Carbometalation of Cyclopropene. Diastereoselective cis-Addition of Zincated Amides, Esters, and Hydrazones

Journal of Organic Chemistry

Volumn 62, Issue 4, 1997, Pages 792-793

  Nakamura, Eiichi ^a   Kubota, Katsumi ^b  

^a UNIVERSITY OF TOKYO   (Japan)

^b TOKYO INSTITUTE OF TECHNOLOGY   (Japan)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0001059579     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo962140q     Document Type: Article

References (25)

1. Cf. Addition of transition metal enolates: Ito, Y.; Nakatsuka, M.; Kise, N.; Saegusa, T. Tetrahedron Lett. 1980, 21, 2873-2876.
2. A rare example for main group metal enolates includes addition of a potassium enolate of an active methylene compound to 1-chlorobicyclo[4.1.0]hept-1-ene generated in situ: Arct, J.; Migaj, B. Tetrahedron 1980, 36, 953-956. Arct, J.; Migaj, B.; Leonczynski, A. Tetrahedron 1981, 37, 3689-3692.
3. A rare example for main group metal enolates includes addition of a potassium enolate of an active methylene compound to 1-chlorobicyclo[4.1.0]hept-1-ene generated in situ: Arct, J.; Migaj, B. Tetrahedron 1980, 36, 953-956. Arct, J.; Migaj, B.; Leonczynski, A. Tetrahedron 1981, 37, 3689-3692.
4. (a) The identity of the zinc enolate-like reagent is totally unknown as to whether the reagent bears 1 equiv each of "enolate" and butyl anion and whether the reactive species is a monomer or a dimer. The ca. 50% yield of the addition reaction under a 1:1 "enolate"/1 stoichiometry suggests that the reactive species bears two "enolate" units. The nature of the bonding between the "enolate" unit and the zinc(II) cation is also unclear.
5. (b) Ethylzinc enolate, which was found to be more reactive than the corresponding chlorozinc enolate, is considered to be an oxygen-bound enolate (Hansen, M. M.; Bartlett, P. A.; Heathcock, C. H. Organometallics 1987, 6, 2069-2074).
6. Among scant information, the zinc Reformatsky reagent is dimeric and may be viewed to possess a mixed C- and O-enolate character (Dekker, J.; Boersma, J.; van der Kerk, G. J. M. J. Chem. Soc., Chem. Commun. 1983, 553-555. Dekker, J.; Budzelaar, P. H. M.; Boersma, J.; van der Kerk, G. J. M.; Spek, A. L. Organometallics 1984, 3, 1403-1407) , and lithiated ketone hydrazone has an aza-π-allylic structure (Collum, D. B.; Kahne, D.; Gut, S. A.; DePue, R. T.; Mohamadi, F.; Wanat, R. A.; Clardy, J.; Duyne, G. V. J. Am. Chem. Soc. 1984, 106, 4865-4869. Wanat, R. A.; Collum, D. B. J. Am. Chem. Soc. 1985, 107, 2078-2082. Enders, D.; Bachstadter, G.; Kremer, K. A. M.; Marsch, M.; Harms, K.; Boche, G. Angew. Chem., Int. Ed. Engl. 1988, 27, 1522-1524).
7. Among scant information, the zinc Reformatsky reagent is dimeric and may be viewed to possess a mixed C- and O-enolate character (Dekker, J.; Boersma, J.; van der Kerk, G. J. M. J. Chem. Soc., Chem. Commun. 1983, 553-555. Dekker, J.; Budzelaar, P. H. M.; Boersma, J.; van der Kerk, G. J. M.; Spek, A. L. Organometallics 1984, 3, 1403-1407) , and lithiated ketone hydrazone has an aza-π-allylic structure (Collum, D. B.; Kahne, D.; Gut, S. A.; DePue, R. T.; Mohamadi, F.; Wanat, R. A.; Clardy, J.; Duyne, G. V. J. Am. Chem. Soc. 1984, 106, 4865-4869. Wanat, R. A.; Collum, D. B. J. Am. Chem. Soc. 1985, 107, 2078-2082. Enders, D.; Bachstadter, G.; Kremer, K. A. M.; Marsch, M.; Harms, K.; Boche, G. Angew. Chem., Int. Ed. Engl. 1988, 27, 1522-1524).
8. Among scant information, the zinc Reformatsky reagent is dimeric and may be viewed to possess a mixed C- and O-enolate character (Dekker, J.; Boersma, J.; van der Kerk, G. J. M. J. Chem. Soc., Chem. Commun. 1983, 553-555. Dekker, J.; Budzelaar, P. H. M.; Boersma, J.; van der Kerk, G. J. M.; Spek, A. L. Organometallics 1984, 3, 1403-1407) , and lithiated ketone hydrazone has an aza-π-allylic structure (Collum, D. B.; Kahne, D.; Gut, S. A.; DePue, R. T.; Mohamadi, F.; Wanat, R. A.; Clardy, J.; Duyne, G. V. J. Am. Chem. Soc. 1984, 106, 4865-4869. Wanat, R. A.; Collum, D. B. J. Am. Chem. Soc. 1985, 107, 2078-2082. Enders, D.; Bachstadter, G.; Kremer, K. A. M.; Marsch, M.; Harms, K.; Boche, G. Angew. Chem., Int. Ed. Engl. 1988, 27, 1522-1524).
9. Among scant information, the zinc Reformatsky reagent is dimeric and may be viewed to possess a mixed C- and O-enolate character (Dekker, J.; Boersma, J.; van der Kerk, G. J. M. J. Chem. Soc., Chem. Commun. 1983, 553-555. Dekker, J.; Budzelaar, P. H. M.; Boersma, J.; van der Kerk, G. J. M.; Spek, A. L. Organometallics 1984, 3, 1403-1407) , and lithiated ketone hydrazone has an aza-π-allylic structure (Collum, D. B.; Kahne, D.; Gut, S. A.; DePue, R. T.; Mohamadi, F.; Wanat, R. A.; Clardy, J.; Duyne, G. V. J. Am. Chem. Soc. 1984, 106, 4865-4869. Wanat, R. A.; Collum, D. B. J. Am. Chem. Soc. 1985, 107, 2078-2082. Enders, D.; Bachstadter, G.; Kremer, K. A. M.; Marsch, M.; Harms, K.; Boche, G. Angew. Chem., Int. Ed. Engl. 1988, 27, 1522-1524).
10. Among scant information, the zinc Reformatsky reagent is dimeric and may be viewed to possess a mixed C- and O-enolate character (Dekker, J.; Boersma, J.; van der Kerk, G. J. M. J. Chem. Soc., Chem. Commun. 1983, 553-555. Dekker, J.; Budzelaar, P. H. M.; Boersma, J.; van der Kerk, G. J. M.; Spek, A. L. Organometallics 1984, 3, 1403-1407) , and lithiated ketone hydrazone has an aza-π-allylic structure (Collum, D. B.; Kahne, D.; Gut, S. A.; DePue, R. T.; Mohamadi, F.; Wanat, R. A.; Clardy, J.; Duyne, G. V. J. Am. Chem. Soc. 1984, 106, 4865-4869. Wanat, R. A.; Collum, D. B. J. Am. Chem. Soc. 1985, 107, 2078-2082. Enders, D.; Bachstadter, G.; Kremer, K. A. M.; Marsch, M.; Harms, K.; Boche, G. Angew. Chem., Int. Ed. Engl. 1988, 27, 1522-1524).
11. Nakamura, E. J. Synth. Org. Chem. Jpn. 1994, 52, 935-945. Isaka, M.; Ejiri, S.; Nakamura, E. Tetrahedron, 1992 48, 2045-2057.
12. Nakamura, E. J. Synth. Org. Chem. Jpn. 1994, 52, 935-945. Isaka, M.; Ejiri, S.; Nakamura, E. Tetrahedron, 1992 48, 2045-2057.
13. Kubota, K.; Nakamura, M.; Isaka, M.; Nakamura, E. J. Am. Chem. Soc. 1993, 115, 5867-5868. Nakamura, E. Pure Appl. Chem. 1996, 68, 123-130.
14. Kubota, K.; Nakamura, M.; Isaka, M.; Nakamura, E. J. Am. Chem. Soc. 1993, 115, 5867-5868. Nakamura, E. Pure Appl. Chem. 1996, 68, 123-130.
15. Seebach, D.; Weller, T.; Protschuk, G.; Beck, A. K.; Hoekstra, M. S. Helv. Chim. Acta 1981, 64, 716-735.
16. House, H. O.; Crumrine, D. S.; Teranishi, A. Y.; Olmstead, H. D. J. Am. Chem. Soc. 1973, 95, 3310-3324.
17. An α-anion of a hydrazone of aliphatic ketones may exist in its E-geometry (as viewed as an enolate, see ref 3): Davenport, K. G.; Eichenauer, H.; Enders, D.; Newcomb, M.; Bergbreiter, D. E. J. Am. Chem. Soc. 1979, 101, 5654-5659.
18. Nakamura, M.; Nakamura, E.; Koga, N.; Morokuma, K. J. Chem. Soc., Faraday Trans. 1994, 90, 1789-1798. Nakamura, M.; Nakamura, E. Computational Studies on Diastereo- and Enantioselectivities of Allylmetalation of Cyclopropenone Acetals. In Electronic Conference Heterocyclic Chemistry; Rzepa, H. S., Snyder, J., Leach, C., Eds.; Royal Society of Chemistry: London, 1997; in press (ISBN 0-85404-894-4).
19. Nakamura, M.; Nakamura, E.; Koga, N.; Morokuma, K. J. Chem. Soc., Faraday Trans. 1994, 90, 1789-1798. Nakamura, M.; Nakamura, E. Computational Studies on Diastereo- and Enantioselectivities of Allylmetalation of Cyclopropenone Acetals. In Electronic Conference Heterocyclic Chemistry; Rzepa, H. S., Snyder, J., Leach, C., Eds.; Royal Society of Chemistry: London, 1997; in press (ISBN 0-85404-894-4).
20. 2 in THF (1.01 M, 20 mL, 20 mmol, at 0 °C) and then BuLi (1.58 M in hexane, 12.6 mL, 20 mmol, at -70 °C) were added. After 30 min at 0 °C, 1 (1.4 mL, 10 mmol) was added, and the mixture was stirred for 10 min. A 1/15 N phosphate buffer solution was added, and after extractive workup, an oily crude product (3.28 g) was obtained. Purification on silica gel (10% and then 20% EtOAc in hexane) afforded the desired adduct (2.52 g, 94%) as a 94:6 mixture of diastereomers.
21. Enders, D. Asymmetric Synthesis; Morrison, J. M., Ed.; Academic Press: New York, 1984; Vol. 3, pp 275-339.
22. For the determination of stereochemistry, see footnote a in Table 1.
23. Attempts to achieve enantioselective carbometalation with enolates bearing a chiral metal ligand so far failed (low ee's). Cf.: Nakamura, M.; Arai, M.; Nakamura, E. J. Am. Chem. Soc. 1995, 117, 1179-1180. Nakamura, M.; Hirai, A.; Nakamura, E. J. Am. Chem. Soc. 1996, 118, 8489-8490.
24. Attempts to achieve enantioselective carbometalation with enolates bearing a chiral metal ligand so far failed (low ee's). Cf.: Nakamura, M.; Arai, M.; Nakamura, E. J. Am. Chem. Soc. 1995, 117, 1179-1180. Nakamura, M.; Hirai, A.; Nakamura, E. J. Am. Chem. Soc. 1996, 118, 8489-8490.
25. The author has deposited atomic coordinates for (1′R*,2S*)-2-(3-aza-3-methyl-2-oxocyclohexyl)cyclopropanone 1,3-(2,2-dimethylpropanediyl acetal) with the Cambridge Crystallographic Data Centre. The coordinates can be obtained, on request, from the Director, Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge, CB2 1EZ, UK