Divergent kinetic control of classical versus ozonolytic lactonization: Mechanism-based diastereoselection

Journal of the American Chemical Society

Volumn 127, Issue 23, 2005, Pages 8256-8257

  Hoye, Thomas R ^a   Ryba, Troy D ^a  

^a UNIVERSITY OF MINNESOTA   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

ESTER DERIVATIVE; SODIUM HYDROXIDE;

ARTICLE; CATALYSIS; CHEMICAL ANALYSIS; CHEMICAL INTERACTION; CHEMICAL REACTION; CHEMICAL STRUCTURE; CONFORMATION; CYCLIZATION; ESTERIFICATION; KINETICS; LACTONIZATION; STEREOCHEMISTRY; SYNTHESIS;

BICYCLO COMPOUNDS, HETEROCYCLIC; CYCLIZATION; KINETICS; LACTONES; OZONE; STEREOISOMERISM;

EID: 20444485151     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja051604b     Document Type: Article

References (21)

1. (a) Isolation: West, L. M.; Northcote, P. T.; Battershill, C. N. J. Org. Chem. 2000, 65, 445-449.
2. Total syntheses: (b) Liao, X.; Wu, Y.; De Brabander, J. K. Angew. Chem., Int. Ed. 2003, 42, 1648-1652.
3. (c) Jin, M.; Taylor, R. E. Org. Lett. 2005, 7, 1303-1305.
4. (a) Hoye, T. R.; Peck, D. R.; Swanson, T. A. J. Am. Chem. Soc. 1984, 106, 2738-2739. For reviews of desymmetrizing reactions and strategies, see:
5. (b) Schreiber, S. L.; Poss, C. S. Acc. Chem. Res. 1994, 27, 9-17.
6. (c) Magnuson, S. R. Tetrahedron 1995, 51, 2167-2213.
7. This "breakthrough ratio" of 5-trans:5-cis was measured at the earliest time, where the less rapidly formed diastereomer could be quantified.
8. 8-THF). Substantial differences in reaction rates were observed. For example, DBU is the fastest, but products 3 begin to deteriorate at longer reaction times, probably via α- deprotonation events. Thus, an equilibrium value for 3-trans:3-cis has not been observed under basic (or acidic, MOM ether cleavage) conditions.
9. It is interesting to consider the possibility that Felkin-Ahn factors might be controlling the stereochemical outcome of an addition reaction to a carboxyl functional group rather than the usual aldehyde or ketone carbonyl. Ahn, N. T.; Eisenstein, O. Nouv. J. Chim. 1977, 1, 61-70.
10. Stereoelectronic factors also dictate that the departing methoxy group occupies an axial site for the collapse of hemiortho esters to lactones, as is the case in 7-r and 7-s. See: Deslongchamps, P. In Stereoelectronic Effects in Organic Chemistry; Baldwin, J. E., Ed.; Organic Chemistry Series; Pergamon Press: Elmsford, NY, 1983; Vol. 1, pp 54-90.
11. (a) The following fundamental tenet, surprisingly often overlooked, is always operative: a rate is a rate constant times a concentration (i.e., rate = k × [A]).
12. (b) The analysis of Curtin-Hammett controlled processes often benefits from breakdown of the competing events into these individual components of rate constant and concentration.
13. (a) Kilpatrick, M. J. Am. Chem. Soc. 1928, 50, 2891-2902.
14. (b) Jencks, W. P.; Carriuolo, J. J. Am. Chem. Soc. 1961, 83, 1743-1750.
15. (a) Marshall, J. A.; Garofalo, A. W. J. Org. Chem. 1993, 58, 3675-3680. This development capitalized on the observations that aldehydes are smoothly oxidized by ozone to esters at -78 °C in alcohol solutions of NaOH:
16. (b) Sundararaman, P.; Walker, E. C.; Djerassi, C. Tetrahedron Lett. 1978, 19, 1627-1628. Acetals are oxidized to esters by ozone at widely varying rates, governed by Stereoelectronic features:
17. (c) Deslongchamps, P.; Atlani, P.; Fréhel, D.; Malaval, A.; Moreau, C. Can. J. Chem. 1974, 52, 3651-3664.
18. Since 4S rapidly lactonizes upon handling (interestingly, considerably faster than 1), the yield of purified (and coeluting) 5-cis and 5-trans was determined after complete lactonization of 4S.
19. It is relevant that primary ozonides derived from terminal alkenes bearing allylic ethers cleave regioselectively to α-alkoxy aldehydes and the formaldehyde carbonyl oxide: Kawamura, S.; Yamakoshi, H.; Nojima, M. J. Org. Chem. 1996, 61, 5953-5958.
20. .-) formed by reaction between ozone and hydroxide. Forni, L.; Bahnemann, D.; Hart, E. J. J. Phys. Chem. 1982, 86, 255-259.
21. a of acetaldehyde hydrate in water is 13.5. Bell, R. P.; McTigue, P. T. J. Chem. Soc. 1960, 2983-2994.