Novel migrating group in 1,2-anionotropic reactions: Cobalt complexation facilitates 1,2-shift of alkynyl groups

Journal of the American Chemical Society

Volumn 118, Issue 37, 1996, Pages 8949-8950

  Nagasawa, Tetsuya ^a   Taya, Kimiko ^a   Kitamura, Mitsuru ^a   Suzuki, Keisuke ^a,b  

^a KEIO UNIVERSITY   (Japan)

^b TOKYO INSTITUTE OF TECHNOLOGY   (Japan)

Author keywords

[No Author keywords available]

Indexed keywords

ALKYNE DERIVATIVE; COBALT COMPLEX;

ARTICLE; COMPLEX FORMATION; DRUG SYNTHESIS; REACTION ANALYSIS;

EID: 0029814942     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja961030y     Document Type: Article

References (39)

1. (a) For a review, see: Nicholas, K. M. Acc. Chem. Res. 1987, 20, 207. (b) Olah, G. A.; Reddy, V. P.; Prakash, G. K. Chem. Rev. 1992, 92, 69 and references cited therein.
2. (a) For a review, see: Nicholas, K. M. Acc. Chem. Res. 1987, 20, 207. (b) Olah, G. A.; Reddy, V. P.; Prakash, G. K. Chem. Rev. 1992, 92, 69 and references cited therein.
3. (a) Hoffman, D. M.; Hoffmann, R.; Fisel, C. R. J. Am. Chem. Soc. 1982, 104, 3858 and references cited therein.
4. (b) Schreiber, S. L.; Sammakia, T.; Crowe, W. E. J. Am. Chem. Soc: 1986, 116, 5505.
5. (c) Schreiber, S. L., Klimas, M. T.; Sammakia, T. J. Am. Chem. Soc. 1987, 109, 5749.
6. For the 1,2-shift of cyclopropyl groups, see: (a) Shono, T.; Fujita, K.; Kumai, S.; Watanabe, T.; Nishiguchi, I. Tetrahedron Lett. 1972, 3249. (b) Shimazaki, M.; Hara, H.; Suzuki, K. Tetrahedron Lett. 1989, 30, 5443.
7. For the 1,2-shift of cyclopropyl groups, see: (a) Shono, T.; Fujita, K.; Kumai, S.; Watanabe, T.; Nishiguchi, I. Tetrahedron Lett. 1972, 3249. (b) Shimazaki, M.; Hara, H.; Suzuki, K. Tetrahedron Lett. 1989, 30, 5443.
8. For reviews on 1,2-anionotropic reactions, see: (a) Saunders, M.; Chandrasekhar, J. ; Schleyer, P. v. R. In Rearrangement in Ground and Excited States; Mayo, P. de. Ed.; Academic Press: New York, 1980; Vol. 1, p 1. (b) Shubin, V. G. In Topics in Current Chemistry; Rees, C., Ed.; Springer: Berlin, 1984; Vol, 116-117, p 267. (c) Collins, C. J.; Eastham, J. F. The Chemistry of the Carbonyl Group (The Chemistry of Functional Groups); Patai, S., Ed.; Wiley: New York, 1966; Chapter 15, p 761. (d) Bartok, M.; Molnár, A. The Chemistry of Functional Groups, Supplement E; Patai, S., Ed.; Wiley: New York, 1980; Chapter 16, p 721. For reviews on pinacol rearrangement, see: (e) Rickborn, B. In Comprehensive Organic Synthesis; Trost, B. M., Fleming, I., Eds.; Pergamon: Oxford, 1991; Vol. 3, Chapter 3.2, p 721. (f) Suzuki, K. J. Synth. Org. Chem., Jpn. 1988, 46, 365.
9. For reviews on 1,2-anionotropic reactions, see: (a) Saunders, M.; Chandrasekhar, J. ; Schleyer, P. v. R. In Rearrangement in Ground and Excited States; Mayo, P. de. Ed.; Academic Press: New York, 1980; Vol. 1, p 1. (b) Shubin, V. G. In Topics in Current Chemistry; Rees, C., Ed.; Springer: Berlin, 1984; Vol, 116-117, p 267. (c) Collins, C. J.; Eastham, J. F. The Chemistry of the Carbonyl Group (The Chemistry of Functional Groups); Patai, S., Ed.; Wiley: New York, 1966; Chapter 15, p 761. (d) Bartok, M.; Molnár, A. The Chemistry of Functional Groups, Supplement E; Patai, S., Ed.; Wiley: New York, 1980; Chapter 16, p 721. For reviews on pinacol rearrangement, see: (e) Rickborn, B. In Comprehensive Organic Synthesis; Trost, B. M., Fleming, I., Eds.; Pergamon: Oxford, 1991; Vol. 3, Chapter 3.2, p 721. (f) Suzuki, K. J. Synth. Org. Chem., Jpn. 1988, 46, 365.
10. For reviews on 1,2-anionotropic reactions, see: (a) Saunders, M.; Chandrasekhar, J. ; Schleyer, P. v. R. In Rearrangement in Ground and Excited States; Mayo, P. de. Ed.; Academic Press: New York, 1980; Vol. 1, p 1. (b) Shubin, V. G. In Topics in Current Chemistry; Rees, C., Ed.; Springer: Berlin, 1984; Vol, 116-117, p 267. (c) Collins, C. J.; Eastham, J. F. The Chemistry of the Carbonyl Group (The Chemistry of Functional Groups); Patai, S., Ed.; Wiley: New York, 1966; Chapter 15, p 761. (d) Bartok, M.; Molnár, A. The Chemistry of Functional Groups, Supplement E; Patai, S., Ed.; Wiley: New York, 1980; Chapter 16, p 721. For reviews on pinacol rearrangement, see: (e) Rickborn, B. In Comprehensive Organic Synthesis; Trost, B. M., Fleming, I., Eds.; Pergamon: Oxford, 1991; Vol. 3, Chapter 3.2, p 721. (f) Suzuki, K. J. Synth. Org. Chem., Jpn. 1988, 46, 365.
11. For reviews on 1,2-anionotropic reactions, see: (a) Saunders, M.; Chandrasekhar, J. ; Schleyer, P. v. R. In Rearrangement in Ground and Excited States; Mayo, P. de. Ed.; Academic Press: New York, 1980; Vol. 1, p 1. (b) Shubin, V. G. In Topics in Current Chemistry; Rees, C., Ed.; Springer: Berlin, 1984; Vol, 116-117, p 267. (c) Collins, C. J.; Eastham, J. F. The Chemistry of the Carbonyl Group (The Chemistry of Functional Groups); Patai, S., Ed.; Wiley: New York, 1966; Chapter 15, p 761. (d) Bartok, M.; Molnár, A. The Chemistry of Functional Groups, Supplement E; Patai, S., Ed.; Wiley: New York, 1980; Chapter 16, p 721. For reviews on pinacol rearrangement, see: (e) Rickborn, B. In Comprehensive Organic Synthesis; Trost, B. M., Fleming, I., Eds.; Pergamon: Oxford, 1991; Vol. 3, Chapter 3.2, p 721. (f) Suzuki, K. J. Synth. Org. Chem., Jpn. 1988, 46, 365.
12. For reviews on 1,2-anionotropic reactions, see: (a) Saunders, M.; Chandrasekhar, J. ; Schleyer, P. v. R. In Rearrangement in Ground and Excited States; Mayo, P. de. Ed.; Academic Press: New York, 1980; Vol. 1, p 1. (b) Shubin, V. G. In Topics in Current Chemistry; Rees, C., Ed.; Springer: Berlin, 1984; Vol, 116-117, p 267. (c) Collins, C. J.; Eastham, J. F. The Chemistry of the Carbonyl Group (The Chemistry of Functional Groups); Patai, S., Ed.; Wiley: New York, 1966; Chapter 15, p 761. (d) Bartok, M.; Molnár, A. The Chemistry of Functional Groups, Supplement E; Patai, S., Ed.; Wiley: New York, 1980; Chapter 16, p 721. For reviews on pinacol rearrangement, see: (e) Rickborn, B. In Comprehensive Organic Synthesis; Trost, B. M., Fleming, I., Eds.; Pergamon: Oxford, 1991; Vol. 3, Chapter 3.2, p 721. (f) Suzuki, K. J. Synth. Org. Chem., Jpn. 1988, 46, 365.
13. For reviews on 1,2-anionotropic reactions, see: (a) Saunders, M.; Chandrasekhar, J. ; Schleyer, P. v. R. In Rearrangement in Ground and Excited States; Mayo, P. de. Ed.; Academic Press: New York, 1980; Vol. 1, p 1. (b) Shubin, V. G. In Topics in Current Chemistry; Rees, C., Ed.; Springer: Berlin, 1984; Vol, 116-117, p 267. (c) Collins, C. J.; Eastham, J. F. The Chemistry of the Carbonyl Group (The Chemistry of Functional Groups); Patai, S., Ed.; Wiley: New York, 1966; Chapter 15, p 761. (d) Bartok, M.; Molnár, A. The Chemistry of Functional Groups, Supplement E; Patai, S., Ed.; Wiley: New York, 1980; Chapter 16, p 721. For reviews on pinacol rearrangement, see: (e) Rickborn, B. In Comprehensive Organic Synthesis; Trost, B. M., Fleming, I., Eds.; Pergamon: Oxford, 1991; Vol. 3, Chapter 3.2, p 721. (f) Suzuki, K. J. Synth. Org. Chem., Jpn. 1988, 46, 365.
14. The poor migratory aptitude of an alkynyl group is attributed to the deficiency of its π-electrons to participate to the neighboring cationic species in terms of electronic (the sp hybridization) and/or spatial (the linearity) factors. Computational studies showed that the activation energy of the ethynyl shift is larger than, for example, that of the vinyl migration by 10.5 kcal/mol. Nakamura, K.; Osamura, Y. J. Am. Chem. Soc. 1993, 115, 9112.
15. (a) Wender, P. A.; Holt, D. A.; Sieburth, S. M. J. Am. Chem. Soc. 1983, 105, 3348.
16. (b) Suzuki, K.; Ohkuma, T.; Miyazawa, M.; Tsuchihashi, G. Tetrahedron Lett. 1986, 27, 373.
17. (c) Shoenen, F. J.; Porco, J. A.; Schreiber, S. L.; VanDuyne, G. D.; Clardy, J. Tetrahedron Lett. 1989, 30, 3765.
18. For preparation of the chlorohydrins. see supporting information.
19. 13C NMR, IR), high-resolution MS, and/or combustion analysis (see supporting information).
20. 2.
21. Note that the reactions proceed at lower temperatures in runs 2 and 3. Origin of the substituent effect is under investigation. At present, we assume that the migratory aptitude is enhanced by a substituent that stabilizes a positive charge that would develop at the migrating cluster during the 1,2-shift by analogy with the α-cation stabilization (see A and A′).
22. For organoaluminum-promoted 1,2-shift of aryl groups in β-mesyloxy alcohols, see: (a) Suzuki, K.; Katayama, E.; Tsuchihashi, G. Tetrahedron Lett. 1983, 24, 4997. For a classical example under solvolytic conditions, see: (b) Winstein, S.; Lindegren, C. R.; Marshall, H.; Ingraham, L. L. J. Am. Chem. Soc. 1953, 75, 147.
23. For organoaluminum-promoted 1,2-shift of aryl groups in β-mesyloxy alcohols, see: (a) Suzuki, K.; Katayama, E.; Tsuchihashi, G. Tetrahedron Lett. 1983, 24, 4997. For a classical example under solvolytic conditions, see: (b) Winstein, S.; Lindegren, C. R.; Marshall, H.; Ingraham, L. L. J. Am. Chem. Soc. 1953, 75, 147.
24. 3Al. It is also a significant point to note that, stereochemically, the 1,2-shift of mesyloxy alcohols proceeds with inversion (cf. double inversion for the epoxide mechanism).
25. 3Al. It is also a significant point to note that, stereochemically, the 1,2-shift of mesyloxy alcohols proceeds with inversion (cf. double inversion for the epoxide mechanism).
26. In the reaction of the noncomplexed congener of 5a, the 1.2-shift of the phenyl group prevailed over that of the 1-hexynyl group (selectivity: 9/1). Since the reaction only occurred at 20 °C, the carbonyls in the products were thoroughly methylated (96% combined yield).
27. The migratory aptitude of the p-methoxyphenyl group is reportedly 500 times higher than that of the phenyl group in pinacol rearrangement. Acheson, R. M. Acc. Chem. Res. 1971, 4, 177.
28. (a) Suzuki, K.; Katayama, E.; Tsuchihashi, G. Tetrahedron Lett. 1984, 25, 1817.
29. (b) Suzuki, K.; Tomooka, K.; Katayama, E.; Matsumoto, T.; Tsuchihashi, G. J. Am. Chem. Soc. 1986, 108, 5221.
30. A 1/1 diastereomeric mixture. For the ee analysis by chiral capillary GC, see supporting information.
31. For a review, see Martin, S. F. Tetrahedron 1980, 36, 419.
32. For stereospecific synthesis of α,α-disubstituted aldols via epoxy silyl ether (epoxy alcohol) rearrangements, see: Shimazaki. M.; Hara, H.; Suzuki, K.; Tsuchihashi, G. Tetrahedron Lett. 1987, 28, 5891. For review. see ref 6f. See also: (a) Maruoka, K.; Hasegawa, M.; Yamamoto, H.; Suzuki, K.; Shimazaki, M.; Tsuchihashi, G. J. Am. Chem. Soc. 1986, 108, 3827. (c) Suzuki, K.; Miyazawa, M.; Tsuchihashi, G. Tetrahedron Lett. 1987, 28, 3515. (d) Suzuki, K.; Miyazawa, M.; Shimazaki, M.; Tsuchihashi, G. Tetrahedron 1988, 44, 4061.
33. For stereospecific synthesis of α,α-disubstituted aldols via epoxy silyl ether (epoxy alcohol) rearrangements, see: Shimazaki. M.; Hara, H.; Suzuki, K.; Tsuchihashi, G. Tetrahedron Lett. 1987, 28, 5891. For review. see ref 6f. See also: (a) Maruoka, K.; Hasegawa, M.; Yamamoto, H.; Suzuki, K.; Shimazaki, M.; Tsuchihashi, G. J. Am. Chem. Soc. 1986, 108, 3827. (c) Suzuki, K.; Miyazawa, M.; Tsuchihashi, G. Tetrahedron Lett. 1987, 28, 3515. (d) Suzuki, K.; Miyazawa, M.; Shimazaki, M.; Tsuchihashi, G. Tetrahedron 1988, 44, 4061.
34. For stereospecific synthesis of α,α-disubstituted aldols via epoxy silyl ether (epoxy alcohol) rearrangements, see: Shimazaki. M.; Hara, H.; Suzuki, K.; Tsuchihashi, G. Tetrahedron Lett. 1987, 28, 5891. For review. see ref 6f. See also: (a) Maruoka, K.; Hasegawa, M.; Yamamoto, H.; Suzuki, K.; Shimazaki, M.; Tsuchihashi, G. J. Am. Chem. Soc. 1986, 108, 3827. (c) Suzuki, K.; Miyazawa, M.; Tsuchihashi, G. Tetrahedron Lett. 1987, 28, 3515. (d) Suzuki, K.; Miyazawa, M.; Shimazaki, M.; Tsuchihashi, G. Tetrahedron 1988, 44, 4061.
35. For stereospecific synthesis of α,α-disubstituted aldols via epoxy silyl ether (epoxy alcohol) rearrangements, see: Shimazaki. M.; Hara, H.; Suzuki, K.; Tsuchihashi, G. Tetrahedron Lett. 1987, 28, 5891. For review. see ref 6f. See also: (a) Maruoka, K.; Hasegawa, M.; Yamamoto, H.; Suzuki, K.; Shimazaki, M.; Tsuchihashi, G. J. Am. Chem. Soc. 1986, 108, 3827. (c) Suzuki, K.; Miyazawa, M.; Tsuchihashi, G. Tetrahedron Lett. 1987, 28, 3515. (d) Suzuki, K.; Miyazawa, M.; Shimazaki, M.; Tsuchihashi, G. Tetrahedron 1988, 44, 4061.
36. Silyl ethers 16, 17, 20 are epimeric mixture with respect to the tertor sec-siloxy substituted carbon. No noticeable difference in the reactivity was seen for the epimers.
37. For the stereostructure of aldols 18 and 19, see supporting information.
38. 6). Diagnostic signals appear at δ4.13 (dq) for 18 and at δ3.97 (q) for 19. It should be noted that partial isomerization (18 → 19 and vice versa) occurs upon prolonged exposure to silica gel.
39. Saito, T.; Morimoto, M.; Akiyama, C.; Matsumoto, T.; Suzuki, K. J. Am. Chem. Soc. 1995, 117, 10757.