Chelation-aided generation of ketone α,β-dianions and their use as copper ate complexes. Unprecedented enolate intervention in the conjugate addition to enones [3]

Journal of the American Chemical Society

Volumn 122, Issue 6, 2000, Pages 1219-1220

  Ryu, Ilhyong ^b   Nakahira, Hiroyuki ^b   Ikebe, Masanobu ^b   Sonoda, Noboru ^a,b   Yamato, Shin Ya ^b   Komatsu, Mitsuo ^b  

^a KANSAI UNIVERSITY   (Japan)

^b OSAKA UNIVERSITY   (Japan)

Author keywords

[No Author keywords available]

Indexed keywords

ANION; COPPER DERIVATIVE; KETONE DERIVATIVE;

CHELATION; CHEMICAL REACTION; CHEMICAL STRUCTURE; CONJUGATE; CONJUGATION; CONTROLLED STUDY; LETTER; REACTION ANALYSIS; STEREOCHEMISTRY; SYNTHESIS;

EID: 0034673373     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja993577t     Document Type: Letter

References (25)

1. For recent reviews, see: (a) Hoppe, D.; Hense, T. Angew. Chem., Int. Ed. Engl. 1997, 36, 2282. (b) Marek, I.; Normant, J. F. Chem. Rev. 1996, 96, 3241. (c) Beak, P.; Basu, A.; Gallagher, D. J.; Park, Y. S.; Thayumanavan, S. Acc. Chem. Rev. 1996, 29, 552.
2. For recent reviews, see: (a) Hoppe, D.; Hense, T. Angew. Chem., Int. Ed. Engl. 1997, 36, 2282. (b) Marek, I.; Normant, J. F. Chem. Rev. 1996, 96, 3241. (c) Beak, P.; Basu, A.; Gallagher, D. J.; Park, Y. S.; Thayumanavan, S. Acc. Chem. Rev. 1996, 29, 552.
3. For recent reviews, see: (a) Hoppe, D.; Hense, T. Angew. Chem., Int. Ed. Engl. 1997, 36, 2282. (b) Marek, I.; Normant, J. F. Chem. Rev. 1996, 96, 3241. (c) Beak, P.; Basu, A.; Gallagher, D. J.; Park, Y. S.; Thayumanavan, S. Acc. Chem. Rev. 1996, 29, 552.
4. Nakahira, H.; Ryu, I.; Ikebe, M.; Kambe, N.; Sonoda, N. Angew. Chem., Int. Ed. Engl. 1991, 30, 177.
5. For a pertinent review on enolate chemistry, see: Heathcock, C. H. In Modern Synthetic Methods; Scheffold, R., Ed.; VCH: New York, 1992; pp 3-102.
6. Nakahira, H.; Ryu, I.; Ikebe, M.; Oku, Y.; Ogawa, A.; Kambe, N.; Sonoda, N.; Murai, S. J. Org. Chem. 1992, 57, 27.
7. β-Dichlorobutylstannyl ketones are readily available from siloxycyclopropanes and butyltrichlorotin, see ref 4.
8. Treatment of 1b with 3 equiv of n-BuLi al -78°C and the subsequent chlorosilane quenching at that temperature gave the Z-enol silyl ether of the corresponding β-tributylstannyl ketone in 72% yield, supporting the idea that the β-tributylstannyl ketone enolate is a precursor of the dianion 2b.
9. 4 and the subsequent Michael addition of n-BuLi, was difficult to suppress.
10. For recent theoretical and mechanistic studies on the cuprate addition to enones, see: (a) Krause, N.; Wagner, R.; Gerold, A. J. Am. Chem. Soc. 1994, 116, 381. (b) Dorgio, A. E.; Wanner, J.; Schleyer, P. v. R. Angew. Chem., Int. Ed. Engl. 1995, 34, 476. (c) Nakamura, E.; Mori, S.; Morokuma, K. J. Am. Chem. Soc. 1997, 119, 4900. (d) Kingsbury, C. L.; Smith, R. A. J. J. Org. Chem. 1997, 62, 4629. (e) Ericksson, M.; Iliefski, T.; Nilsson, M.; Olsson, T. J. Org. Chem. 1997, 62, 182. (f) Vellekoop, A. S.; Smith, R. A. J. J. Am. Chem. Soc. 1994, 116, 2902. (g) Snyder, J. P. J. Am. Chem. Soc. 1995, 117, 11025. Also see reviews: (h) Lipshutz, B. H.; Sengupta, S. Org. React. 1992, 41, 135. (i) Krause, N.; Gerold, A. Angew. Chem., Int. Ed. Engel. 1997, 36, 186.
11. For recent theoretical and mechanistic studies on the cuprate addition to enones, see: (a) Krause, N.; Wagner, R.; Gerold, A. J. Am. Chem. Soc. 1994, 116, 381. (b) Dorgio, A. E.; Wanner, J.; Schleyer, P. v. R. Angew. Chem., Int. Ed. Engl. 1995, 34, 476. (c) Nakamura, E.; Mori, S.; Morokuma, K. J. Am. Chem. Soc. 1997, 119, 4900. (d) Kingsbury, C. L.; Smith, R. A. J. J. Org. Chem. 1997, 62, 4629. (e) Ericksson, M.; Iliefski, T.; Nilsson, M.; Olsson, T. J. Org. Chem. 1997, 62, 182. (f) Vellekoop, A. S.; Smith, R. A. J. J. Am. Chem. Soc. 1994, 116, 2902. (g) Snyder, J. P. J. Am. Chem. Soc. 1995, 117, 11025. Also see reviews: (h) Lipshutz, B. H.; Sengupta, S. Org. React. 1992, 41, 135. (i) Krause, N.; Gerold, A. Angew. Chem., Int. Ed. Engel. 1997, 36, 186.
12. For recent theoretical and mechanistic studies on the cuprate addition to enones, see: (a) Krause, N.; Wagner, R.; Gerold, A. J. Am. Chem. Soc. 1994, 116, 381. (b) Dorgio, A. E.; Wanner, J.; Schleyer, P. v. R. Angew. Chem., Int. Ed. Engl. 1995, 34, 476. (c) Nakamura, E.; Mori, S.; Morokuma, K. J. Am. Chem. Soc. 1997, 119, 4900. (d) Kingsbury, C. L.; Smith, R. A. J. J. Org. Chem. 1997, 62, 4629. (e) Ericksson, M.; Iliefski, T.; Nilsson, M.; Olsson, T. J. Org. Chem. 1997, 62, 182. (f) Vellekoop, A. S.; Smith, R. A. J. J. Am. Chem. Soc. 1994, 116, 2902. (g) Snyder, J. P. J. Am. Chem. Soc. 1995, 117, 11025. Also see reviews: (h) Lipshutz, B. H.; Sengupta, S. Org. React. 1992, 41, 135. (i) Krause, N.; Gerold, A. Angew. Chem., Int. Ed. Engel. 1997, 36, 186.
13. For recent theoretical and mechanistic studies on the cuprate addition to enones, see: (a) Krause, N.; Wagner, R.; Gerold, A. J. Am. Chem. Soc. 1994, 116, 381. (b) Dorgio, A. E.; Wanner, J.; Schleyer, P. v. R. Angew. Chem., Int. Ed. Engl. 1995, 34, 476. (c) Nakamura, E.; Mori, S.; Morokuma, K. J. Am. Chem. Soc. 1997, 119, 4900. (d) Kingsbury, C. L.; Smith, R. A. J. J. Org. Chem. 1997, 62, 4629. (e) Ericksson, M.; Iliefski, T.; Nilsson, M.; Olsson, T. J. Org. Chem. 1997, 62, 182. (f) Vellekoop, A. S.; Smith, R. A. J. J. Am. Chem. Soc. 1994, 116, 2902. (g) Snyder, J. P. J. Am. Chem. Soc. 1995, 117, 11025. Also see reviews: (h) Lipshutz, B. H.; Sengupta, S. Org. React. 1992, 41, 135. (i) Krause, N.; Gerold, A. Angew. Chem., Int. Ed. Engel. 1997, 36, 186.
14. For recent theoretical and mechanistic studies on the cuprate addition to enones, see: (a) Krause, N.; Wagner, R.; Gerold, A. J. Am. Chem. Soc. 1994, 116, 381. (b) Dorgio, A. E.; Wanner, J.; Schleyer, P. v. R. Angew. Chem., Int. Ed. Engl. 1995, 34, 476. (c) Nakamura, E.; Mori, S.; Morokuma, K. J. Am. Chem. Soc. 1997, 119, 4900. (d) Kingsbury, C. L.; Smith, R. A. J. J. Org. Chem. 1997, 62, 4629. (e) Ericksson, M.; Iliefski, T.; Nilsson, M.; Olsson, T. J. Org. Chem. 1997, 62, 182. (f) Vellekoop, A. S.; Smith, R. A. J. J. Am. Chem. Soc. 1994, 116, 2902. (g) Snyder, J. P. J. Am. Chem. Soc. 1995, 117, 11025. Also see reviews: (h) Lipshutz, B. H.; Sengupta, S. Org. React. 1992, 41, 135. (i) Krause, N.; Gerold, A. Angew. Chem., Int. Ed. Engel. 1997, 36, 186.
15. For recent theoretical and mechanistic studies on the cuprate addition to enones, see: (a) Krause, N.; Wagner, R.; Gerold, A. J. Am. Chem. Soc. 1994, 116, 381. (b) Dorgio, A. E.; Wanner, J.; Schleyer, P. v. R. Angew. Chem., Int. Ed. Engl. 1995, 34, 476. (c) Nakamura, E.; Mori, S.; Morokuma, K. J. Am. Chem. Soc. 1997, 119, 4900. (d) Kingsbury, C. L.; Smith, R. A. J. J. Org. Chem. 1997, 62, 4629. (e) Ericksson, M.; Iliefski, T.; Nilsson, M.; Olsson, T. J. Org. Chem. 1997, 62, 182. (f) Vellekoop, A. S.; Smith, R. A. J. J. Am. Chem. Soc. 1994, 116, 2902. (g) Snyder, J. P. J. Am. Chem. Soc. 1995, 117, 11025. Also see reviews: (h) Lipshutz, B. H.; Sengupta, S. Org. React. 1992, 41, 135. (i) Krause, N.; Gerold, A. Angew. Chem., Int. Ed. Engel. 1997, 36, 186.
16. For recent theoretical and mechanistic studies on the cuprate addition to enones, see: (a) Krause, N.; Wagner, R.; Gerold, A. J. Am. Chem. Soc. 1994, 116, 381. (b) Dorgio, A. E.; Wanner, J.; Schleyer, P. v. R. Angew. Chem., Int. Ed. Engl. 1995, 34, 476. (c) Nakamura, E.; Mori, S.; Morokuma, K. J. Am. Chem. Soc. 1997, 119, 4900. (d) Kingsbury, C. L.; Smith, R. A. J. J. Org. Chem. 1997, 62, 4629. (e) Ericksson, M.; Iliefski, T.; Nilsson, M.; Olsson, T. J. Org. Chem. 1997, 62, 182. (f) Vellekoop, A. S.; Smith, R. A. J. J. Am. Chem. Soc. 1994, 116, 2902. (g) Snyder, J. P. J. Am. Chem. Soc. 1995, 117, 11025. Also see reviews: (h) Lipshutz, B. H.; Sengupta, S. Org. React. 1992, 41, 135. (i) Krause, N.; Gerold, A. Angew. Chem., Int. Ed. Engel. 1997, 36, 186.
17. For recent theoretical and mechanistic studies on the cuprate addition to enones, see: (a) Krause, N.; Wagner, R.; Gerold, A. J. Am. Chem. Soc. 1994, 116, 381. (b) Dorgio, A. E.; Wanner, J.; Schleyer, P. v. R. Angew. Chem., Int. Ed. Engl. 1995, 34, 476. (c) Nakamura, E.; Mori, S.; Morokuma, K. J. Am. Chem. Soc. 1997, 119, 4900. (d) Kingsbury, C. L.; Smith, R. A. J. J. Org. Chem. 1997, 62, 4629. (e) Ericksson, M.; Iliefski, T.; Nilsson, M.; Olsson, T. J. Org. Chem. 1997, 62, 182. (f) Vellekoop, A. S.; Smith, R. A. J. J. Am. Chem. Soc. 1994, 116, 2902. (g) Snyder, J. P. J. Am. Chem. Soc. 1995, 117, 11025. Also see reviews: (h) Lipshutz, B. H.; Sengupta, S. Org. React. 1992, 41, 135. (i) Krause, N.; Gerold, A. Angew. Chem., Int. Ed. Engel. 1997, 36, 186.
18. For recent theoretical and mechanistic studies on the cuprate addition to enones, see: (a) Krause, N.; Wagner, R.; Gerold, A. J. Am. Chem. Soc. 1994, 116, 381. (b) Dorgio, A. E.; Wanner, J.; Schleyer, P. v. R. Angew. Chem., Int. Ed. Engl. 1995, 34, 476. (c) Nakamura, E.; Mori, S.; Morokuma, K. J. Am. Chem. Soc. 1997, 119, 4900. (d) Kingsbury, C. L.; Smith, R. A. J. J. Org. Chem. 1997, 62, 4629. (e) Ericksson, M.; Iliefski, T.; Nilsson, M.; Olsson, T. J. Org. Chem. 1997, 62, 182. (f) Vellekoop, A. S.; Smith, R. A. J. J. Am. Chem. Soc. 1994, 116, 2902. (g) Snyder, J. P. J. Am. Chem. Soc. 1995, 117, 11025. Also see reviews: (h) Lipshutz, B. H.; Sengupta, S. Org. React. 1992, 41, 135. (i) Krause, N.; Gerold, A. Angew. Chem., Int. Ed. Engel. 1997, 36, 186.
19. For carbocupration mechansims in the conjugate addition to α,β-unsaturated carbonyl compounds, see: (a) Nilsson, K.; Andersson, T.; Ullenius, C.; Gerold, A.; Krause, N. Chem. Eur. J. 1998, 4, 2051. (b) Nilsson, K.; Ullenius, C.; Kraus, N. J. Am. Chem. Soc. 1996, 118, 4194. (c) Eriksson, M.; Hjelmencrantz, A.; Nilsson, M.; Olsson, T. Tetrahedron 1995, 51, 12631. (d) Krause, N. J. Org. Chem. 1992, 57, 3509. (e) Berlan, J.; Battioni, J.; Koosha, K. J. Organomet. Chem. 1978, 152, 359. (f) Nakamura, E.; Yamanaka, M. J. Am. Chem. Soc. 1999, 121, 8941.
20. For carbocupration mechansims in the conjugate addition to α,β- unsaturated carbonyl compounds, see: (a) Nilsson, K.; Andersson, T.; Ullenius, C.; Gerold, A.; Krause, N. Chem. Eur. J. 1998, 4, 2051. (b) Nilsson, K.; Ullenius, C.; Kraus, N. J. Am. Chem. Soc. 1996, 118, 4194. (c) Eriksson, M.; Hjelmencrantz, A.; Nilsson, M.; Olsson, T. Tetrahedron 1995, 51, 12631. (d) Krause, N. J. Org. Chem. 1992, 57, 3509. (e) Berlan, J.; Battioni, J.; Koosha, K. J. Organomet. Chem. 1978, 152, 359. (f) Nakamura, E.; Yamanaka, M. J. Am. Chem. Soc. 1999, 121, 8941.
21. For carbocupration mechansims in the conjugate addition to α,β- unsaturated carbonyl compounds, see: (a) Nilsson, K.; Andersson, T.; Ullenius, C.; Gerold, A.; Krause, N. Chem. Eur. J. 1998, 4, 2051. (b) Nilsson, K.; Ullenius, C.; Kraus, N. J. Am. Chem. Soc. 1996, 118, 4194. (c) Eriksson, M.; Hjelmencrantz, A.; Nilsson, M.; Olsson, T. Tetrahedron 1995, 51, 12631. (d) Krause, N. J. Org. Chem. 1992, 57, 3509. (e) Berlan, J.; Battioni, J.; Koosha, K. J. Organomet. Chem. 1978, 152, 359. (f) Nakamura, E.; Yamanaka, M. J. Am. Chem. Soc. 1999, 121, 8941.
22. For carbocupration mechansims in the conjugate addition to α,β- unsaturated carbonyl compounds, see: (a) Nilsson, K.; Andersson, T.; Ullenius, C.; Gerold, A.; Krause, N. Chem. Eur. J. 1998, 4, 2051. (b) Nilsson, K.; Ullenius, C.; Kraus, N. J. Am. Chem. Soc. 1996, 118, 4194. (c) Eriksson, M.; Hjelmencrantz, A.; Nilsson, M.; Olsson, T. Tetrahedron 1995, 51, 12631. (d) Krause, N. J. Org. Chem. 1992, 57, 3509. (e) Berlan, J.; Battioni, J.; Koosha, K. J. Organomet. Chem. 1978, 152, 359. (f) Nakamura, E.; Yamanaka, M. J. Am. Chem. Soc. 1999, 121, 8941.
23. For carbocupration mechansims in the conjugate addition to α,β- unsaturated carbonyl compounds, see: (a) Nilsson, K.; Andersson, T.; Ullenius, C.; Gerold, A.; Krause, N. Chem. Eur. J. 1998, 4, 2051. (b) Nilsson, K.; Ullenius, C.; Kraus, N. J. Am. Chem. Soc. 1996, 118, 4194. (c) Eriksson, M.; Hjelmencrantz, A.; Nilsson, M.; Olsson, T. Tetrahedron 1995, 51, 12631. (d) Krause, N. J. Org. Chem. 1992, 57, 3509. (e) Berlan, J.; Battioni, J.; Koosha, K. J. Organomet. Chem. 1978, 152, 359. (f) Nakamura, E.; Yamanaka, M. J. Am. Chem. Soc. 1999, 121, 8941.
24. For carbocupration mechansims in the conjugate addition to α,β- unsaturated carbonyl compounds, see: (a) Nilsson, K.; Andersson, T.; Ullenius, C.; Gerold, A.; Krause, N. Chem. Eur. J. 1998, 4, 2051. (b) Nilsson, K.; Ullenius, C.; Kraus, N. J. Am. Chem. Soc. 1996, 118, 4194. (c) Eriksson, M.; Hjelmencrantz, A.; Nilsson, M.; Olsson, T. Tetrahedron 1995, 51, 12631. (d) Krause, N. J. Org. Chem. 1992, 57, 3509. (e) Berlan, J.; Battioni, J.; Koosha, K. J. Organomet. Chem. 1978, 152, 359. (f) Nakamura, E.; Yamanaka, M. J. Am. Chem. Soc. 1999, 121, 8941.
25. 2O quenching, this chemoselective protonation, if it occurs, should also demand high stereoselection of the re/si faces of the enolate, which we think highly unlikely. We are grateful to one referee who suggested a mechanistic possibility involving π-complexation of the copper on the enolate portion or oxo-π-allylcopper formation.