Iron-Catalyzed Regio- And Stereoselective Substitution of γ,δ-Epoxy-α,β-unsaturated Esters and Amides with Grignard Reagents

Organic Letters

Volumn 12, Issue 5, 2010, Pages 1012-1014

  Hata, Takeshi ^a   Bannai, Rie ^a   Otsuki, Mamoru ^a   Urabe, Hirokazu ^a  

^a TOKYO INSTITUTE OF TECHNOLOGY   (Japan)

Author keywords

[No Author keywords available]

Indexed keywords

ALCOHOL DERIVATIVE; AMIDE; DYES, REAGENTS, INDICATORS, MARKERS AND BUFFERS; ESTER; IRON;

ARTICLE; CATALYSIS; CHEMISTRY; ENZYME SPECIFICITY; STEREOISOMERISM;

ALCOHOLS; AMIDES; CATALYSIS; ESTERS; INDICATORS AND REAGENTS; IRON; STEREOISOMERISM; SUBSTRATE SPECIFICITY;

EID: 77749254904     PISSN: 15237060     EISSN: 15237052     Source Type: Journal    
DOI: 10.1021/ol100022w     Document Type: Article

References (47)

1. (a) Olofsson, B.; Somfai, P. In Aziridiens and Epoxides in Organic Synthesis; Yudin, A. K., Ed.; Wiley-VCH: Weinheim, 2006; pp 315-347. For substitution of epoxides with Grignard reagents, see:
2. (b) Urabe, H.; Sato, F. In Handbook of Grignard Reactions; Silverman, G. S., Rakita, P. E., Eds.; Marcel Dekker: New York, 1996; pp 577-632.
3. Substitution of functionalized diene monoepoxides with various nucleophiles has been reported. With oxygen or nitrogen nucleophiles: (a) Yu, X.-Q.; Yoshimura, F.; Ito, F.; Sasaki, M.; Hirai, A.; Tanino, K.; Miyashita, M. Angew. Chem., Int. Ed. 2008, 47, 750-754.
4. (b) Miyashita, M.; Mizutani, T.; Tadano, G.; Iwata, Y.; Miyazawa, M.; Tanino, K. Angew. Chem., Int. Ed. 2005, 44, 5094-5097.
5. (c) Fagnou, K.; Lautens, M. Org. Lett. 2000, 2, 2319-2321.
6. (d) Tsuda, T.; Horii, Y.; Nakagawa, Y.; Ishida, T.; Saegusa, T. J. Org. Chem. 1989, 54, 977-979. With active methylene compounds under Pd catalysis (which shows different regioselection to form allyl alcohols rather than, homoallyl alcohols):
7. (e) Tsuji, J.; Kataoka, H.; Kobayashi, Y. Tetrahedron Lett. 1981, 22, 2575-2578.
8. (f) Nemoto, H.; Ibaragi, T.; Bando, M.; Kido, M.; Shibuya, M. Tetrahedron Lett. 1999, 40, 1319-1322. With, hydride under Pd catalysis:
9. (g) Oshima, M.; Yamazaki, H.; Shimizu, I.; Nisar, M.; Tsuji, J. J. Am. Chem. Soc. 1989, 111, 6280-6287. With electron:
10. (h) Molander, G. A.; Bella, B. E. L.; Hahn, G. J. Org. Chem. 1986, 51, 5259-5264.
11. (i) Yadav, J. S.; Shekharam, T.; Srinivas, D. Tetrahedron Lett. 1992, 33, 7973-7976.
12. With methyl- or ethylaluminum reagents: (a) Miyashita, M.; Hoshino, M.; Yoshikoshi, A. J. Org. Chem. 1991, 56, 6483-6485.
13. (b) Shanmugam, P.; Miyashita, M. Org. Lett. 2003, 5, 3265-3268.
14. For application to natural product synthesis, see: (c) Komatsu, K.; Tanino, K.; Miyashita, M. Angew. Chem., Int. Ed. 2004, 43, 4341-4353.
15. (d) Nakamura, R.; Tanino, K.; Miyashita, M. Org. Lett. 2003, 5, 3579-3582.
16. With organocopper reagents (which shows different regioselection to form allyl alcohols rather than homoallyl alcohols): Hirai, A.; Matsui, A.; Komatsu, K.; Tanino, K.; Miyashita, M. Chem. Commun. 2002, 1970-1971.
17. For reviews on iron-promoted organic reactions, see: (a) Correa, A.; Mancheño , O. G.; Bolm, C. Chem. Soc. Rev. 2008, 37, 1108-1117.
18. (b) Enthaler, S.; Junge, K.; Beller, M. Angew. Chem., Int. Ed. 2008, 47, 3317-3321.
19. (c) Bolm, C.; Legros, J.; Le Paih, J.; Zani, L. Chem. Rev. 2004, 104, 6217-6254.
20. For diene, enyne, and diyne cyclizations, see: (d) Michelet, V.; Toullec, P. Y.; Genêt, J.-P. Angew. Chem.Int. Ed. 2008, 47, 4268-4315. For coupling reactions, see:
21. (e) Sherry, B. D.; Fürstner, A. Acc. Chem. Res. 2008, 41, 1500-1511.
22. (f) Fürstner, A.; Martin, R. Chem. Lett. 2005, 34, 624-629.
23. For iron-catalyzed or -mediated reactions from our laboratory, see: (a) Okada, S.; Arayama, K.; Murayama, R.; Ishizuka, T.; Hara, K.; Hirone, N.; Hata, T.; Urabe, H. Angew. Chem., Int. Ed. 2008, 47, 6860-6864.
24. (b) Hata, T.; Hirone, N.; Sujaku, S.; Nakano, K.; Urabe, H. Org. Lett. 2008, 10, 5051-5053.
25. (c) Fukuhara, K.; Urabe, H. Tetrahedron Lett. 2005, 46, 603-606.
26. Unsuitable copper catalysis for this purpose was expected from the results of ref 4. See, for example: Buchwald, S. L.; Bolm, C. Angew. Chem., Int. Ed 2009, 48, 5586-5587.
27. 1H NMR spectroscopy.
28. Nagumo, S.; Ono, M.; Kakimoto, Y.; Furukawa, T.; Hisano, T.; Mizukami, M.; Kawahara, N.; Akita, H. J. Org. Chem. 2002, 67, 6618-6622.
29. As cited in reference 3 this type of carbon-carbon bond formation is so far viable with only methyl- or ethylaluminum reagents.
30. Delacroix, T.; Bérillon, L.; Cahiez, G.; Knöchel, P. J. Org. Chem. 2000, 65, 8108-8110.
31. Iron-catalyzed allylic substitution with Grignard reagents has been reported, (a) Kauffmann, T. Angew. Chem., Int. Ed. Engl, 1996, 35, 386-403.
32. (b) Yanagisawa, A.; Nomura, N.; Yamamoto, H. Synlett 1991, 513-514.
33. (c) Urabe, H.; Inami, H.; Sato, F. J. Chem. Soc., Chem. Commun. 1993, 1595-1597.
34. (d) Nakamura, M.; Matsuo, K.; Inoue, T.; Nakamura, E. Org. Lett. 2003, 5, 1373-1375. With functionalized (achiral) allyl bromide, see:
35. (e) Fürstner, A.; Martin, R.; Krause, H.; Seidel, G.; Goddard, R.; Lehmann, C. W. J. Am. Chem. Soc. 2008, 130, 8773-8787. With alkynylepoxides, see:
36. (f) Fürstner, A.; Méndez, M. Angew. Chem., Int. Ed. 2003, 42, 5355-5357.
37. (g) Fürstner, A.; Kattnig, E.; Lepage, O. J. Am. Chem. Soc. 2006, 128, 9194-9204. With vinylcyclopropanes, see:
38. (h) Sherry, B. D.; Fürstner, A. Commun. Commun. 2009, 7116-7118.
39. Regio- and stereochemical aspects of iron-catalyzed allylic substitution, with soft nucleophiles such as malonates and amines have been, disclosed, (a) Silverman, G. S.; Strickland, S.; Nicholas, K. M. Organometallics 1986, 5, 2117-2124.
40. (b) Xu, Y.; Zhou, B. J. Org. Chem. 1987, 52, 974-977.
41. (c) Zhou, B.; Xu, Y. J. Org. Chem. 1988, 53, 4419-4422.
42. (d) Plietker, B. Angew. Chem., Int. Ed. 2006, 45, 1469-1473.
43. (e) Plietker, B. Angew. Chem., Int. Ed. 2006, 45, 6053-6056.
44. (f) Åkermark, B.; Sjögren, M. P. T. Adv. Synth. Catal. 2007, 349, 2641-2646.
45. (g) Plietker, B.; Dieskau, A.; Mows, K.; Jatsch, A. Angew. Chem., Int. Ed. 2008, 47, 198-201. For review, see:
46. (h) Plietker, B.; Dieskau, A. Eur. J. Org. Chem. 2009, 775-787.
47. To the best of our knowledge, this is the first example disclosing the stereochemical course of iron-catalyzed allylic substitution at an optically active system, with Grignard reagent, which is categorized as a hard nucleophile.