Free radical mediated double carbonylations of alk-4-enyl iodides

Journal of the American Chemical Society

Volumn 118, Issue 43, 1996, Pages 10670-10671

  Tsunoi, Shinji ^a   Ryu, Ilhyong ^a   Yamasaki, Sumiaki ^a   Fukushima, Hiroshi ^a   Tanaka, Minoru ^a   Komatsu, Mitsuo ^a   Sonoda, Noboru ^a  

^a OSAKA UNIVERSITY   (Japan)

Author keywords

[No Author keywords available]

Indexed keywords

2 OXABICYCLO[3.3.0]OCTANE DERIVATIVE; BICYCLO[3.3.0]OCTANE DERIVATIVE; CYCLOPENTANE DERIVATIVE; LACTONE DERIVATIVE; UNCLASSIFIED DRUG;

ARTICLE; CHIRALITY; DRUG SYNTHESIS; REACTION ANALYSIS;

EID: 0029796219     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja962879h     Document Type: Article

References (24)

1. For leading reviews, see: (a) Giese, B. Radicals in Organic Synthesis: Formation of Carbon-Carbon Bonds; Pergamon Press: Oxford, 1986. (b) Curran, D. P. Synthesis 1988, 417, 489. Motherwell, W. B.; Crich, D. Best Synthetic Methods, Free Radical Chain Reactions in Organic Synthesis; Academic Press: London, 1992. Curran, D. P. In Comprehensive Organic Synthesis; Trost, B. M., Ed.; Pergamon: Oxford, 1991; Vol. 4, Chapters 4.1 and 4.2.
2. For leading reviews, see: (a) Giese, B. Radicals in Organic Synthesis: Formation of Carbon-Carbon Bonds; Pergamon Press: Oxford, 1986. (b) Curran, D. P. Synthesis 1988, 417, 489. Motherwell, W. B.; Crich, D. Best Synthetic Methods, Free Radical Chain Reactions in Organic Synthesis; Academic Press: London, 1992. Curran, D. P. In Comprehensive Organic Synthesis; Trost, B. M., Ed.; Pergamon: Oxford, 1991; Vol. 4, Chapters 4.1 and 4.2.
3. For leading reviews, see: (a) Giese, B. Radicals in Organic Synthesis: Formation of Carbon-Carbon Bonds; Pergamon Press: Oxford, 1986. (b) Curran, D. P. Synthesis 1988, 417, 489. (c) Motherwell, W. B.; Crich, D. Best Synthetic Methods, Free Radical Chain Reactions in Organic Synthesis; Academic Press: London, 1992. Curran, D. P. In Comprehensive Organic Synthesis; Trost, B. M., Ed.; Pergamon: Oxford, 1991; Vol. 4, Chapters 4.1 and 4.2.
4. For leading reviews, see: (a) Giese, B. Radicals in Organic Synthesis: Formation of Carbon-Carbon Bonds; Pergamon Press: Oxford, 1986. (b) Curran, D. P. Synthesis 1988, 417, 489. (c) Motherwell, W. B.; Crich, D. Best Synthetic Methods, Free Radical Chain Reactions in Organic Synthesis; Academic Press: London, 1992. (d) Curran, D. P. In Comprehensive Organic Synthesis; Trost, B. M., Ed.; Pergamon: Oxford, 1991; Vol. 4, Chapters 4.1 and 4.2.
5. For reviews, see: (a) Ryu, I.; Sonoda, N.; Curran, D. P. Chem. Rev. 1996, 96, 177. (b) Ryu, I.; Sonoda, N. Angew. Chem., Int. Ed. Engl. 1996, 35, 1050.
6. For reviews, see: (a) Ryu, I.; Sonoda, N.; Curran, D. P. Chem. Rev. 1996, 96, 177. (b) Ryu, I.; Sonoda, N. Angew. Chem., Int. Ed. Engl. 1996, 35, 1050.
7. (a) Lusztyk, J.; Lusztyk, E.; Maillard, B.; Ingold, K. U. J. Am. Chem. Soc. 1984, 106, 2923.
8. (b) Ryu, I.; Kusano, K.; Hasegawa, M.; Kambe, N.; Sonoda, N. J. Chem. Soc., Chem. Commun. 1991, 1018.
9. (c) Ballestri, M.; Chatgilialoglu, C; Cardi, N.; Sommazzi, A. Tetrahedron Lett. 1992, 33, 1787.
10. (d) Riemann, H.; Capomaggi, A. S.; Strauss, T.; Oliveto, E. P.; Barton, D.H. R. J. Am. Chem. Soc. 1961, 83, 4481.
11. (e) Gimisis, T.; Ballestri, M.; Ferreri, C.; Chatgilialoglu, C. Tetrahedron Lett. 1995, 36, 3897.
12. Also see (a review): (f) Dowd, P.; Zhang, W. Chem. Rev. 1993, 93, 2091. (g) Chatgilialoglu, C.; Ferreri, C.; Sommazzi, A. J. Am. Chem. Soc. 1996, 118, 7223.
13. Also see (a review): (f) Dowd, P.; Zhang, W. Chem. Rev. 1993, 93, 2091. (g) Chatgilialoglu, C.; Ferreri, C.; Sommazzi, A. J. Am. Chem. Soc. 1996, 118, 7223.
14. Experimental details are provided in the Supporting Information. The yields of this reaction require optimization: Single carbonylation products constitute main byproducts, and a small amount of six-membered double carbonylation products were also detected (1-4%).
15. Tributylgermyl hydride is a poorer hydrogen donor to alkyl radicals than tributyltin hydride, see: Johnston, L. J.; Lusztyk, J.; Wayner, D. D. M.: Abeywickreyma, A. N.; Beckwith, A. L. J.; Scaiano, J. C.; Ingold, K. U. J. Am. Chem. Soc. 1985, 107, 4594.
16. Chatgilialoglu, C. Acc. Chem. Res. 1992, 25, 188.
17. Rare examples of 5-endo cyclizations of acyl radicals are restricted to cyclizations onto conjugated carbonyls. For recent examples, see: (a) Mendenhall, G. D.; Protasiewicz, J. D.; Brown, C. E.; Ingold, K. U.; Lusztyk, J. J. Am. Chem. Soc. 1994, 116, 1718, 5525. (b) Yamamoto, Y.; Ohno, M.: Eguchi, S. J. Am. Chem. Soc. 1995, 117, 9653.
18. Rare examples of 5-endo cyclizations of acyl radicals are restricted to cyclizations onto conjugated carbonyls. For recent examples, see: (a) Mendenhall, G. D.; Protasiewicz, J. D.; Brown, C. E.; Ingold, K. U.; Lusztyk, J. J. Am. Chem. Soc. 1994, 116, 1718, 5525. (b) Yamamoto, Y.; Ohno, M.: Eguchi, S. J. Am. Chem. Soc. 1995, 117, 9653.
19. 3SnH, secondary iodides 1e and 1f gave lactones 3e and 3f as minor products, respectively (runs 10 and 12). This may be related to the known fact that secondary iodides are more prone to undergo atom transfer than primary iodides. (a) Newcomb, M.; Sanchez, R. M.; Kaplan, J. J. Am. Chem. Soc. 1987, 109, 1195. Also see: Curran, D. P.; Chang, C.-T. J. Org. Chem. 1989, 54, 3140 and references cited therein.
20. 3SnH, secondary iodides 1e and 1f gave lactones 3e and 3f as minor products, respectively (runs 10 and 12). This may be related to the known fact that secondary iodides are more prone to undergo atom transfer than primary iodides. (a) Newcomb, M.; Sanchez, R. M.; Kaplan, J. J. Am. Chem. Soc. 1987, 109, 1195. Also see: Curran, D. P.; Chang, C.-T. J. Org. Chem. 1989, 54, 3140 and references cited therein.
21. To the best of our knowledge, we are not aware of any precedent for this type of atom transfer reaction. Ab initio calculations (3-21G(*)) show that iodine atom transfer from alkyl iodide to acyl radical is energically unfavorable (ΔH = 4.83 kcal/mol for primary alkyl iodide, 1.92 kcal/mol for secondary alkyl iodide). As one possibility, we suspect that the subsequent conversion of acid iodide E to the pseudoacid iodide F might be sufficiently smooth to override this energetic disadvantage. For this cyclization step, a single electron transfer from acyl iodide to internal ketone carbonyl, followed by the coupling of the resulting ion pair or a spontaneously ionic path might be possible. Cf.: Heathcock, C. H.; Davidsen, S. K.; Mills, S. G.; Sanner, M. A. J. Org. Chem. 1992, 57, 2531.
22. 3GeH/CO in ethanol and potassium carbonate gave the corrresponding 4-keto ester in 21% yield. For details, see the Supporting Information. As for the formation of F, the detection of a small amount of unsaturated lactone 3e′ in the case of secondary iodide 1e, may document the existence of F in this reaction system. For mechanistic discussion on related transformations, see: (a) Bowman, W. R.; Heaney, H.; Jordan, B. M. Tetrahedron 1991, 47, 10119. (b) Curran, D. P.; Yu. H.; Liu, H. Tetrahedron 1994, 50, 7343. Beckwith, A. L. J.; Storey, J. M. D. J. Chem. Soc., Chem. Commun. 1995, 977.
23. 3GeH/CO in ethanol and potassium carbonate gave the corrresponding 4-keto ester in 21% yield. For details, see the Supporting Information. As for the formation of F, the detection of a small amount of unsaturated lactone 3e′ in the case of secondary iodide 1e, may document the existence of F in this reaction system. For mechanistic discussion on related transformations, see: (a) Bowman, W. R.; Heaney, H.; Jordan, B. M. Tetrahedron 1991, 47, 10119. (b) Curran, D. P.; Yu. H.; Liu, H. Tetrahedron 1994, 50, 7343. Beckwith, A. L. J.; Storey, J. M. D. J. Chem. Soc., Chem. Commun. 1995, 977.
24. 3GeH/CO in ethanol and potassium carbonate gave the corrresponding 4-keto ester in 21% yield. For details, see the Supporting Information. As for the formation of F, the detection of a small amount of unsaturated lactone 3e′ in the case of secondary iodide 1e, may document the existence of F in this reaction system. For mechanistic discussion on related transformations, see: (a) Bowman, W. R.; Heaney, H.; Jordan, B. M. Tetrahedron 1991, 47, 10119. (b) Curran, D. P.; Yu. H.; Liu, H. Tetrahedron 1994, 50, 7343. (c) Beckwith, A. L. J.; Storey, J. M. D. J. Chem. Soc., Chem. Commun. 1995, 977.