Triorganothallium Reagents in Organic Chemistry. 1. A Simple, Efficient, and Versatile Preparation of Ketones from Acid Chlorides

Journal of Organic Chemistry

Volumn 55, Issue 10, 1990, Pages 3368-3370

  Markó, István E ^a   Southern, J Mike ^a  

^a UNIVERSITY OF SHEFFIELD   (United Kingdom)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0001489549     PISSN: 00223263     EISSN: 15206904     Source Type: Journal    
DOI: 10.1021/jo00297a069     Document Type: Article

References (29)

1. House, H. O. Modern Synthetic Reactions; W. A. Benjamin, Inc.: London, 1972.
2. March, J. Advanced Organic Chemistry; J. Wiley and Sons: New York, 1985.
3. For some leading references discussing the scope and the use of organometallic reagents, other than organocadmium and organocopper, in the transformation of acid chlorides into ketones, see: Collman, J. P., Hegedus, L. S., Norton, J. R., Finke, R. G. Principles and Applications of Organotransition Metal Chemistry; University Science Books: Mill Valley. CA. 1987.
4. Posner, G. H. Organic Reactions; J. Wiley and Sons: New York, 1975; Vol. 22, p 253.
5. Castro, C. E.; Havlin, R.; Honwad, V. K.; Malte, A.: Moie, S. J. Am. Chem. Soc. 1969. 91, 6464.
6. Cason, J.; Fessenden, R. j. Org. Chem. 1960, 25, 477.
7. Typical problems associated with this simple transformation are (a) the overaddition of the organometallic reagent, leading to tertiary alcohols, (b) decomposition or racemization of the starting material under the rigorous conditions required for some reagents, e.g., organocadmiums, (c) instability of the organometallic reagent, e.g., organocuprates, (d) difficulties in preparing branched organometallic reagents and therefore in forming branched ketones. Numerous branched triorganothallium compounds have been prepared (ref 9) by classical organometallic reactions. They are much more stable than their copper, cadmium, and zinc counterparts. Ketone synthesis using these branched derivatives will be reported in due course.
8. Gilman, H.; Jones, R. G. J. Am. Chem. Soc. 1946, 68, 517.
9. Gilman, H.; Jones, R. G. J. Am. Chem. Soc. 1950, 72, 1760.
10. Groll, H. P. A. J. Am. Chem. Soc. 1930, 52, 2998.
11. Rochow, E. G.; Dennis, L. M. J. Am. Chem. Soc. 1935, 57, 486.
12. Birch, S. F. J. Chem. Soc. 1934, 1132.
13. Birch, S. F. J. Chem. Soc. 1934, 1132.
14. Gilman, H.; Jones, R. G. J. Am. Chem. Soc. 1939, 61, 1513.
15. Lee, A. G. The Chemistry of Thallium; Elsevier: Barking, U.K. 1971.
16. Kurosawa, H. Comprehensive Organometallic Chemistry; Wilkinson. G., Ed.: Pergamon Press: Oxford. 1982: Vol. 1. p 725.
17. Okhlobystin, O. Y.; Bilevitch, K. A.; Zakharkin, L. J. J. Organomet. Chem. 1964, 2, 281.
18. Triorganothallium compounds are highly reactive, as exemplified by the weakness of the TI-C bond, e.g., the mean value for the Ti-C bond dissociation energy in trimethylthallium is 27.4 kcal/mol as compared to 70.5 kcal/mol for monomeric trimethvlaluminum.
19. For example, trimethylthallium reacts with an equimolar mixture of 2-butanone and decanoyl chloride to produce 2-undecanone. No 2-methyl-2-butanol could be detected.
20. Lee, A. G. J. Chem. Soc. A 1970, 2157.
21. Nast, R., Kab, K. J. Organomet. Chem. 1966. 6. 456.
22. Not every mixed triorganothallium reagent transfers their ligands with such high selectivity, e.g., dimethylphenylthallium reacts with decanoyl chloride to give a 2/3 mixture of 2-undecanone and phenyl no-nanyl ketone.
23. Trimethylindium reacts similarly with acid chlorides, giving methyl ketones in high yields. However, in contrast with triorganothallium reagents that transfer only one group—giving the highly stable diorganothallium(III) halides—all three groups of trimethylindium are used in this reaction, leading to indium trichloride (Markó, I. E. Unpublished results).
24. Browning, E. C. Toxicity of Industrial Metals; Butterworths: London, 1961
25. Grunfeld, O.; Hinostroza, G. Arch. Int. Med. 1964, 114, 132.
26. Taylor, E. C.; McKillop, A. Acc. Chem. Res. 1970, 338.
27. For antidotes, see: Heydlaug, H. Eur. J. Pharm. 1969, 6, 340.
28. For useful references concerning the handling of organothallium compounds, see: (c) Organic Synthesis, Vol. 6, 348, 488, 709, 791.
29. McKillop, A.; Taylor, E. C. Comprehensive Organometallic Chemistry, Vol. 7, 1982.