (e) Y. Ban, K. Yoshida, J. Goto and T. Oishi, J. Am. Chem. Soc., 1981, 103, 6990; (f) T. Gallagher, P. Magnus and J. Huffman, J. Am. Chem. Soc., 1982, 104, 1140; (g) E. Wenkert and T. Hudlicky, J. Org. Chem., 1988, 53, 1953; (h) S. B. Mandal, Y S. Giri, M. S. Sabeena and S. C. Pakrashi, J. Org. Chem., 1988, 53, 4236; (i) A. I. Myers and D. Berney, J. Org. Chem., 1989, 54, 4673; (j) M. Node, H. Nagasawa and K. Fuji, J. Org. Chem., 1990, 55, 517; (k) P. Le Menez, N. Kunesch, S. Liu and E. Wenkert, J. Org. Chem., 1991, 56, 2915; (l) D. Desmaële and J. d'Angelo, J. Org. Chem., 1994, 59, 2292; (m) E. Wenkert and S. Liu, J. Org. Chem., 1994, 59, 7677; (n) P. Forns, A. Diez and M. Rubiralta, J. Org. Chem., 1996, 61, 7882; (o) A. G. Schultz and L. Pettus, J. Org. Chem., 1997, 62, 6855; (p) O. Callaghan, C. Lampard, A. R. Kennedy and J. A. Murphy, J. Chem. Soc., Perkin Trans. 1, 1999, 995; (q) R. Iyengar, K. Schildknegt and J. Aubé, Org. Lett., 2000, 2, 1625; (r) M. A. Toczko and C. H. Heathcock, J. Org. Chem., 2000, 65, 2642; (s) B. Patro and J. A. Murphy, Org. Lett., 2000, 2, 3599; (t) S. A. Kozmin, T. Iwama, Y. Huang and V H. Rawal, J. Am. Chem. Soc., 2002, 124, 4628; (u) M. G. Banwell and J. A. Smith, J. Chem. Sac., Perkin Trans. 1, 2002, 2613; (v) J. P. Marino, M. B. Rubio, G. Cao and A. de Dios, J. Am. Chem. Soc., 2002, 124, 13398; (w) D. Gnecco, E. Vázquez, A. Galindo, J. L. Terán, L. Orea, S. Bernès and R. G. Enríquez, ARKIVOC, 2003, xi, 185; (x) H. Tanino, K. Fukuishi, M. Ushiyama and K. Okada, Tetrahedron, 2004, 60, 3273.
31. For previously reported total syntheses of aspidospermidine see; (a) G. Stork and J. E. Dolfini, J. Am. Chem. Soc., 1963, 85, 2872; (b) A. Camerman, N. Camerman, J. P. Kutney, E. Piers and J. Trotter, Tetrahedron Lett., 1965, 637; (c) J. Harley-Mason and M. Kaplan, J. Chem. Soc., Chem. Commun., 1967, 915; (d)J.-Y. Laronze, J. Laronze-Fontaine, J. Lévy and J. Le Men, Tetrahedron Lett., 1974, 491; (e) Y. Ban, K. Yoshida, J. Goto and T. Oishi, J. Am. Chem. Soc., 1981, 103, 6990; (f) T. Gallagher, P. Magnus and J. Huffman, J. Am. Chem. Soc., 1982, 104, 1140; (g) E. Wenkert and T. Hudlicky, J. Org. Chem., 1988, 53, 1953; (h) S. B. Mandal, Y S. Giri, M. S. Sabeena and S. C. Pakrashi, J. Org. Chem., 1988, 53, 4236; (i) A. I. Myers and D. Berney, J. Org. Chem., 1989, 54, 4673; (j) M. Node, H. Nagasawa and K. Fuji, J. Org. Chem., 1990, 55, 517; (k) P. Le Menez, N. Kunesch, S. Liu and E. Wenkert, J. Org. Chem., 1991, 56, 2915; (l) D. Desmaële and J. d'Angelo, J. Org. Chem., 1994, 59, 2292; (m) E. Wenkert and S. Liu, J. Org. Chem., 1994, 59, 7677; (n) P. Forns, A. Diez and M. Rubiralta, J. Org. Chem., 1996, 61, 7882; (o) A. G. Schultz and L. Pettus, J. Org. Chem., 1997, 62, 6855; (p) O. Callaghan, C. Lampard, A. R. Kennedy and J. A. Murphy, J. Chem. Soc., Perkin Trans. 1, 1999, 995; (q) R. Iyengar, K. Schildknegt and J. Aubé, Org. Lett., 2000, 2, 1625; (r) M. A. Toczko and C. H. Heathcock, J. Org. Chem., 2000, 65, 2642; (s) B. Patro and J. A. Murphy, Org. Lett., 2000, 2, 3599; (t) S. A. Kozmin, T. Iwama, Y. Huang and V H. Rawal, J. Am. Chem. Soc., 2002, 124, 4628; (u) M. G. Banwell and J. A. Smith, J. Chem. Sac., Perkin Trans. 1, 2002, 2613; (v) J. P. Marino, M. B. Rubio, G. Cao and A. de Dios, J. Am. Chem. Soc., 2002, 124, 13398; (w) D. Gnecco, E. Vázquez, A. Galindo, J. L. Terán, L. Orea, S. Bernès and R. G. Enríquez, ARKIVOC, 2003, xi, 185; (x) H. Tanino, K. Fukuishi, M. Ushiyama and K. Okada, Tetrahedron, 2004, 60, 3273.
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42. The triazoline derived from thermolysis of the des-ethyl analogue of compound 14 is an isolable and crystalline species that has been characterised by single-crystal X-ray analysis. Full details will be reported in due course.