Allylmagnesation and diallylation of acetylenic compounds catalyzed by manganese salts

Journal of the American Chemical Society

Volumn 118, Issue 25, 1996, Pages 6076-6077

  Okada, Kenji ^a   Oshima, Koichiro ^a   Utimoto, Kiitiro ^a  

^a KYOTO UNIVERSITY   (Japan)

Author keywords

[No Author keywords available]

Indexed keywords

ALLYL COMPOUND; MANGANESE;

ARTICLE; CATALYSIS; CHIRALITY; DRUG SYNTHESIS; REACTION ANALYSIS;

EID: 0030037920     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja960791y     Document Type: Article

References (27)

1. Yamamoto, Y.; Asao, N. Chem. Rev. 1993, 93, 2207 and references cited therein. Recently conjugate addition of allylic copper species has been reported: Lipshutz, B. H.; Hackmann, C. J. Org. Chem. 1994, 59, 7437.
2. Yamamoto, Y.; Asao, N. Chem. Rev. 1993, 93, 2207 and references cited therein. Recently conjugate addition of allylic copper species has been reported: Lipshutz, B. H.; Hackmann, C. J. Org. Chem. 1994, 59, 7437.
3. Knochel, P. Carbometallation of Alkenes and Alkynes. In Comprehensive Organic Synthesis; Pergamon Press: Oxford, 1991; Vol. 4, p 865. Oppolzer, W. Metallo-ene Reactions. In Comprehensive Organic Synthesis; Pergamon Press: Oxford, 1991; Vol. 5, p 29.
4. Knochel, P. Carbometallation of Alkenes and Alkynes. In Comprehensive Organic Synthesis; Pergamon Press: Oxford, 1991; Vol. 4, p 865. Oppolzer, W. Metallo-ene Reactions. In Comprehensive Organic Synthesis; Pergamon Press: Oxford, 1991; Vol. 5, p 29.
5. Normant, J. F.; Alexakis, A. Synthesis 1981, 841. von Rein, F. W.; Richey, H. G., Jr. Tetrahedron Lett. 1971, 3777.
6. Normant, J. F.; Alexakis, A. Synthesis 1981, 841. von Rein, F. W.; Richey, H. G., Jr. Tetrahedron Lett. 1971, 3777.
7. Jousseaume, B.; Duboudin, J.-G. J. Organomet. Chem. 1975, 91, C1.
8. Bernadou, F.; Miginiac, L. Tetrahedron Lett. 1976, 3083. Mauze, B.; Nivert, C.; Miginiac, L. J. Organomet. Chem. 1972, 44, 69. Bellassoued, M.; Frangin, Y. Synthesis 1978, 838.
9. Bernadou, F.; Miginiac, L. Tetrahedron Lett. 1976, 3083. Mauze, B.; Nivert, C.; Miginiac, L. J. Organomet. Chem. 1972, 44, 69. Bellassoued, M.; Frangin, Y. Synthesis 1978, 838.
10. Bernadou, F.; Miginiac, L. Tetrahedron Lett. 1976, 3083. Mauze, B.; Nivert, C.; Miginiac, L. J. Organomet. Chem. 1972, 44, 69. Bellassoued, M.; Frangin, Y. Synthesis 1978, 838.
11. Further examples about the addition of other allylic organometallic reagents to alkynes are as follows. Allylic aluminum reagents: Miller, J. A.; Negishi, E. Tetrahedron Lett. 1984, 25, 5863. Negishi, E.; Takahashi, T. Synthesis 1988, 1. Allylic indium reagents: Araki, S.; Imai, A.; Shimizu, K.; Butsugan, Y. Tetrahedron Lett. 1992, 33, 2581. Allylic boron reagents: Mikhailov, B. M. Pure Appl. Chem. 1974, 39, 505. Mikhailov, B. Organomet. Chem. Rev. 1972, 8 (A), 1.
12. Further examples about the addition of other allylic organometallic reagents to alkynes are as follows. Allylic aluminum reagents: Miller, J. A.; Negishi, E. Tetrahedron Lett. 1984, 25, 5863. Negishi, E.; Takahashi, T. Synthesis 1988, 1. Allylic indium reagents: Araki, S.; Imai, A.; Shimizu, K.; Butsugan, Y. Tetrahedron Lett. 1992, 33, 2581. Allylic boron reagents: Mikhailov, B. M. Pure Appl. Chem. 1974, 39, 505. Mikhailov, B. Organomet. Chem. Rev. 1972, 8 (A), 1.
13. Further examples about the addition of other allylic organometallic reagents to alkynes are as follows. Allylic aluminum reagents: Miller, J. A.; Negishi, E. Tetrahedron Lett. 1984, 25, 5863. Negishi, E.; Takahashi, T. Synthesis 1988, 1. Allylic indium reagents: Araki, S.; Imai, A.; Shimizu, K.; Butsugan, Y. Tetrahedron Lett. 1992, 33, 2581. Allylic boron reagents: Mikhailov, B. M. Pure Appl. Chem. 1974, 39, 505. Mikhailov, B. Organomet. Chem. Rev. 1972, 8 (A), 1.
14. Further examples about the addition of other allylic organometallic reagents to alkynes are as follows. Allylic aluminum reagents: Miller, J. A.; Negishi, E. Tetrahedron Lett. 1984, 25, 5863. Negishi, E.; Takahashi, T. Synthesis 1988, 1. Allylic indium reagents: Araki, S.; Imai, A.; Shimizu, K.; Butsugan, Y. Tetrahedron Lett. 1992, 33, 2581. Allylic boron reagents: Mikhailov, B. M. Pure Appl. Chem. 1974, 39, 505. Mikhailov, B. Organomet. Chem. Rev. 1972, 8 (A), 1.
15. Further examples about the addition of other allylic organometallic reagents to alkynes are as follows. Allylic aluminum reagents: Miller, J. A.; Negishi, E. Tetrahedron Lett. 1984, 25, 5863. Negishi, E.; Takahashi, T. Synthesis 1988, 1. Allylic indium reagents: Araki, S.; Imai, A.; Shimizu, K.; Butsugan, Y. Tetrahedron Lett. 1992, 33, 2581. Allylic boron reagents: Mikhailov, B. M. Pure Appl. Chem. 1974, 39, 505. Mikhailov, B. Organomet. Chem. Rev. 1972, 8 (A), 1.
16. Allylic manganese reagent derived from allylic bromide and Mn(0) has been reported to react with aldehydes providing homoallylic alcohols. Hiyama, T.; Obayashi, M.; Nakamura, A. Organometallics 1982, 1, 1249.
17. +) have been reported. Normant, J. F.; Cahiez, G. Organomanganous reagents. In Modern Synthetic Methods; Scheffold, R., Ed.; Otto Salle Verlag GmbH & Co.: Frankfurt am Main, 1983; Vol. 3.
18. 2, ether was used because of its solubility.
19. Burton, D. J.; Hartgraves, G. A.; Hsu, J. Tetrahedron Lett. 1990, 31, 3699. Westmijze, H.; Vermeer, P. Ibid. 1979, 4101. Tadema, G.; Everhardus, R. H.; Westmijze, H.; Vermeer, P. Ibid. 1978, 3935. Marek, I.; Mangeney, P.; Alexakis, A.; Normant, J. F. Ibid. 1986, 27, 5499.
20. Burton, D. J.; Hartgraves, G. A.; Hsu, J. Tetrahedron Lett. 1990, 31, 3699. Westmijze, H.; Vermeer, P. Ibid. 1979, 4101. Tadema, G.; Everhardus, R. H.; Westmijze, H.; Vermeer, P. Ibid. 1978, 3935. Marek, I.; Mangeney, P.; Alexakis, A.; Normant, J. F. Ibid. 1986, 27, 5499.
21. Burton, D. J.; Hartgraves, G. A.; Hsu, J. Tetrahedron Lett. 1990, 31, 3699. Westmijze, H.; Vermeer, P. Ibid. 1979, 4101. Tadema, G.; Everhardus, R. H.; Westmijze, H.; Vermeer, P. Ibid. 1978, 3935. Marek, I.; Mangeney, P.; Alexakis, A.; Normant, J. F. Ibid. 1986, 27, 5499.
22. Burton, D. J.; Hartgraves, G. A.; Hsu, J. Tetrahedron Lett. 1990, 31, 3699. Westmijze, H.; Vermeer, P. Ibid. 1979, 4101. Tadema, G.; Everhardus, R. H.; Westmijze, H.; Vermeer, P. Ibid. 1978, 3935. Marek, I.; Mangeney, P.; Alexakis, A.; Normant, J. F. Ibid. 1986, 27, 5499.
23. The formation of lib as a mixture of Z/E = 10/90 starting from 7b (Z/E = 90/10) might suggest that both intramolecular carbomanganation and deoxymanganation proceed in syn fashion.
24. 3MnMgMe has been reported. Hibino, J.; Nakatsukasa, S.; Fugami, K.; Matsubara, S.; Oshima, K.; Nozaki, H. J. Am. Chem. Soc. 1985, 107, 6416. Fugami, K.; Hibino, J.; Nakatsukasa, S.; Matsubara, S.; Oshima, K.; Utimoto, K.; Nozaki, H. Tetrahedron 1988, 44, 4277.
25. 3MnMgMe has been reported. Hibino, J.; Nakatsukasa, S.; Fugami, K.; Matsubara, S.; Oshima, K.; Nozaki, H. J. Am. Chem. Soc. 1985, 107, 6416. Fugami, K.; Hibino, J.; Nakatsukasa, S.; Matsubara, S.; Oshima, K.; Utimoto, K.; Nozaki, H. Tetrahedron 1988, 44, 4277.
26. We are tempted to assume that reductive elimination from alkenyl-manganese intermediate 13 affords the diallylated product and low-valent manganese which is oxidized by air to manganese active species: equation presented.
27. Treatment of allyl propargyl ether 14 with allylmagnesium bromide under the same reaction conditions gave furan derivative 15 in only 27% yield in addition to allenic product 6 (15%): equation presented