Carboxylation and Mitsunobu reaction of amines to give carbamates: Retention vs inversion of configuration is substituent-dependent

Organic Letters

Volumn 6, Issue 17, 2004, Pages 2885-2888

  Dinsmore, Christopher J ^a   Mercer, Swati P ^a  

^a MERCK RESEARCH LABORATORIES   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

AMINE; AMINOALCOHOL; CARBAMIC ACID DERIVATIVE; CARBON; CARBON DIOXIDE; HYDROCARBON SUBSTITUENT; HYDROGEN;

ARTICLE; CARBOXYLATION; MITSUNOBU REACTION; STEREOCHEMISTRY; SUBSTITUTION REACTION; SYNTHESIS;

EID: 4444239165     PISSN: 15237060     EISSN: None     Source Type: Journal    
DOI: 10.1021/ol0491080     Document Type: Article

References (31)

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13. 2, met with limited success, affording only partial conversion of 4a to 6a. For reports of amine carboxylation using carbonate salts, see: (a) Butcher, J. K. Synlett 1994, 825. (b) Inesi, A.; Mucciante, V.; Rossi, L. J. Org. Chem. 1998, 63, 1337. (c) Salvatore, R. N.; Chu. F.; Nagle, A. S.; Kapxhiu, E. A.; Cross, R. M.; Jung, K. W. Tetrahedron 2002, 58, 3329.
14. 2, met with limited success, affording only partial conversion of 4a to 6a. For reports of amine carboxylation using carbonate salts, see: (a) Butcher, J. K. Synlett 1994, 825. (b) Inesi, A.; Mucciante, V.; Rossi, L. J. Org. Chem. 1998, 63, 1337. (c) Salvatore, R. N.; Chu. F.; Nagle, A. S.; Kapxhiu, E. A.; Cross, R. M.; Jung, K. W. Tetrahedron 2002, 58, 3329.
15. 3P and DBAD are added is unknown. See: Hampe, E. M.; Rudkevich, D. M. Tetrahedron 2003, 59, 9619.
16. 3P promoted inversion in the case of 4c → 6c. No secondary amine substrates were evaluated for stereochemical outcome.
17. Retention of configuration in the Mitsunobu reaction: (a) Ahn, C.; DeShong, P. J. Org. Chem. 2002, 67, 1754. (b) Smith, A. B.; Safonov, I. G.; Corbett, R. M. J. Am. Chem. Soc. 2002, 124, 11102. (c) Liao, X.; Wu, Y.; De Brabander, J. K. Angew. Chem., Int. Ed. 2003, 42, 1648.
18. Retention of configuration in the Mitsunobu reaction: (a) Ahn, C.; DeShong, P. J. Org. Chem. 2002, 67, 1754. (b) Smith, A. B.; Safonov, I. G.; Corbett, R. M. J. Am. Chem. Soc. 2002, 124, 11102. (c) Liao, X.; Wu, Y.; De Brabander, J. K. Angew. Chem., Int. Ed. 2003, 42, 1648.
19. Retention of configuration in the Mitsunobu reaction: (a) Ahn, C.; DeShong, P. J. Org. Chem. 2002, 67, 1754. (b) Smith, A. B.; Safonov, I. G.; Corbett, R. M. J. Am. Chem. Soc. 2002, 124, 11102. (c) Liao, X.; Wu, Y.; De Brabander, J. K. Angew. Chem., Int. Ed. 2003, 42, 1648.
20. +) 219.1872; found 219.1875.
21. Mechanistic studies of the Mitsunobu reaction: (a) Hughes, D. L.; Reamer, R. A.; Bergan, J. J.; Grabowski, E. J. J. J. Am. Chem. Soc. 1988, 110, 6487. (b) Camp, D.; Jenkins, I. D. J. Org. Chem. 1989, 54, 3045. (c) Camp, D.; Jenkins, I. D. J. Org. Chem. 1989, 54, 3049. (d) Wilson, S. R.; Perez, J.; Pasternak, A. J. Am. Chem. Soc. 1993, 115, 1994. (e) Hughes, D. L.; Reamer, R. A. J. Org. Chem. 1996, 61, 2967. (f) Ahn, C.; Correia, R.; DeShong, P. J. Org. Chem. 2002, 67, 1751. (g) McNulty, J.; Capretta, A.; Laritchev, V.; Dyck, J.; Robertson, A. J. Angew. Chem., Int. Ed. 2003, 42, 4051.
22. Mechanistic studies of the Mitsunobu reaction: (a) Hughes, D. L.; Reamer, R. A.; Bergan, J. J.; Grabowski, E. J. J. J. Am. Chem. Soc. 1988, 110, 6487. (b) Camp, D.; Jenkins, I. D. J. Org. Chem. 1989, 54, 3045. (c) Camp, D.; Jenkins, I. D. J. Org. Chem. 1989, 54, 3049. (d) Wilson, S. R.; Perez, J.; Pasternak, A. J. Am. Chem. Soc. 1993, 115, 1994. (e) Hughes, D. L.; Reamer, R. A. J. Org. Chem. 1996, 61, 2967. (f) Ahn, C.; Correia, R.; DeShong, P. J. Org. Chem. 2002, 67, 1751. (g) McNulty, J.; Capretta, A.; Laritchev, V.; Dyck, J.; Robertson, A. J. Angew. Chem., Int. Ed. 2003, 42, 4051.
23. Mechanistic studies of the Mitsunobu reaction: (a) Hughes, D. L.; Reamer, R. A.; Bergan, J. J.; Grabowski, E. J. J. J. Am. Chem. Soc. 1988, 110, 6487. (b) Camp, D.; Jenkins, I. D. J. Org. Chem. 1989, 54, 3045. (c) Camp, D.; Jenkins, I. D. J. Org. Chem. 1989, 54, 3049. (d) Wilson, S. R.; Perez, J.; Pasternak, A. J. Am. Chem. Soc. 1993, 115, 1994. (e) Hughes, D. L.; Reamer, R. A. J. Org. Chem. 1996, 61, 2967. (f) Ahn, C.; Correia, R.; DeShong, P. J. Org. Chem. 2002, 67, 1751. (g) McNulty, J.; Capretta, A.; Laritchev, V.; Dyck, J.; Robertson, A. J. Angew. Chem., Int. Ed. 2003, 42, 4051.
24. Mechanistic studies of the Mitsunobu reaction: (a) Hughes, D. L.; Reamer, R. A.; Bergan, J. J.; Grabowski, E. J. J. J. Am. Chem. Soc. 1988, 110, 6487. (b) Camp, D.; Jenkins, I. D. J. Org. Chem. 1989, 54, 3045. (c) Camp, D.; Jenkins, I. D. J. Org. Chem. 1989, 54, 3049. (d) Wilson, S. R.; Perez, J.; Pasternak, A. J. Am. Chem. Soc. 1993, 115, 1994. (e) Hughes, D. L.; Reamer, R. A. J. Org. Chem. 1996, 61, 2967. (f) Ahn, C.; Correia, R.; DeShong, P. J. Org. Chem. 2002, 67, 1751. (g) McNulty, J.; Capretta, A.; Laritchev, V.; Dyck, J.; Robertson, A. J. Angew. Chem., Int. Ed. 2003, 42, 4051.
25. Mechanistic studies of the Mitsunobu reaction: (a) Hughes, D. L.; Reamer, R. A.; Bergan, J. J.; Grabowski, E. J. J. J. Am. Chem. Soc. 1988, 110, 6487. (b) Camp, D.; Jenkins, I. D. J. Org. Chem. 1989, 54, 3045. (c) Camp, D.; Jenkins, I. D. J. Org. Chem. 1989, 54, 3049. (d) Wilson, S. R.; Perez, J.; Pasternak, A. J. Am. Chem. Soc. 1993, 115, 1994. (e) Hughes, D. L.; Reamer, R. A. J. Org. Chem. 1996, 61, 2967. (f) Ahn, C.; Correia, R.; DeShong, P. J. Org. Chem. 2002, 67, 1751. (g) McNulty, J.; Capretta, A.; Laritchev, V.; Dyck, J.; Robertson, A. J. Angew. Chem., Int. Ed. 2003, 42, 4051.
26. Mechanistic studies of the Mitsunobu reaction: (a) Hughes, D. L.; Reamer, R. A.; Bergan, J. J.; Grabowski, E. J. J. J. Am. Chem. Soc. 1988, 110, 6487. (b) Camp, D.; Jenkins, I. D. J. Org. Chem. 1989, 54, 3045. (c) Camp, D.; Jenkins, I. D. J. Org. Chem. 1989, 54, 3049. (d) Wilson, S. R.; Perez, J.; Pasternak, A. J. Am. Chem. Soc. 1993, 115, 1994. (e) Hughes, D. L.; Reamer, R. A. J. Org. Chem. 1996, 61, 2967. (f) Ahn, C.; Correia, R.; DeShong, P. J. Org. Chem. 2002, 67, 1751. (g) McNulty, J.; Capretta, A.; Laritchev, V.; Dyck, J.; Robertson, A. J. Angew. Chem., Int. Ed. 2003, 42, 4051.
27. Mechanistic studies of the Mitsunobu reaction: (a) Hughes, D. L.; Reamer, R. A.; Bergan, J. J.; Grabowski, E. J. J. J. Am. Chem. Soc. 1988, 110, 6487. (b) Camp, D.; Jenkins, I. D. J. Org. Chem. 1989, 54, 3045. (c) Camp, D.; Jenkins, I. D. J. Org. Chem. 1989, 54, 3049. (d) Wilson, S. R.; Perez, J.; Pasternak, A. J. Am. Chem. Soc. 1993, 115, 1994. (e) Hughes, D. L.; Reamer, R. A. J. Org. Chem. 1996, 61, 2967. (f) Ahn, C.; Correia, R.; DeShong, P. J. Org. Chem. 2002, 67, 1751. (g) McNulty, J.; Capretta, A.; Laritchev, V.; Dyck, J.; Robertson, A. J. Angew. Chem., Int. Ed. 2003, 42, 4051.
28. (a) Matsushita, M.; Maeda, H.; Kodama, M. Tetrahedron Lett. 1998, 39, 3749.
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30. 14b is unsatisfactory, since the analogous pathway from E would afford the same aziridine intermediate (E → F → C) and therefore the same product distribution (C → D but not G). Since 4d and 4e provide different products (6d and 6e respectively), an aziridine pathway is unlikely. (Equation Presented)
31. (b) Banks, M. R.; Cadogan, J. I. G.; Gosney, I.; Hodgson, P. K. G.; Thomson, D. E. J. Chem. Soc., Perkin Trans. 1 1991, 961.