Reactions of cyclopropenes with organoaluminum compounds and other organometallic compounds: Formation of ring-opened products

Organometallics

Volumn 26, Issue 3, 2007, Pages 609-616

  Smith, Mark A ^a   Richey Jr , Herman G ^a  

^a PENNSYLVANIA STATE UNIVERSITY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

CYCLOPROPENE DOUBLE BONDS; CYCLOPROPENES; ORGANOALUMINUM COMPOUNDS; RING OPENED PRODUCTS;

ALUMINUM COMPOUNDS; CHEMICAL BONDS; ORGANOMETALLICS; REACTION KINETICS;

OLEFINS;

EID: 33847279988     PISSN: 02767333     EISSN: None     Source Type: Journal    
DOI: 10.1021/om060766t     Document Type: Article

References (53)

1. Richey, H. G., Jr.; Kubala, B.; Smith, M. A. Tetrahedron Lett. 1981, 22 3471.
2. Binger, P.; Schäfer, H. Tetrahedron Lett. 1975, 4673.
3. Jackman, L. M.; Sternhell, S. Applications of Nuclear Magnetic Resonance Spectroscopy in Organic Chemistry, 2nd ed.; Pergamon: Oxford, 1969; Chapter 4-2.
4. Wiberg, K. B.; Barth, D. E.; Schertier, P. H. J. Org. Chem. 1973, 38, 378.
5. The stereochemistry of the alkene function of 8, 9, 10, 12, or 21 is not known with certainty.
6. The following review many aspects of properties, preparations, and reactions of organoaluminum compounds. Mole, T.; Jeffery, E. A. Organoaluminum Compounds; Elsevier: Amsterdam, 1972.
7. Eisch, J. J. In Comprehensive Organometallic Chemistry; Wilkinson, G., Stone, F. G. A., Abel, E. A., Eds.; Pergamon: Oxford, 1982; Vol. 1, Chapter 6.
8. Eisch, J. J. In Comprehensive Organometallic Chemistry II; Abel, E. A., Stone, F. G. A., Wilkinson, G., Eds.; Pergamon: Oxford, 1995; Vol. 1, Chapter 10.
9. A review of carboalumination and other reactions of organoaluminum compounds with organic substrates: Eisch, J. J. In Comprehensive Organometallic Chemistry; Abel, E. A., Stone, F. G. A., Wilkinson, G., Eds.; Pergamon: Oxford, 1995; Vol. 11, Chapter 6.
10. A review of carbometalation by organoaluminum, organoboron, organomagnesium, organozinc, organocopper, and organolithium compounds: Knochel, P. In Comprehensive Organic Synthesis; Trost, B. M., Fleming, I., Eds.; Pergamon: Oxford, 1991; Vol. 4, Chapter 4.4.
11. A review of current developments in cyclopropene chemistry including carbometalation and a source of references to other reviews: Rubin, M.; Rubina, M.; Gevorgyan, V. Synthesis 2006, 1221.
12. Material balances were generally good, although small amounts of higher molecular weight products were sometimes noted in GC traces.
13. 3Al to 4 or 7 was 0.3 indicate that more than one ethyl group of EtsAl became incorporated into the products.
14. For example, no significant amount of product was observed from a reaction for 1 h at 0°C (each reactant 0.15 M in benzene-hexane (5:1, v/v)); in a similar reaction at ambient temperature, product was still forming after 3 days.
15. Neither 4 nor 13 contained excess deuterium when a reaction was quenched with 0:0.
16. Nefedov, O. M.; Dolgii, I. E.; Bulusheva, E. V.; Shteinshneider, A. Ya. Bull. Acad. Sci. USSR, Div. Chem. Sci. (Engl Transl.) 1979, 1422.
17. Izv. Akad. Nauk. SSSR, Ser. Khim. 1979, 1535.
18. The stereochemistry of 14 or 15 is not known with certainty.
19. 3Al are not strictly comparable.
20. It was not determined if any 23 remained since its GC retention time was close to that of the solvent.
21. 3Al, even at -100°C, produced mainly polymeric products.
22. A review: Eisch, J. J. J. Organomet. Chem. 1995, 500, 101.
23. Hata, G. Chem. Commun. 1968, 7. Dolzine, T. W.;
24. Oliver, J. P. J. Am. Chem. Soc. 1974, 96, 1737.
25. Dolzine, T. W.; Oliver, J. P. J. Organomet. Chem. 1974, 78, 165.
26. For MO calculations about carboalumination of alkenes, see the following and references therein: Bundens, J. W.; Yudenfreund, J.; Francl, M. M. Organometallics 1999, 18, 3913.
27. Sankararaman, S. Pericyclic Reactions-A Textbook; Wiley-VCH: Weinheim, 2005; pp 32-37.
28. Sorenson, T. S.; Rauk, A. In Pericyclic Reactions; Marchand, A. P., Lehr, R. E., Eds.; Academic: New York, 1977; Vol. 2, pp 3-19.
29. Attachment at the more substituted carbon is also often observed for allylic compounds of other metals, e.g., zinc: Nakamura, M; Inoue, T.; Sato, A.; Nakamura, E. Org. Lett. 2000, 2, 2193, and references therein.
30. 6,7 aluminum at the less-substituted alkene carbon and isomerization then would lead to a different placement of ethyl groups in the product than is observed.
31. Could addition of the allylic organoaluminum compound be so extremely rapid that addition products result from reactions of the firstformed allylic isomer rather than from an equilibrium mixture of the allylic isomers? That cannot be the case in the reactions of 4 since the results indicate that addition of an allylic species is similar in rate to addition of EtsAl, which is not extremely fast since some 4 is recovered from reactions at low temperatures.
32. 3Al. Bubnov, Yu. N.; Nesmeyanova, O. A.; Rudashevskaya, T. Yu.; Mikhailov, B. M.; Kazansky, B. A. Tetrahedron Lett. 1971, 2153.
33. Mikhailov, B. M.; Bubnov, Yu. N.; Nesmeyanova, O. A.; Kieselev, V. G.; Rudashevskaya, T. Yu.; Kazansky, B. A. Tetrahedron Lett. 1972, 4627.
34. Bubnov, Yu. N.; Nesmeyanova, O. A.; Rudashevskaya, T. Yu.; Mikhailov, B. M.; Kazanskii, B. A. J. Gen. Chem. USSR (Engl. Transl.) 1973, 43, 125;
35. Zh. Obshch. Khim. 1973, 43, 127.
36. Bubnov, Yu. N.; Nesmeyanova, O. A.; Rudashevskaya, T. Yu.; Mikhailov, B. M.; Kazanskii, B. A. J. Gen. Chem. USSR (Engl. Transl.) 1973, 43, 132;
37. Zh. Obshch. Khim. 1973, 43, 135.
38. Bubnov, Yu. N.; Kazanskii, B. A.; Nesmeyanova, O. A.; Rudashevskaya, T. Yu.; Mikhailov, B. M. Bull. Acad. Sci. USSR, Div. Chem. Sci. (Engl. Transl.) 1979, 2358;
39. Izv. Akad. Nauk SSSR, Ser. Khim. 1979, 2538.
40. Addition of organomagnesium compounds to cyclopropenes without rearrangement is well known. Ref 27 and Richey, H. G., Jr. In Inorganic Reactions and Methods; Hagen, A. P., Ed.; VCH: New York, 1989; Vol. 10, Section 5.4.2.5.1.
41. Watkins, E. K.; Richey, H. G., Jr. Organometallics 1992, 11, 3785.
42. Reactions of diborane and cyclopropenes have been observed to give addition (but no rearrangement) products: Köster, R.; Arora, S.; Binger, P. Angew. Chem., Int. Ed. Engl. 1969, 8, 205.
43. Zimmerman, H. E.; Nuss, J. M.; Tantillo, A. W. J. Org. Chem. 1988, 53, 3792.
44. For MO calculations about hydroboration see: Wang, X.; Li, Y.; Wu, Y.-D.; Paddon-Row, M. N.; Rondan, N. G.; Houk, K. N. J. Org. Chem. 1990, 55, 2601, and references therein.
45. 27
46. For example: Lehmkuhl, H.; Olbrysch, O.; Reinehr, D.; Schomburg, G.; Henneberg, D. Liebigs Ann. Chem. 1975, 145.
47. Also see: Lehmkuhl, H.; Bergstein, W.; Henneberg, D.; Janssen, E.; Olbrysch, O.; Reinehr, D.; Schomburg, G. Liebigs Ann. Chem. 1975, 1176.
48. A product corresponding to 9 was not observed, indicating that the allylic precursors of 21 and 22 did not add to the more hindered alkene function of 7.
49. For carbene insertion into C-H bonds see: Smith, M. B.; March, J. March's Advanced Organic Chemistry, 5th ed.; Wiley: New York, 2001; pp 251 and 788-791.
50. Insertion exclusively at the methylene of diethyl ether rather than also at the methyl indicates considerable selectivity by the carbene.
51. Greater steric demands may be another factor contributing to more rearrangement in reactions with trivalent compounds (B, Al, Ga) than with divalent compounds (Mg, Zn, Cd).
52. This compound has been reported before, but no mp was given. Boche, G.; Buckl, K. Angew. Chem., Int. Ed. Engl. 1978, 17, 284.
53. 2Cd solution contained a small amount of diethyl ether.