Copper-Mediated N-Alkynylation of Carbamates, Ureas, and Sulfonamides. A General Method for the Synthesis of Ynamides

Organic Letters

Volumn 5, Issue 21, 2003, Pages 4011-4014

  Dunetz, Joshua R ^a   Danheiser, Rick L ^a  

^a MASSACHUSETTS INSTITUTE OF TECHNOLOGY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

ALKYNYL GROUP; AMIDE; BROMINE DERIVATIVE; CARBAMIC ACID DERIVATIVE; COPPER; KETONE DERIVATIVE; SULFONAMIDE; UREA DERIVATIVE;

AMINATION; ARTICLE; CHEMICAL REACTION; CHIRALITY; N ALKYNYLATION; PROTON TRANSPORT; SUBSTITUTION REACTION;

ALKYNES; AMIDES; CARBAMATES; COPPER; MOLECULAR STRUCTURE; SULFONAMIDES; UREA;

EID: 0242459899     PISSN: 15237060     EISSN: None     Source Type: Journal    
DOI: 10.1021/ol035647d     Document Type: Article

References (51)

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33. In the case where Z is an acyl or sulfonyl group, it is not clear if a 1,2-shift is involved or whether the mechanism proceeds via an addition-elimination pathway.
34. 3) produced the desired ynamides 4 in 15-20% yield.
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37. 4, and 0.1 equiv of a diamine ligand in toluene or dioxane at 110°C for 15-24 h.
38. Also encouraging were recent reports on the preparation of enamides and enamines via amidation and amination of vinyl halides and triflates. See: (a) Ogawa, T.; Kiji, T.; Hayami, K.; Suzuki, H. Chem. Lett. 1991, 1443. (b) Shen, R.; Porco, J. A. Org. Lett. 2000, 2, 1333. (c) Arterburn, J. B.; Pannala, M.; Gonzalez, A. M. Tetrahedron Lett. 2001, 42, 1475. (d) Barluenga, J.; Fernández, M. A.; Aznar, F.; Valdés, C. J. Chem. Soc., Chem. Commun. 2002, 2362. (e) Kozawa, Y.; Mori, M. Tetrahedron Lett. 2002, 43, 111. (f) Lebedev, A. Y.; Izmer, V. V.; Kazyul'kin, D. N.; Beletskaya, I. P.; Voskoboynikov, A. Z. Org. Lett. 2002, 4, 623. (g) Willis, M. C.; Brace, G. N. Tetrahedron Lett. 2002, 43, 9085.
39. Also encouraging were recent reports on the preparation of enamides and enamines via amidation and amination of vinyl halides and triflates. See: (a) Ogawa, T.; Kiji, T.; Hayami, K.; Suzuki, H. Chem. Lett. 1991, 1443. (b) Shen, R.; Porco, J. A. Org. Lett. 2000, 2, 1333. (c) Arterburn, J. B.; Pannala, M.; Gonzalez, A. M. Tetrahedron Lett. 2001, 42, 1475. (d) Barluenga, J.; Fernández, M. A.; Aznar, F.; Valdés, C. J. Chem. Soc., Chem. Commun. 2002, 2362. (e) Kozawa, Y.; Mori, M. Tetrahedron Lett. 2002, 43, 111. (f) Lebedev, A. Y.; Izmer, V. V.; Kazyul'kin, D. N.; Beletskaya, I. P.; Voskoboynikov, A. Z. Org. Lett. 2002, 4, 623. (g) Willis, M. C.; Brace, G. N. Tetrahedron Lett. 2002, 43, 9085.
40. Also encouraging were recent reports on the preparation of enamides and enamines via amidation and amination of vinyl halides and triflates. See: (a) Ogawa, T.; Kiji, T.; Hayami, K.; Suzuki, H. Chem. Lett. 1991, 1443. (b) Shen, R.; Porco, J. A. Org. Lett. 2000, 2, 1333. (c) Arterburn, J. B.; Pannala, M.; Gonzalez, A. M. Tetrahedron Lett. 2001, 42, 1475. (d) Barluenga, J.; Fernández, M. A.; Aznar, F.; Valdés, C. J. Chem. Soc., Chem. Commun. 2002, 2362. (e) Kozawa, Y.; Mori, M. Tetrahedron Lett. 2002, 43, 111. (f) Lebedev, A. Y.; Izmer, V. V.; Kazyul'kin, D. N.; Beletskaya, I. P.; Voskoboynikov, A. Z. Org. Lett. 2002, 4, 623. (g) Willis, M. C.; Brace, G. N. Tetrahedron Lett. 2002, 43, 9085.
41. Also encouraging were recent reports on the preparation of enamides and enamines via amidation and amination of vinyl halides and triflates. See: (a) Ogawa, T.; Kiji, T.; Hayami, K.; Suzuki, H. Chem. Lett. 1991, 1443. (b) Shen, R.; Porco, J. A. Org. Lett. 2000, 2, 1333. (c) Arterburn, J. B.; Pannala, M.; Gonzalez, A. M. Tetrahedron Lett. 2001, 42, 1475. (d) Barluenga, J.; Fernández, M. A.; Aznar, F.; Valdés, C. J. Chem. Soc., Chem. Commun. 2002, 2362. (e) Kozawa, Y.; Mori, M. Tetrahedron Lett. 2002, 43, 111. (f) Lebedev, A. Y.; Izmer, V. V.; Kazyul'kin, D. N.; Beletskaya, I. P.; Voskoboynikov, A. Z. Org. Lett. 2002, 4, 623. (g) Willis, M. C.; Brace, G. N. Tetrahedron Lett. 2002, 43, 9085.
42. Also encouraging were recent reports on the preparation of enamides and enamines via amidation and amination of vinyl halides and triflates. See: (a) Ogawa, T.; Kiji, T.; Hayami, K.; Suzuki, H. Chem. Lett. 1991, 1443. (b) Shen, R.; Porco, J. A. Org. Lett. 2000, 2, 1333. (c) Arterburn, J. B.; Pannala, M.; Gonzalez, A. M. Tetrahedron Lett. 2001, 42, 1475. (d) Barluenga, J.; Fernández, M. A.; Aznar, F.; Valdés, C. J. Chem. Soc., Chem. Commun. 2002, 2362. (e) Kozawa, Y.; Mori, M. Tetrahedron Lett. 2002, 43, 111. (f) Lebedev, A. Y.; Izmer, V. V.; Kazyul'kin, D. N.; Beletskaya, I. P.; Voskoboynikov, A. Z. Org. Lett. 2002, 4, 623. (g) Willis, M. C.; Brace, G. N. Tetrahedron Lett. 2002, 43, 9085.
43. Also encouraging were recent reports on the preparation of enamides and enamines via amidation and amination of vinyl halides and triflates. See: (a) Ogawa, T.; Kiji, T.; Hayami, K.; Suzuki, H. Chem. Lett. 1991, 1443. (b) Shen, R.; Porco, J. A. Org. Lett. 2000, 2, 1333. (c) Arterburn, J. B.; Pannala, M.; Gonzalez, A. M. Tetrahedron Lett. 2001, 42, 1475. (d) Barluenga, J.; Fernández, M. A.; Aznar, F.; Valdés, C. J. Chem. Soc., Chem. Commun. 2002, 2362. (e) Kozawa, Y.; Mori, M. Tetrahedron Lett. 2002, 43, 111. (f) Lebedev, A. Y.; Izmer, V. V.; Kazyul'kin, D. N.; Beletskaya, I. P.; Voskoboynikov, A. Z. Org. Lett. 2002, 4, 623. (g) Willis, M. C.; Brace, G. N. Tetrahedron Lett. 2002, 43, 9085.
44. Also encouraging were recent reports on the preparation of enamides and enamines via amidation and amination of vinyl halides and triflates. See: (a) Ogawa, T.; Kiji, T.; Hayami, K.; Suzuki, H. Chem. Lett. 1991, 1443. (b) Shen, R.; Porco, J. A. Org. Lett. 2000, 2, 1333. (c) Arterburn, J. B.; Pannala, M.; Gonzalez, A. M. Tetrahedron Lett. 2001, 42, 1475. (d) Barluenga, J.; Fernández, M. A.; Aznar, F.; Valdés, C. J. Chem. Soc., Chem. Commun. 2002, 2362. (e) Kozawa, Y.; Mori, M. Tetrahedron Lett. 2002, 43, 111. (f) Lebedev, A. Y.; Izmer, V. V.; Kazyul'kin, D. N.; Beletskaya, I. P.; Voskoboynikov, A. Z. Org. Lett. 2002, 4, 623. (g) Willis, M. C.; Brace, G. N. Tetrahedron Lett. 2002, 43, 9085.
45. For reviews of the chemistry of halo acetylenes, see: (a) Hopf, H.; Witulski, B. In Modern Acetylene Chemistry; Stang, P. J., Diederich, F., Eds.; VCH: Weinheim, 1995; pp 33-66. (b) Brandsma, L. Preparative Acetylenic Chemistry; Elsevier: New York, 1988.
46. For reviews of the chemistry of halo acetylenes, see: (a) Hopf, H.; Witulski, B. In Modern Acetylene Chemistry; Stang, P. J., Diederich, F., Eds.; VCH: Weinheim, 1995; pp 33-66. (b) Brandsma, L. Preparative Acetylenic Chemistry; Elsevier: New York, 1988.
47. 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.
48. For two early reports of the observation of copper-promoted formation of ynamines and ynamides from reactions of amine derivatives with terminal alkynes, see: (a) Peterson, L. I. Tetrahedron Lett. 1968, 9, 5357. (b) Balsamo, A.; Macchia, B.; Macchia, F.; Rossello, A.; Domiano, P. Tetrahedron Lett. 1985, 26, 4141.
49. For two early reports of the observation of copper-promoted formation of ynamines and ynamides from reactions of amine derivatives with terminal alkynes, see: (a) Peterson, L. I. Tetrahedron Lett. 1968, 9, 5357. (b) Balsamo, A.; Macchia, B.; Macchia, F.; Rossello, A.; Domiano, P. Tetrahedron Lett. 1985, 26, 4141.
50. Interestingly, Hsung found that the yields of ynamides decrease when more than 1 equiv of alkynyl halide is employed under the Buchwald amidation conditions (which are catalytic in copper salt); see Supporting Information in ref 18.
51. 4, filtered, and concentrated to provide 4.397 g of a dark red oil. Column chromatography on 120 g of silica gel (gradient elution with 0-3% EtOAc-hexanes) furnished 2.309 g (76%) of ynamide 9a as a yellow oil.