Pauson-Khand cycloaddition reactions of chiral ynamides. Observation of an unusual endo-addition with norbornadiene

Tetrahedron Letters

Volumn 44, Issue 52, 2003, Pages 9353-9358

  Shen, Lichun ^a   Hsung, Richard P ^a  

^a University of Minnesota   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

AMIDE; AMINE; NORBORNADIENE DERIVATIVE; UNCLASSIFIED DRUG; YNAMIDE DERIVATIVE;

ADDITION REACTION; ARTICLE; CHEMICAL STRUCTURE; CHIRALITY; CYCLOADDITION; STEREOCHEMISTRY;

EID: 0345171709     PISSN: 00404039     EISSN: None     Source Type: Journal    
DOI: 10.1016/j.tetlet.2003.10.064     Document Type: Article

References (67)

1. For reviews on ynamides, see: (a) Zificsak, C. A.; Mulder, J. A.; Hsung, R. P.; Rameshkumar, C.; Wei, L.-L. Tetrahedron 2001, 57, 7575; (b) Mulder, J. A.; Kurtz, K. C. M.; Hsung, R. P. Synlett 2003, 1379. For the first preparations of ynamides, see: (c) Janousek, Z.; Collard, J.; Viehe, H. G. Angew. Chem., Int. Ed. Engl. 1972, 11, 917.
2. For reviews on ynamides, see: (a) Zificsak, C. A.; Mulder, J. A.; Hsung, R. P.; Rameshkumar, C.; Wei, L.-L. Tetrahedron 2001, 57, 7575; (b) Mulder, J. A.; Kurtz, K. C. M.; Hsung, R. P. Synlett 2003, 1379. For the first preparations of ynamides, see: (c) Janousek, Z.; Collard, J.; Viehe, H. G. Angew. Chem., Int. Ed. Engl. 1972, 11, 917.
3. For reviews on ynamides, see: (a) Zificsak, C. A.; Mulder, J. A.; Hsung, R. P.; Rameshkumar, C.; Wei, L.-L. Tetrahedron 2001, 57, 7575; (b) Mulder, J. A.; Kurtz, K. C. M.; Hsung, R. P. Synlett 2003, 1379. For the first preparations of ynamides, see: (c) Janousek, Z.; Collard, J.; Viehe, H. G. Angew. Chem., Int. Ed. Engl. 1972, 11, 917.
4. For recent efforts in synthesis and applications of ynamides, see: (a) Witulski, B.; Alayrac, C.; Tevzaadze-Saeftel, L. Angew. Chem., Int. Ed. 2003, 42, 4257; (b) Tanaka, R.; Hirano, S.; Urabe, H.; Sato, F. Org. Lett. 2003, 5, 67; (c) Witulski, B.; Lumtscher, J.; Bergsträßer, U. Synlett 2003, 708; (d) Naud, S.; Cintrat, J.-C. Synthesis 2003, 1391; (e) Witulski, B.; Alayrac, C. Angew. Chem., Int. Ed. 2002, 41, 3281; (f) Saito, N.; Sato, Y.; Mori, M. Org. Lett. 2002, 4, 803; (g) Timbert, J.-C.; Cintrat, J.-C. Chem. Eur. J. 2002, 8, 1637; (h) Minière, S.; Cintrat, J.-C. Synthesis 2001, 705; (i) Minière, S.; Cintrat, J.-C. J. Org. Chem. 2001, 66, 7385; (j) Hoffmann, R. W.; Brückner, D. New. J. Chem. 2001, 25, 369; (k) For citations that appeared before 2001, see Refs. 1a and 1b.
5. For recent efforts in synthesis and applications of ynamides, see: (a) Witulski, B.; Alayrac, C.; Tevzaadze-Saeftel, L. Angew. Chem., Int. Ed. 2003, 42, 4257; (b) Tanaka, R.; Hirano, S.; Urabe, H.; Sato, F. Org. Lett. 2003, 5, 67; (c) Witulski, B.; Lumtscher, J.; Bergsträßer, U. Synlett 2003, 708; (d) Naud, S.; Cintrat, J.-C. Synthesis 2003, 1391; (e) Witulski, B.; Alayrac, C. Angew. Chem., Int. Ed. 2002, 41, 3281; (f) Saito, N.; Sato, Y.; Mori, M. Org. Lett. 2002, 4, 803; (g) Timbert, J.-C.; Cintrat, J.-C. Chem. Eur. J. 2002, 8, 1637; (h) Minière, S.; Cintrat, J.-C. Synthesis 2001, 705; (i) Minière, S.; Cintrat, J.-C. J. Org. Chem. 2001, 66, 7385; (j) Hoffmann, R. W.; Brückner, D. New. J. Chem. 2001, 25, 369; (k) For citations that appeared before 2001, see Refs. 1a and 1b.
6. For recent efforts in synthesis and applications of ynamides, see: (a) Witulski, B.; Alayrac, C.; Tevzaadze-Saeftel, L. Angew. Chem., Int. Ed. 2003, 42, 4257; (b) Tanaka, R.; Hirano, S.; Urabe, H.; Sato, F. Org. Lett. 2003, 5, 67; (c) Witulski, B.; Lumtscher, J.; Bergsträßer, U. Synlett 2003, 708; (d) Naud, S.; Cintrat, J.-C. Synthesis 2003, 1391; (e) Witulski, B.; Alayrac, C. Angew. Chem., Int. Ed. 2002, 41, 3281; (f) Saito, N.; Sato, Y.; Mori, M. Org. Lett. 2002, 4, 803; (g) Timbert, J.-C.; Cintrat, J.-C. Chem. Eur. J. 2002, 8, 1637; (h) Minière, S.; Cintrat, J.-C. Synthesis 2001, 705; (i) Minière, S.; Cintrat, J.-C. J. Org. Chem. 2001, 66, 7385; (j) Hoffmann, R. W.; Brückner, D. New. J. Chem. 2001, 25, 369; (k) For citations that appeared before 2001, see Refs. 1a and 1b.
7. For recent efforts in synthesis and applications of ynamides, see: (a) Witulski, B.; Alayrac, C.; Tevzaadze-Saeftel, L. Angew. Chem., Int. Ed. 2003, 42, 4257; (b) Tanaka, R.; Hirano, S.; Urabe, H.; Sato, F. Org. Lett. 2003, 5, 67; (c) Witulski, B.; Lumtscher, J.; Bergsträßer, U. Synlett 2003, 708; (d) Naud, S.; Cintrat, J.-C. Synthesis 2003, 1391; (e) Witulski, B.; Alayrac, C. Angew. Chem., Int. Ed. 2002, 41, 3281; (f) Saito, N.; Sato, Y.; Mori, M. Org. Lett. 2002, 4, 803; (g) Timbert, J.-C.; Cintrat, J.-C. Chem. Eur. J. 2002, 8, 1637; (h) Minière, S.; Cintrat, J.-C. Synthesis 2001, 705; (i) Minière, S.; Cintrat, J.-C. J. Org. Chem. 2001, 66, 7385; (j) Hoffmann, R. W.; Brückner, D. New. J. Chem. 2001, 25, 369; (k) For citations that appeared before 2001, see Refs. 1a and 1b.
8. For recent efforts in synthesis and applications of ynamides, see: (a) Witulski, B.; Alayrac, C.; Tevzaadze-Saeftel, L. Angew. Chem., Int. Ed. 2003, 42, 4257; (b) Tanaka, R.; Hirano, S.; Urabe, H.; Sato, F. Org. Lett. 2003, 5, 67; (c) Witulski, B.; Lumtscher, J.; Bergsträßer, U. Synlett 2003, 708; (d) Naud, S.; Cintrat, J.-C. Synthesis 2003, 1391; (e) Witulski, B.; Alayrac, C. Angew. Chem., Int. Ed. 2002, 41, 3281; (f) Saito, N.; Sato, Y.; Mori, M. Org. Lett. 2002, 4, 803; (g) Timbert, J.-C.; Cintrat, J.-C. Chem. Eur. J. 2002, 8, 1637; (h) Minière, S.; Cintrat, J.-C. Synthesis 2001, 705; (i) Minière, S.; Cintrat, J.-C. J. Org. Chem. 2001, 66, 7385; (j) Hoffmann, R. W.; Brückner, D. New. J. Chem. 2001, 25, 369; (k) For citations that appeared before 2001, see Refs. 1a and 1b.
9. For recent efforts in synthesis and applications of ynamides, see: (a) Witulski, B.; Alayrac, C.; Tevzaadze-Saeftel, L. Angew. Chem., Int. Ed. 2003, 42, 4257; (b) Tanaka, R.; Hirano, S.; Urabe, H.; Sato, F. Org. Lett. 2003, 5, 67; (c) Witulski, B.; Lumtscher, J.; Bergsträßer, U. Synlett 2003, 708; (d) Naud, S.; Cintrat, J.-C. Synthesis 2003, 1391; (e) Witulski, B.; Alayrac, C. Angew. Chem., Int. Ed. 2002, 41, 3281; (f) Saito, N.; Sato, Y.; Mori, M. Org. Lett. 2002, 4, 803; (g) Timbert, J.-C.; Cintrat, J.-C. Chem. Eur. J. 2002, 8, 1637; (h) Minière, S.; Cintrat, J.-C. Synthesis 2001, 705; (i) Minière, S.; Cintrat, J.-C. J. Org. Chem. 2001, 66, 7385; (j) Hoffmann, R. W.; Brückner, D. New. J. Chem. 2001, 25, 369; (k) For citations that appeared before 2001, see Refs. 1a and 1b.
10. For recent efforts in synthesis and applications of ynamides, see: (a) Witulski, B.; Alayrac, C.; Tevzaadze-Saeftel, L. Angew. Chem., Int. Ed. 2003, 42, 4257; (b) Tanaka, R.; Hirano, S.; Urabe, H.; Sato, F. Org. Lett. 2003, 5, 67; (c) Witulski, B.; Lumtscher, J.; Bergsträßer, U. Synlett 2003, 708; (d) Naud, S.; Cintrat, J.-C. Synthesis 2003, 1391; (e) Witulski, B.; Alayrac, C. Angew. Chem., Int. Ed. 2002, 41, 3281; (f) Saito, N.; Sato, Y.; Mori, M. Org. Lett. 2002, 4, 803; (g) Timbert, J.-C.; Cintrat, J.-C. Chem. Eur. J. 2002, 8, 1637; (h) Minière, S.; Cintrat, J.-C. Synthesis 2001, 705; (i) Minière, S.; Cintrat, J.-C. J. Org. Chem. 2001, 66, 7385; (j) Hoffmann, R. W.; Brückner, D. New. J. Chem. 2001, 25, 369; (k) For citations that appeared before 2001, see Refs. 1a and 1b.
11. For recent efforts in synthesis and applications of ynamides, see: (a) Witulski, B.; Alayrac, C.; Tevzaadze-Saeftel, L. Angew. Chem., Int. Ed. 2003, 42, 4257; (b) Tanaka, R.; Hirano, S.; Urabe, H.; Sato, F. Org. Lett. 2003, 5, 67; (c) Witulski, B.; Lumtscher, J.; Bergsträßer, U. Synlett 2003, 708; (d) Naud, S.; Cintrat, J.-C. Synthesis 2003, 1391; (e) Witulski, B.; Alayrac, C. Angew. Chem., Int. Ed. 2002, 41, 3281; (f) Saito, N.; Sato, Y.; Mori, M. Org. Lett. 2002, 4, 803; (g) Timbert, J.-C.; Cintrat, J.-C. Chem. Eur. J. 2002, 8, 1637; (h) Minière, S.; Cintrat, J.-C. Synthesis 2001, 705; (i) Minière, S.; Cintrat, J.-C. J. Org. Chem. 2001, 66, 7385; (j) Hoffmann, R. W.; Brückner, D. New. J. Chem. 2001, 25, 369; (k) For citations that appeared before 2001, see Refs. 1a and 1b.
12. For recent efforts in synthesis and applications of ynamides, see: (a) Witulski, B.; Alayrac, C.; Tevzaadze-Saeftel, L. Angew. Chem., Int. Ed. 2003, 42, 4257; (b) Tanaka, R.; Hirano, S.; Urabe, H.; Sato, F. Org. Lett. 2003, 5, 67; (c) Witulski, B.; Lumtscher, J.; Bergsträßer, U. Synlett 2003, 708; (d) Naud, S.; Cintrat, J.-C. Synthesis 2003, 1391; (e) Witulski, B.; Alayrac, C. Angew. Chem., Int. Ed. 2002, 41, 3281; (f) Saito, N.; Sato, Y.; Mori, M. Org. Lett. 2002, 4, 803; (g) Timbert, J.-C.; Cintrat, J.-C. Chem. Eur. J. 2002, 8, 1637; (h) Minière, S.; Cintrat, J.-C. Synthesis 2001, 705; (i) Minière, S.; Cintrat, J.-C. J. Org. Chem. 2001, 66, 7385; (j) Hoffmann, R. W.; Brückner, D. New. J. Chem. 2001, 25, 369; (k) For citations that appeared before 2001, see Refs. 1a and 1b.
13. For recent efforts in synthesis and applications of ynamides, see: (a) Witulski, B.; Alayrac, C.; Tevzaadze-Saeftel, L. Angew. Chem., Int. Ed. 2003, 42, 4257; (b) Tanaka, R.; Hirano, S.; Urabe, H.; Sato, F. Org. Lett. 2003, 5, 67; (c) Witulski, B.; Lumtscher, J.; Bergsträßer, U. Synlett 2003, 708; (d) Naud, S.; Cintrat, J.-C. Synthesis 2003, 1391; (e) Witulski, B.; Alayrac, C. Angew. Chem., Int. Ed. 2002, 41, 3281; (f) Saito, N.; Sato, Y.; Mori, M. Org. Lett. 2002, 4, 803; (g) Timbert, J.-C.; Cintrat, J.-C. Chem. Eur. J. 2002, 8, 1637; (h) Minière, S.; Cintrat, J.-C. Synthesis 2001, 705; (i) Minière, S.; Cintrat, J.-C. J. Org. Chem. 2001, 66, 7385; (j) Hoffmann, R. W.; Brückner, D. New. J. Chem. 2001, 25, 369; (k) For citations that appeared before 2001, see Refs. 1a and 1b.
14. For recent efforts in synthesis and applications of ynamides, see: (a) Witulski, B.; Alayrac, C.; Tevzaadze-Saeftel, L. Angew. Chem., Int. Ed. 2003, 42, 4257; (b) Tanaka, R.; Hirano, S.; Urabe, H.; Sato, F. Org. Lett. 2003, 5, 67; (c) Witulski, B.; Lumtscher, J.; Bergsträßer, U. Synlett 2003, 708; (d) Naud, S.; Cintrat, J.-C. Synthesis 2003, 1391; (e) Witulski, B.; Alayrac, C. Angew. Chem., Int. Ed. 2002, 41, 3281; (f) Saito, N.; Sato, Y.; Mori, M. Org. Lett. 2002, 4, 803; (g) Timbert, J.-C.; Cintrat, J.-C. Chem. Eur. J. 2002, 8, 1637; (h) Minière, S.; Cintrat, J.-C. Synthesis 2001, 705; (i) Minière, S.; Cintrat, J.-C. J. Org. Chem. 2001, 66, 7385; (j) Hoffmann, R. W.; Brückner, D. New. J. Chem. 2001, 25, 369; (k) For citations that appeared before 2001, see Refs. 1a and 1b.
15. For our syntheses of ynamides, see: (a) Frederick, M. O.; Mulder, J. A.; Tracey, M. R.; Hsung, R. P.; Huang, J.; Kurtz, K. C. M.; Shen, L.; Douglas, C. J. J. Am. Chem. Soc. 2003, 125, 2368; (b) For a related account, see: Dunetz, J. R.; Danheiser, R. L. Org. Lett. 2003, 5, 4011.
16. For our syntheses of ynamides, see: (a) Frederick, M. O.; Mulder, J. A.; Tracey, M. R.; Hsung, R. P.; Huang, J.; Kurtz, K. C. M.; Shen, L.; Douglas, C. J. J. Am. Chem. Soc. 2003, 125, 2368; (b) For a related account, see: Dunetz, J. R.; Danheiser, R. L. Org. Lett. 2003, 5, 4011.
17. For our applications of ynamides, see: (a) Frederick, M. O; Hsung, R. P. ; Lambeth, R. H.; Mulder, J. A. Tracey, M. R. Org. Lett. 2003, 5, 2663; (b) Mulder, J. A.; Kurtz, K. C. M.; Hsung, R. P.; Coverdale, H. A.; Frederick, M. O.; Shen, L.; Zificsak, C. A. Org. Lett. 2003, 5, 1547; (c) Huang, J.; Xiong, H.; Hsung, R. P.; Rameshkumar, C.; Mulder, J. A.; Grebe, T. P. Org. Lett. 2002, 4, 2417; (d) Mulder, J. A.; Hsung, R. P.; Frederick, M. O.; Tracey, M. R.; Zificsak, C. A. Org. Lett. 2002, 4, 1383; (e) Wei, L.-L.; Mulder, J. A.; Xiong, H.; Zificsak, C. A.; Douglas, C. J.; Hsung, R. P. Tetrahedron 2001, 57, 459; (f) Hsung, R. P.; Zificsak, C.; Wei, L.-L.; Douglas, C. J.; Xiong, H.; Mulder, J. Org. Lett. 1999, 1, 1237.
18. For our applications of ynamides, see: (a) Frederick, M. O; Hsung, R. P. ; Lambeth, R. H.; Mulder, J. A. Tracey, M. R. Org. Lett. 2003, 5, 2663; (b) Mulder, J. A.; Kurtz, K. C. M.; Hsung, R. P.; Coverdale, H. A.; Frederick, M. O.; Shen, L.; Zificsak, C. A. Org. Lett. 2003, 5, 1547; (c) Huang, J.; Xiong, H.; Hsung, R. P.; Rameshkumar, C.; Mulder, J. A.; Grebe, T. P. Org. Lett. 2002, 4, 2417; (d) Mulder, J. A.; Hsung, R. P.; Frederick, M. O.; Tracey, M. R.; Zificsak, C. A. Org. Lett. 2002, 4, 1383; (e) Wei, L.-L.; Mulder, J. A.; Xiong, H.; Zificsak, C. A.; Douglas, C. J.; Hsung, R. P. Tetrahedron 2001, 57, 459; (f) Hsung, R. P.; Zificsak, C.; Wei, L.-L.; Douglas, C. J.; Xiong, H.; Mulder, J. Org. Lett. 1999, 1, 1237.
19. For our applications of ynamides, see: (a) Frederick, M. O; Hsung, R. P. ; Lambeth, R. H.; Mulder, J. A. Tracey, M. R. Org. Lett. 2003, 5, 2663; (b) Mulder, J. A.; Kurtz, K. C. M.; Hsung, R. P.; Coverdale, H. A.; Frederick, M. O.; Shen, L.; Zificsak, C. A. Org. Lett. 2003, 5, 1547; (c) Huang, J.; Xiong, H.; Hsung, R. P.; Rameshkumar, C.; Mulder, J. A.; Grebe, T. P. Org. Lett. 2002, 4, 2417; (d) Mulder, J. A.; Hsung, R. P.; Frederick, M. O.; Tracey, M. R.; Zificsak, C. A. Org. Lett. 2002, 4, 1383; (e) Wei, L.-L.; Mulder, J. A.; Xiong, H.; Zificsak, C. A.; Douglas, C. J.; Hsung, R. P. Tetrahedron 2001, 57, 459; (f) Hsung, R. P.; Zificsak, C.; Wei, L.-L.; Douglas, C. J.; Xiong, H.; Mulder, J. Org. Lett. 1999, 1, 1237.
20. For our applications of ynamides, see: (a) Frederick, M. O; Hsung, R. P. ; Lambeth, R. H.; Mulder, J. A. Tracey, M. R. Org. Lett. 2003, 5, 2663; (b) Mulder, J. A.; Kurtz, K. C. M.; Hsung, R. P.; Coverdale, H. A.; Frederick, M. O.; Shen, L.; Zificsak, C. A. Org. Lett. 2003, 5, 1547; (c) Huang, J.; Xiong, H.; Hsung, R. P.; Rameshkumar, C.; Mulder, J. A.; Grebe, T. P. Org. Lett. 2002, 4, 2417; (d) Mulder, J. A.; Hsung, R. P.; Frederick, M. O.; Tracey, M. R.; Zificsak, C. A. Org. Lett. 2002, 4, 1383; (e) Wei, L.-L.; Mulder, J. A.; Xiong, H.; Zificsak, C. A.; Douglas, C. J.; Hsung, R. P. Tetrahedron 2001, 57, 459; (f) Hsung, R. P.; Zificsak, C.; Wei, L.-L.; Douglas, C. J.; Xiong, H.; Mulder, J. Org. Lett. 1999, 1, 1237.
21. For our applications of ynamides, see: (a) Frederick, M. O; Hsung, R. P. ; Lambeth, R. H.; Mulder, J. A. Tracey, M. R. Org. Lett. 2003, 5, 2663; (b) Mulder, J. A.; Kurtz, K. C. M.; Hsung, R. P.; Coverdale, H. A.; Frederick, M. O.; Shen, L.; Zificsak, C. A. Org. Lett. 2003, 5, 1547; (c) Huang, J.; Xiong, H.; Hsung, R. P.; Rameshkumar, C.; Mulder, J. A.; Grebe, T. P. Org. Lett. 2002, 4, 2417; (d) Mulder, J. A.; Hsung, R. P.; Frederick, M. O.; Tracey, M. R.; Zificsak, C. A. Org. Lett. 2002, 4, 1383; (e) Wei, L.-L.; Mulder, J. A.; Xiong, H.; Zificsak, C. A.; Douglas, C. J.; Hsung, R. P. Tetrahedron 2001, 57, 459; (f) Hsung, R. P.; Zificsak, C.; Wei, L.-L.; Douglas, C. J.; Xiong, H.; Mulder, J. Org. Lett. 1999, 1, 1237.
22. For our applications of ynamides, see: (a) Frederick, M. O; Hsung, R. P. ; Lambeth, R. H.; Mulder, J. A. Tracey, M. R. Org. Lett. 2003, 5, 2663; (b) Mulder, J. A.; Kurtz, K. C. M.; Hsung, R. P.; Coverdale, H. A.; Frederick, M. O.; Shen, L.; Zificsak, C. A. Org. Lett. 2003, 5, 1547; (c) Huang, J.; Xiong, H.; Hsung, R. P.; Rameshkumar, C.; Mulder, J. A.; Grebe, T. P. Org. Lett. 2002, 4, 2417; (d) Mulder, J. A.; Hsung, R. P.; Frederick, M. O.; Tracey, M. R.; Zificsak, C. A. Org. Lett. 2002, 4, 1383; (e) Wei, L.-L.; Mulder, J. A.; Xiong, H.; Zificsak, C. A.; Douglas, C. J.; Hsung, R. P. Tetrahedron 2001, 57, 459; (f) Hsung, R. P.; Zificsak, C.; Wei, L.-L.; Douglas, C. J.; Xiong, H.; Mulder, J. Org. Lett. 1999, 1, 1237.
23. For reviews on chemistry of ynamines, see: (a) Himbert, G. In Methoden Der Organischen Chemie (Houben-Weyl); Kropf, H.; Schaumann, E., Eds.; Georg Thieme Verlag: Stuttgart, 1993; pp. 3267-3443; (b) Collard-Motte, J.; Janousek, Z. Top. Curr. Chem. 1986, 130, 89; (c) Ficini, J. Tetrahedron 1976, 32, 1448.
24. For reviews on chemistry of ynamines, see: (a) Himbert, G. In Methoden Der Organischen Chemie (Houben-Weyl); Kropf, H.; Schaumann, E., Eds.; Georg Thieme Verlag: Stuttgart, 1993; pp. 3267-3443; (b) Collard-Motte, J.; Janousek, Z. Top. Curr. Chem. 1986, 130, 89; (c) Ficini, J. Tetrahedron 1976, 32, 1448.
25. For reviews on chemistry of ynamines, see: (a) Himbert, G. In Methoden Der Organischen Chemie (Houben-Weyl); Kropf, H.; Schaumann, E., Eds.; Georg Thieme Verlag: Stuttgart, 1993; pp. 3267-3443; (b) Collard-Motte, J.; Janousek, Z. Top. Curr. Chem. 1986, 130, 89; (c) Ficini, J. Tetrahedron 1976, 32, 1448.
26. For the only account using chiral ynamines before 1997, see: (a) van Elburg, P. A.; Honig, G. W. N.; Reinhoudt, D. N. Tetrahedron Lett. 1987, 28, 6397; (b) For a recent account using ynamines to prepare optically enriched γ-butanolides, see: (b) Movassaghi, M.; Jasobsen, E. N. J. Am. Chem. Soc. 2002, 124, 2456.
27. For the only account using chiral ynamines before 1997, see: (a) van Elburg, P. A.; Honig, G. W. N.; Reinhoudt, D. N. Tetrahedron Lett. 1987, 28, 6397; (b) For a recent account using ynamines to prepare optically enriched γ-butanolides, see: (b) Movassaghi, M.; Jasobsen, E. N. J. Am. Chem. Soc. 2002, 124, 2456.
28. For the recent two accounts of chemistry of chiral ynamines, see: (a) Balsells, J.; Vázquez, J.; Moyano, A.; Pericàs, M. A.; Riera, A. J. Org. Chem. 2000, 65, 7291; (b) Roth, G.; Reindl, D.; Gockel, M.; Troll, C.; Fischer, H. Organometallics. 1998, 17, 1393; (c) Fischer, H.; Podschadly, O.; Roth, G.; Herminghaus, S.; Klewitz, S.; Heck, J.; Houbrechts, S.; Meyer, T. J. Organomet. Chem. 1997, 541, 321.
29. For the recent two accounts of chemistry of chiral ynamines, see: (a) Balsells, J.; Vázquez, J.; Moyano, A.; Pericàs, M. A.; Riera, A. J. Org. Chem. 2000, 65, 7291; (b) Roth, G.; Reindl, D.; Gockel, M.; Troll, C.; Fischer, H. Organometallics. 1998, 17, 1393; (c) Fischer, H.; Podschadly, O.; Roth, G.; Herminghaus, S.; Klewitz, S.; Heck, J.; Houbrechts, S.; Meyer, T. J. Organomet. Chem. 1997, 541, 321.
30. For the recent two accounts of chemistry of chiral ynamines, see: (a) Balsells, J.; Vázquez, J.; Moyano, A.; Pericàs, M. A.; Riera, A. J. Org. Chem. 2000, 65, 7291; (b) Roth, G.; Reindl, D.; Gockel, M.; Troll, C.; Fischer, H. Organometallics. 1998, 17, 1393; (c) Fischer, H.; Podschadly, O.; Roth, G.; Herminghaus, S.; Klewitz, S.; Heck, J.; Houbrechts, S.; Meyer, T. J. Organomet. Chem. 1997, 541, 321.
31. For the only intramolecular reaction using ynamine, see: Genet J.P., Kahn P., Ficini J. Tetrahedron Lett. 21:1980;1521.
32. For reviews, see: (a) Brummond, K. M.; Kent, J. L. Tetrahedron 2000, 56, 3263; (b) Comely, A. C.; Gibson, S. E. J. Chem. Soc., Perkin Trans. 1 1999, 223; (c) Chung, Y. K. Coord. Chem. Rev. 1999, 188, 297; (d) Geis, O.; Schmalz, H.-G. Angew. Chem., Int. Ed. 1998, 37, 911; (e) Lautens, M.; Klute, W.; Tam, W. Chem. Rev. 1996, 96, 49; (f) Ojima, I.; Tzamarioudaki, M.; Li, Z.; Donovan, R. J. Chem. Rev. 1996, 96, 635; (g) Frühauf, H.-W. Chem. Rev. 1997, 97, 523; (h) Schore, N. E. Comprehensiv Organometallic Chemistry II; Hegedus, L. S., Ed. ; Oxford: Pergamon, 1995; Vol. 12, pp. 703-739; (i) Schore, N. E. Chem. Rev. 1988, 88, 1081.
33. For reviews, see: (a) Brummond, K. M.; Kent, J. L. Tetrahedron 2000, 56, 3263; (b) Comely, A. C.; Gibson, S. E. J. Chem. Soc., Perkin Trans. 1 1999, 223; (c) Chung, Y. K. Coord. Chem. Rev. 1999, 188, 297; (d) Geis, O.; Schmalz, H.-G. Angew. Chem., Int. Ed. 1998, 37, 911; (e) Lautens, M.; Klute, W.; Tam, W. Chem. Rev. 1996, 96, 49; (f) Ojima, I.; Tzamarioudaki, M.; Li, Z.; Donovan, R. J. Chem. Rev. 1996, 96, 635; (g) Frühauf, H.-W. Chem. Rev. 1997, 97, 523; (h) Schore, N. E. Comprehensiv Organometallic Chemistry II; Hegedus, L. S., Ed. ; Oxford: Pergamon, 1995; Vol. 12, pp. 703-739; (i) Schore, N. E. Chem. Rev. 1988, 88, 1081.
34. For reviews, see: (a) Brummond, K. M.; Kent, J. L. Tetrahedron 2000, 56, 3263; (b) Comely, A. C.; Gibson, S. E. J. Chem. Soc., Perkin Trans. 1 1999, 223; (c) Chung, Y. K. Coord. Chem. Rev. 1999, 188, 297; (d) Geis, O.; Schmalz, H.-G. Angew. Chem., Int. Ed. 1998, 37, 911; (e) Lautens, M.; Klute, W.; Tam, W. Chem. Rev. 1996, 96, 49; (f) Ojima, I.; Tzamarioudaki, M.; Li, Z.; Donovan, R. J. Chem. Rev. 1996, 96, 635; (g) Frühauf, H.-W. Chem. Rev. 1997, 97, 523; (h) Schore, N. E. Comprehensiv Organometallic Chemistry II; Hegedus, L. S., Ed. ; Oxford: Pergamon, 1995; Vol. 12, pp. 703-739; (i) Schore, N. E. Chem. Rev. 1988, 88, 1081.
35. For reviews, see: (a) Brummond, K. M.; Kent, J. L. Tetrahedron 2000, 56, 3263; (b) Comely, A. C.; Gibson, S. E. J. Chem. Soc., Perkin Trans. 1 1999, 223; (c) Chung, Y. K. Coord. Chem. Rev. 1999, 188, 297; (d) Geis, O.; Schmalz, H.-G. Angew. Chem., Int. Ed. 1998, 37, 911; (e) Lautens, M.; Klute, W.; Tam, W. Chem. Rev. 1996, 96, 49; (f) Ojima, I.; Tzamarioudaki, M.; Li, Z.; Donovan, R. J. Chem. Rev. 1996, 96, 635; (g) Frühauf, H.-W. Chem. Rev. 1997, 97, 523; (h) Schore, N. E. Comprehensiv Organometallic Chemistry II; Hegedus, L. S., Ed. ; Oxford: Pergamon, 1995; Vol. 12, pp. 703-739; (i) Schore, N. E. Chem. Rev. 1988, 88, 1081.
36. For reviews, see: (a) Brummond, K. M.; Kent, J. L. Tetrahedron 2000, 56, 3263; (b) Comely, A. C.; Gibson, S. E. J. Chem. Soc., Perkin Trans. 1 1999, 223; (c) Chung, Y. K. Coord. Chem. Rev. 1999, 188, 297; (d) Geis, O.; Schmalz, H.-G. Angew. Chem., Int. Ed. 1998, 37, 911; (e) Lautens, M.; Klute, W.; Tam, W. Chem. Rev. 1996, 96, 49; (f) Ojima, I.; Tzamarioudaki, M.; Li, Z.; Donovan, R. J. Chem. Rev. 1996, 96, 635; (g) Frühauf, H.-W. Chem. Rev. 1997, 97, 523; (h) Schore, N. E. Comprehensiv Organometallic Chemistry II; Hegedus, L. S., Ed. ; Oxford: Pergamon, 1995; Vol. 12, pp. 703-739; (i) Schore, N. E. Chem. Rev. 1988, 88, 1081.
37. For reviews, see: (a) Brummond, K. M.; Kent, J. L. Tetrahedron 2000, 56, 3263; (b) Comely, A. C.; Gibson, S. E. J. Chem. Soc., Perkin Trans. 1 1999, 223; (c) Chung, Y. K. Coord. Chem. Rev. 1999, 188, 297; (d) Geis, O.; Schmalz, H.-G. Angew. Chem., Int. Ed. 1998, 37, 911; (e) Lautens, M.; Klute, W.; Tam, W. Chem. Rev. 1996, 96, 49; (f) Ojima, I.; Tzamarioudaki, M.; Li, Z.; Donovan, R. J. Chem. Rev. 1996, 96, 635; (g) Frühauf, H.-W. Chem. Rev. 1997, 97, 523; (h) Schore, N. E. Comprehensiv Organometallic Chemistry II; Hegedus, L. S., Ed. ; Oxford: Pergamon, 1995; Vol. 12, pp. 703-739; (i) Schore, N. E. Chem. Rev. 1988, 88, 1081.
38. For reviews, see: (a) Brummond, K. M.; Kent, J. L. Tetrahedron 2000, 56, 3263; (b) Comely, A. C.; Gibson, S. E. J. Chem. Soc., Perkin Trans. 1 1999, 223; (c) Chung, Y. K. Coord. Chem. Rev. 1999, 188, 297; (d) Geis, O.; Schmalz, H.-G. Angew. Chem., Int. Ed. 1998, 37, 911; (e) Lautens, M.; Klute, W.; Tam, W. Chem. Rev. 1996, 96, 49; (f) Ojima, I.; Tzamarioudaki, M.; Li, Z.; Donovan, R. J. Chem. Rev. 1996, 96, 635; (g) Frühauf, H.-W. Chem. Rev. 1997, 97, 523; (h) Schore, N. E. Comprehensiv Organometallic Chemistry II; Hegedus, L. S., Ed. ; Oxford: Pergamon, 1995; Vol. 12, pp. 703-739; (i) Schore, N. E. Chem. Rev. 1988, 88, 1081.
39. For reviews, see: (a) Brummond, K. M.; Kent, J. L. Tetrahedron 2000, 56, 3263; (b) Comely, A. C.; Gibson, S. E. J. Chem. Soc., Perkin Trans. 1 1999, 223; (c) Chung, Y. K. Coord. Chem. Rev. 1999, 188, 297; (d) Geis, O.; Schmalz, H.-G. Angew. Chem., Int. Ed. 1998, 37, 911; (e) Lautens, M.; Klute, W.; Tam, W. Chem. Rev. 1996, 96, 49; (f) Ojima, I.; Tzamarioudaki, M.; Li, Z.; Donovan, R. J. Chem. Rev. 1996, 96, 635; (g) Frühauf, H.-W. Chem. Rev. 1997, 97, 523; (h) Schore, N. E. Comprehensiv Organometallic Chemistry II; Hegedus, L. S., Ed. ; Oxford: Pergamon, 1995; Vol. 12, pp. 703-739; (i) Schore, N. E. Chem. Rev. 1988, 88, 1081.
40. For reviews, see: (a) Brummond, K. M.; Kent, J. L. Tetrahedron 2000, 56, 3263; (b) Comely, A. C.; Gibson, S. E. J. Chem. Soc., Perkin Trans. 1 1999, 223; (c) Chung, Y. K. Coord. Chem. Rev. 1999, 188, 297; (d) Geis, O.; Schmalz, H.-G. Angew. Chem., Int. Ed. 1998, 37, 911; (e) Lautens, M.; Klute, W.; Tam, W. Chem. Rev. 1996, 96, 49; (f) Ojima, I.; Tzamarioudaki, M.; Li, Z.; Donovan, R. J. Chem. Rev. 1996, 96, 635; (g) Frühauf, H.-W. Chem. Rev. 1997, 97, 523; (h) Schore, N. E. Comprehensiv Organometallic Chemistry II; Hegedus, L. S., Ed. ; Oxford: Pergamon, 1995; Vol. 12, pp. 703-739; (i) Schore, N. E. Chem. Rev. 1988, 88, 1081.
41. Rainier J.D., Imbriglio J.E. J. Org. Chem. 65:2000;7272.
42. Rainier J.D., Imbriglio J.E. Org. Lett. 1:1999;2037.
43. Witulski B., Gößmann M. Synlett. 2000;1793.
44. Witulski B., Gößmann M. Chem. Commun. 1999;1879.
45. Witulski B., Stengel T. Angew. Chem., Int. Ed. 37:1998;489.
46. Schottelius M.J., Chen P. Helv. Chim. Acta. 81:1998;2341.
47. For some recent examples of Pauson-Khand type cycloadditions, see: (a) Reichwein, J. F.; Iacono, S. T.; Pagenkopf, B. L. Tetrahedron Lett. 2002, 43, 3813; (b) Brummond, K. M.; Wan, H.; Kent, J. L. J. Org. Chem. 1998, 63, 6535; (c) Brummond, K. M.; Wan, H. Tetrahedron Lett. 1998, 39, 931; (d) Hicks, F. A.; Buchwald, S. L. J. Am. Chem. Soc. 1999, 121, 7026; (e) Hicks, F. A.; Kablaoui, N. M.; Buchwald, S. L. J. Am. Chem. Soc. 1999, 121, 5881; (f) Belanger, D. B.; O'Mahony, D. J.; Livinghouse, T. Tetrahedron Lett. 1998, 39, 7637 and 7641; (g) Ahmar, M.; Locatelli, C.; Colombier, D.; Cazes, B. Tetrahedron Lett. 1997, 38, 5281; (h) Pagenkopf, B. L.; Livinghouse, T. J. Am. Chem. Soc. 1996, 118, 2285.
48. For some recent examples of Pauson-Khand type cycloadditions, see: (a) Reichwein, J. F.; Iacono, S. T.; Pagenkopf, B. L. Tetrahedron Lett. 2002, 43, 3813; (b) Brummond, K. M.; Wan, H.; Kent, J. L. J. Org. Chem. 1998, 63, 6535; (c) Brummond, K. M.; Wan, H. Tetrahedron Lett. 1998, 39, 931; (d) Hicks, F. A.; Buchwald, S. L. J. Am. Chem. Soc. 1999, 121, 7026; (e) Hicks, F. A.; Kablaoui, N. M.; Buchwald, S. L. J. Am. Chem. Soc. 1999, 121, 5881; (f) Belanger, D. B.; O'Mahony, D. J.; Livinghouse, T. Tetrahedron Lett. 1998, 39, 7637 and 7641; (g) Ahmar, M.; Locatelli, C.; Colombier, D.; Cazes, B. Tetrahedron Lett. 1997, 38, 5281; (h) Pagenkopf, B. L.; Livinghouse, T. J. Am. Chem. Soc. 1996, 118, 2285.
49. For some recent examples of Pauson-Khand type cycloadditions, see: (a) Reichwein, J. F.; Iacono, S. T.; Pagenkopf, B. L. Tetrahedron Lett. 2002, 43, 3813; (b) Brummond, K. M.; Wan, H.; Kent, J. L. J. Org. Chem. 1998, 63, 6535; (c) Brummond, K. M.; Wan, H. Tetrahedron Lett. 1998, 39, 931; (d) Hicks, F. A.; Buchwald, S. L. J. Am. Chem. Soc. 1999, 121, 7026; (e) Hicks, F. A.; Kablaoui, N. M.; Buchwald, S. L. J. Am. Chem. Soc. 1999, 121, 5881; (f) Belanger, D. B.; O'Mahony, D. J.; Livinghouse, T. Tetrahedron Lett. 1998, 39, 7637 and 7641; (g) Ahmar, M.; Locatelli, C.; Colombier, D.; Cazes, B. Tetrahedron Lett. 1997, 38, 5281; (h) Pagenkopf, B. L.; Livinghouse, T. J. Am. Chem. Soc. 1996, 118, 2285.
50. For some recent examples of Pauson-Khand type cycloadditions, see: (a) Reichwein, J. F.; Iacono, S. T.; Pagenkopf, B. L. Tetrahedron Lett. 2002, 43, 3813; (b) Brummond, K. M.; Wan, H.; Kent, J. L. J. Org. Chem. 1998, 63, 6535; (c) Brummond, K. M.; Wan, H. Tetrahedron Lett. 1998, 39, 931; (d) Hicks, F. A.; Buchwald, S. L. J. Am. Chem. Soc. 1999, 121, 7026; (e) Hicks, F. A.; Kablaoui, N. M.; Buchwald, S. L. J. Am. Chem. Soc. 1999, 121, 5881; (f) Belanger, D. B.; O'Mahony, D. J.; Livinghouse, T. Tetrahedron Lett. 1998, 39, 7637 and 7641; (g) Ahmar, M.; Locatelli, C.; Colombier, D.; Cazes, B. Tetrahedron Lett. 1997, 38, 5281; (h) Pagenkopf, B. L.; Livinghouse, T. J. Am. Chem. Soc. 1996, 118, 2285.
51. For some recent examples of Pauson-Khand type cycloadditions, see: (a) Reichwein, J. F.; Iacono, S. T.; Pagenkopf, B. L. Tetrahedron Lett. 2002, 43, 3813; (b) Brummond, K. M.; Wan, H.; Kent, J. L. J. Org. Chem. 1998, 63, 6535; (c) Brummond, K. M.; Wan, H. Tetrahedron Lett. 1998, 39, 931; (d) Hicks, F. A.; Buchwald, S. L. J. Am. Chem. Soc. 1999, 121, 7026; (e) Hicks, F. A.; Kablaoui, N. M.; Buchwald, S. L. J. Am. Chem. Soc. 1999, 121, 5881; (f) Belanger, D. B.; O'Mahony, D. J.; Livinghouse, T. Tetrahedron Lett. 1998, 39, 7637 and 7641; (g) Ahmar, M.; Locatelli, C.; Colombier, D.; Cazes, B. Tetrahedron Lett. 1997, 38, 5281; (h) Pagenkopf, B. L.; Livinghouse, T. J. Am. Chem. Soc. 1996, 118, 2285.
52. For some recent examples of Pauson-Khand type cycloadditions, see: (a) Reichwein, J. F.; Iacono, S. T.; Pagenkopf, B. L. Tetrahedron Lett. 2002, 43, 3813; (b) Brummond, K. M.; Wan, H.; Kent, J. L. J. Org. Chem. 1998, 63, 6535; (c) Brummond, K. M.; Wan, H. Tetrahedron Lett. 1998, 39, 931; (d) Hicks, F. A.; Buchwald, S. L. J. Am. Chem. Soc. 1999, 121, 7026; (e) Hicks, F. A.; Kablaoui, N. M.; Buchwald, S. L. J. Am. Chem. Soc. 1999, 121, 5881; (f) Belanger, D. B.; O'Mahony, D. J.; Livinghouse, T. Tetrahedron Lett. 1998, 39, 7637 and 7641; (g) Ahmar, M.; Locatelli, C.; Colombier, D.; Cazes, B. Tetrahedron Lett. 1997, 38, 5281; (h) Pagenkopf, B. L.; Livinghouse, T. J. Am. Chem. Soc. 1996, 118, 2285.
53. For some recent examples of Pauson-Khand type cycloadditions, see: (a) Reichwein, J. F.; Iacono, S. T.; Pagenkopf, B. L. Tetrahedron Lett. 2002, 43, 3813; (b) Brummond, K. M.; Wan, H.; Kent, J. L. J. Org. Chem. 1998, 63, 6535; (c) Brummond, K. M.; Wan, H. Tetrahedron Lett. 1998, 39, 931; (d) Hicks, F. A.; Buchwald, S. L. J. Am. Chem. Soc. 1999, 121, 7026; (e) Hicks, F. A.; Kablaoui, N. M.; Buchwald, S. L. J. Am. Chem. Soc. 1999, 121, 5881; (f) Belanger, D. B.; O'Mahony, D. J.; Livinghouse, T. Tetrahedron Lett. 1998, 39, 7637 and 7641; (g) Ahmar, M.; Locatelli, C.; Colombier, D.; Cazes, B. Tetrahedron Lett. 1997, 38, 5281; (h) Pagenkopf, B. L.; Livinghouse, T. J. Am. Chem. Soc. 1996, 118, 2285.
54. For some recent examples of Pauson-Khand type cycloadditions, see: (a) Reichwein, J. F.; Iacono, S. T.; Pagenkopf, B. L. Tetrahedron Lett. 2002, 43, 3813; (b) Brummond, K. M.; Wan, H.; Kent, J. L. J. Org. Chem. 1998, 63, 6535; (c) Brummond, K. M.; Wan, H. Tetrahedron Lett. 1998, 39, 931; (d) Hicks, F. A.; Buchwald, S. L. J. Am. Chem. Soc. 1999, 121, 7026; (e) Hicks, F. A.; Kablaoui, N. M.; Buchwald, S. L. J. Am. Chem. Soc. 1999, 121, 5881; (f) Belanger, D. B.; O'Mahony, D. J.; Livinghouse, T. Tetrahedron Lett. 1998, 39, 7637 and 7641; (g) Ahmar, M.; Locatelli, C.; Colombier, D.; Cazes, B. Tetrahedron Lett. 1997, 38, 5281; (h) Pagenkopf, B. L.; Livinghouse, T. J. Am. Chem. Soc. 1996, 118, 2285.
55. For an example of using chiral ynol ether in Pauson-Khand cycloaddition, see: Verdaguer S., Moyano A., Pericàs M.A., Riera A., Bernardes V., Greene A.E., Alvarez-Larena A., Piniella J.F. J. Am. Chem. Soc. 116:1994;2153.
56. abstract
57. (a) Pagenkopf, B. L.; Belanger, D. B.; O'Mahony, D. J. R.; Livinghouse, T. Synthesis 2000, 1009.
58. Also see: (b) Adrio, J.; Rivero, M. R.; Carretero, J. C. Chem. Eur. J. 2001, 7, 2435; (c) Adrio, J.; Rivero, M. R.; Carretero, J. C. Angew. Chem., Int. Ed. 2000, 39, 2906.
59. Also see: (b) Adrio, J.; Rivero, M. R.; Carretero, J. C. Chem. Eur. J. 2001, 7, 2435; (c) Adrio, J.; Rivero, M. R.; Carretero, J. C. Angew. Chem., Int. Ed. 2000, 39, 2906.
60. Rios R., Pericàs M.A., Moyano A., Maestro M.A., Mahía J. Org. Lett. 4:2002;1205.
61. Evans D.A. Aldrichim. Acta. 15:1982;23.
62. Heathcock C.H. Aldrichim. Acta. 23:1990;99.
63. Despite being modest, the overall yield implies the cycloaddition step occurred in about 60% since our best yield for the formation of the cobalt complex is around 50%. This is the case with later examples as well.
64. The endo/exo stereochemistry in 26 was not vigorously assigned.
65. We did use other alkenes such as cyclopentene, cyclohexene, and allyl alcohol. Unfortunately, they all led to their respective cycloadducts in ≤10% yield. We are currently examining this limitation.
66. The exo stereochemistry in 29 was assigned using NOE.
67. For an example, see: Powers T.S., Wulff W.D., Quinn J., Shi Y., Jiang W.Q., Hsung R.P., Parisi M., Rahm A., Jiang X.W., Yap G.A., Rheingold A.L. J. Organomet. Chem. 617:2001;182.