Stereoselective preparation of functionalized acyclic alkenylmagnesium reagents using i-PrMgCl-LiCl

Organic Letters

Volumn 6, Issue 23, 2004, Pages 4215-4217

  Ren, Hongjun ^a   Krasovskiy, Arkady ^a   Knochel, Paul ^a  

^a UNIVERSITY OF MUNICH   (Germany)

Author keywords

[No Author keywords available]

Indexed keywords

ALKENYL GROUP; MAGNESIUM DERIVATIVE;

ARTICLE; CHEMICAL REACTION; ESTERIFICATION; GRIGNARD REACTION; STEREOCHEMISTRY;

EID: 9444224983     PISSN: 15237060     EISSN: None     Source Type: Journal    
DOI: 10.1021/ol048363h     Document Type: Article

References (23)

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3. (c) Knochel, P.; Dohle, W.; Gommermann, N.; Kneisel, F. F.; Kopp, F.; Korn, T.; Sapountzis, I.; Vu, V. A. Angew. Chem. 2003, 115, 4438; Angew. Chem., Int. Ed. 2003, 42, 4302.
4. (c) Knochel, P.; Dohle, W.; Gommermann, N.; Kneisel, F. F.; Kopp, F.; Korn, T.; Sapountzis, I.; Vu, V. A. Angew. Chem. 2003, 115, 4438; Angew. Chem., Int. Ed. 2003, 42, 4302.
5. For recent applications see: (a) Klos, A.; Heintzelman, G. R.; Weinreb, S. M. J. Org. Chem. 1997, 62, 3758. (b) Taber, D. F.; Green, J. H.; Geremia, J. M. J. Org. Chem. 1997, 62, 9342. (c) Hayashi, Y.; Shinokubo, H.; Oshima, K. Tetrahedron Lett. 1998, 39, 63. (d) Inoue, A.; Kitagawa, K.; Shinokubo, H.; Oshima, K. J. Org. Chem. 2001, 66, 4333. (e) Heron, N. M.; Adams, J. A.; Hoveyda; A. H. J. Am. Chem. Soc. 1997, 119, 6205. (f) Houri, A. F.; Xa, Z.; Cogan, D. A.; Hoveyda; A. H. J. Am. Chem. Soc. 1995, 117, 2943. (g) Fleming, F. F.; Gudipati, V.; Steward, O. W. Org. Lett. 2002, 4, 659. (h) Fleming, F. F.; Zhang, Z.; Wang, Q.; Steward, O. W. Org. Lett. 2002, 4, 2493.
6. For recent applications see: (a) Klos, A.; Heintzelman, G. R.; Weinreb, S. M. J. Org. Chem. 1997, 62, 3758. (b) Taber, D. F.; Green, J. H.; Geremia, J. M. J. Org. Chem. 1997, 62, 9342. (c) Hayashi, Y.; Shinokubo, H.; Oshima, K. Tetrahedron Lett. 1998, 39, 63. (d) Inoue, A.; Kitagawa, K.; Shinokubo, H.; Oshima, K. J. Org. Chem. 2001, 66, 4333. (e) Heron, N. M.; Adams, J. A.; Hoveyda; A. H. J. Am. Chem. Soc. 1997, 119, 6205. (f) Houri, A. F.; Xa, Z.; Cogan, D. A.; Hoveyda; A. H. J. Am. Chem. Soc. 1995, 117, 2943. (g) Fleming, F. F.; Gudipati, V.; Steward, O. W. Org. Lett. 2002, 4, 659. (h) Fleming, F. F.; Zhang, Z.; Wang, Q.; Steward, O. W. Org. Lett. 2002, 4, 2493.
7. For recent applications see: (a) Klos, A.; Heintzelman, G. R.; Weinreb, S. M. J. Org. Chem. 1997, 62, 3758. (b) Taber, D. F.; Green, J. H.; Geremia, J. M. J. Org. Chem. 1997, 62, 9342. (c) Hayashi, Y.; Shinokubo, H.; Oshima, K. Tetrahedron Lett. 1998, 39, 63. (d) Inoue, A.; Kitagawa, K.; Shinokubo, H.; Oshima, K. J. Org. Chem. 2001, 66, 4333. (e) Heron, N. M.; Adams, J. A.; Hoveyda; A. H. J. Am. Chem. Soc. 1997, 119, 6205. (f) Houri, A. F.; Xa, Z.; Cogan, D. A.; Hoveyda; A. H. J. Am. Chem. Soc. 1995, 117, 2943. (g) Fleming, F. F.; Gudipati, V.; Steward, O. W. Org. Lett. 2002, 4, 659. (h) Fleming, F. F.; Zhang, Z.; Wang, Q.; Steward, O. W. Org. Lett. 2002, 4, 2493.
8. For recent applications see: (a) Klos, A.; Heintzelman, G. R.; Weinreb, S. M. J. Org. Chem. 1997, 62, 3758. (b) Taber, D. F.; Green, J. H.; Geremia, J. M. J. Org. Chem. 1997, 62, 9342. (c) Hayashi, Y.; Shinokubo, H.; Oshima, K. Tetrahedron Lett. 1998, 39, 63. (d) Inoue, A.; Kitagawa, K.; Shinokubo, H.; Oshima, K. J. Org. Chem. 2001, 66, 4333. (e) Heron, N. M.; Adams, J. A.; Hoveyda; A. H. J. Am. Chem. Soc. 1997, 119, 6205. (f) Houri, A. F.; Xa, Z.; Cogan, D. A.; Hoveyda; A. H. J. Am. Chem. Soc. 1995, 117, 2943. (g) Fleming, F. F.; Gudipati, V.; Steward, O. W. Org. Lett. 2002, 4, 659. (h) Fleming, F. F.; Zhang, Z.; Wang, Q.; Steward, O. W. Org. Lett. 2002, 4, 2493.
9. For recent applications see: (a) Klos, A.; Heintzelman, G. R.; Weinreb, S. M. J. Org. Chem. 1997, 62, 3758. (b) Taber, D. F.; Green, J. H.; Geremia, J. M. J. Org. Chem. 1997, 62, 9342. (c) Hayashi, Y.; Shinokubo, H.; Oshima, K. Tetrahedron Lett. 1998, 39, 63. (d) Inoue, A.; Kitagawa, K.; Shinokubo, H.; Oshima, K. J. Org. Chem. 2001, 66, 4333. (e) Heron, N. M.; Adams, J. A.; Hoveyda; A. H. J. Am. Chem. Soc. 1997, 119, 6205. (f) Houri, A. F.; Xa, Z.; Cogan, D. A.; Hoveyda; A. H. J. Am. Chem. Soc. 1995, 117, 2943. (g) Fleming, F. F.; Gudipati, V.; Steward, O. W. Org. Lett. 2002, 4, 659. (h) Fleming, F. F.; Zhang, Z.; Wang, Q.; Steward, O. W. Org. Lett. 2002, 4, 2493.
10. For recent applications see: (a) Klos, A.; Heintzelman, G. R.; Weinreb, S. M. J. Org. Chem. 1997, 62, 3758. (b) Taber, D. F.; Green, J. H.; Geremia, J. M. J. Org. Chem. 1997, 62, 9342. (c) Hayashi, Y.; Shinokubo, H.; Oshima, K. Tetrahedron Lett. 1998, 39, 63. (d) Inoue, A.; Kitagawa, K.; Shinokubo, H.; Oshima, K. J. Org. Chem. 2001, 66, 4333. (e) Heron, N. M.; Adams, J. A.; Hoveyda; A. H. J. Am. Chem. Soc. 1997, 119, 6205. (f) Houri, A. F.; Xa, Z.; Cogan, D. A.; Hoveyda; A. H. J. Am. Chem. Soc. 1995, 117, 2943. (g) Fleming, F. F.; Gudipati, V.; Steward, O. W. Org. Lett. 2002, 4, 659. (h) Fleming, F. F.; Zhang, Z.; Wang, Q.; Steward, O. W. Org. Lett. 2002, 4, 2493.
11. For recent applications see: (a) Klos, A.; Heintzelman, G. R.; Weinreb, S. M. J. Org. Chem. 1997, 62, 3758. (b) Taber, D. F.; Green, J. H.; Geremia, J. M. J. Org. Chem. 1997, 62, 9342. (c) Hayashi, Y.; Shinokubo, H.; Oshima, K. Tetrahedron Lett. 1998, 39, 63. (d) Inoue, A.; Kitagawa, K.; Shinokubo, H.; Oshima, K. J. Org. Chem. 2001, 66, 4333. (e) Heron, N. M.; Adams, J. A.; Hoveyda; A. H. J. Am. Chem. Soc. 1997, 119, 6205. (f) Houri, A. F.; Xa, Z.; Cogan, D. A.; Hoveyda; A. H. J. Am. Chem. Soc. 1995, 117, 2943. (g) Fleming, F. F.; Gudipati, V.; Steward, O. W. Org. Lett. 2002, 4, 659. (h) Fleming, F. F.; Zhang, Z.; Wang, Q.; Steward, O. W. Org. Lett. 2002, 4, 2493.
12. For recent applications see: (a) Klos, A.; Heintzelman, G. R.; Weinreb, S. M. J. Org. Chem. 1997, 62, 3758. (b) Taber, D. F.; Green, J. H.; Geremia, J. M. J. Org. Chem. 1997, 62, 9342. (c) Hayashi, Y.; Shinokubo, H.; Oshima, K. Tetrahedron Lett. 1998, 39, 63. (d) Inoue, A.; Kitagawa, K.; Shinokubo, H.; Oshima, K. J. Org. Chem. 2001, 66, 4333. (e) Heron, N. M.; Adams, J. A.; Hoveyda; A. H. J. Am. Chem. Soc. 1997, 119, 6205. (f) Houri, A. F.; Xa, Z.; Cogan, D. A.; Hoveyda; A. H. J. Am. Chem. Soc. 1995, 117, 2943. (g) Fleming, F. F.; Gudipati, V.; Steward, O. W. Org. Lett. 2002, 4, 659. (h) Fleming, F. F.; Zhang, Z.; Wang, Q.; Steward, O. W. Org. Lett. 2002, 4, 2493.
13. The use of activated magnesium (Rieke-magnesium) has an especially broad reaction scope: (a) Rieke, R. D.; Xiong, H. J. Org. Chem. 1991, 56, 3109. (b) Rieke, R. D. Science 1989, 246, 1260.
14. The use of activated magnesium (Rieke-magnesium) has an especially broad reaction scope: (a) Rieke, R. D.; Xiong, H. J. Org. Chem. 1991, 56, 3109. (b) Rieke, R. D. Science 1989, 246, 1260.
15. (a) Burns, T. P.; Rieke, R. D. J. Org. Chem. 1987, 52, 3674.
16. (b) Sapountzis, I.; Knochel, P. Angew. Chem., Int. Ed. 2002, 41, 1610.
17. Knochel, P.; Normant, J. F. Tetrahedron Lett. 1986, 27, 4431.
18. Rottländer, M.; Boymond, L.; Cahiez, G.; Knochel, P. J. Org. Chem. 1999, 64, 1080.
19. Preparation of Reagent i-PrMgCl-LiCl. Magnesium turnings (110 mmol) and anhydrous LiCl (100 mmol) were placed in an Ar-flushed flask, and THF (25 mL) was added. A solution of i-PrCl (100 mmol) in THF (25 mL) was slowly added at room temperature. The reaction starts within a few minutes. After addition, the reaction mixture was stirred for 12 h at room temperature. The gray solution of i-PrMgCl·LiCl was cannulated to an other flask under Ar and removed in this way from excess of magnesium. A yield of ca. 95-98% of i-PrMgCl·LiCl is obtained.
20. Krasovskiy, A.; Knochel, P. Angew. Chem., Int. Ed. 2004, 43, 3333.
21. For exceptions, see: Kneisel, F. F., Knochel, P. Synlett 2002, 1799.
22. 3CN. Kim, S. S.; Rajagopal, G.; Song, D. H. J. Organomet. Chem. 2004, 689, 1734.
23. 4) and concentrated in vacuo. Purification by flash chromatography (hexane/diethyl ether = 2:1) yielded 99 mg (82% yield) 5k as a colorless oil.