Electrophilic and Nucleophilic Organoselenium Reagents. New Routes to α,β-Unsaturated Carbonyl Compounds

Journal of the American Chemical Society

Volumn 95, Issue 18, 1973, Pages 6137-6139

  Sharpless, K B ^a   Lauer, R F ^a   Teranishi, A Y ^a,b  

^a MASSACHUSETTS INSTITUTE OF TECHNOLOGY   (United States)

^b NATIONAL INSTITUTES OF HEALTH   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 33947085849     PISSN: 00027863     EISSN: 15205126     Source Type: Journal    
DOI: 10.1021/ja00799a062     Document Type: Article

References (11)

1. K. B. Sharpless, M. W. Young, and R. F. Lauer, Tetrahedron Lett., 1979 (1973).
2. K. B. Sharpless and R. F. Lauer, J. Amer. Chem. Soc., 95, 2697 (1973).
3. There are several precedents for the addition of ArSeX (X = Cl and SCN) to ketones; see D. L. Klayman in “Organic Selenium Compounds,” D. L. Klayman and W. H. H. Günther, Ed., Wiley-Interscience, New York, N. Y., 1973, Chapter 4. However, the parent compound PhSeCl had never been added to ketones and no selenium electrophile had ever been added to aldehydes. It should be pointed out that brominations of aldehydes are generally unsuccessful due to oxidation to the acyl bromide. PhSeBr cannot be substituted for PhSeCl in these additions (for the problems encountered upon attempted addition of o-nitrophenylselenenyl bromide to acetone see
4. H. Rheinboldt and M. Perrier, Bull. Soc. Chim. Fr., 17, 759 (1950)). Recently, we have found that the α-selenation of ketones with PhSeCl can be carried out in the presence of other functional groups such as alcohols, esters, and even certain double bonds
5. (R. F. Lauer and K. B. Sharpless, unpublished results).
6. M. W. Rathke and A. Lindert, Tetrahedron Lett., 3995 (1971).
7. M. W. Rathke and A. Lindert, J. Amer. Chem. Soc., 93, 2318 (1971).
8. It should be pointed out that the anion derived from seleno ester 9 (path c) is not the first selenium stabilized anion. Seebach and Peleties have reported a variety of such species: D. Seebach and N. Peleties, Angew. Chem., 81, 465 (1969);
9. Chem. Ber., 105, 511 (1972).
10. C. Y. Hopkins, A. W. Jevans, and R. Boch, Can. J. Biochem., 47. 433 (1969).
11. National Institutes of Health Predoctoral Fellow, 1969-1973.