Stereoselective amino-hydroxylation of the double bond in 7-oxabicyclo[2.2.1]hept-5-en-2-yl derivatives. Remote substituent participation in acid-catalyzed decompositions of aziridines and triazolines
✍ Scribed by Jean-Louis Reymond; Pierre Vogel
- Publisher
- Elsevier Science
- Year
- 1988
- Tongue
- French
- Weight
- 284 KB
- Volume
- 29
- Category
- Article
- ISSN
- 0040-4039
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✦ Synopsis
An qJ?cient method has been developed for the stereoselective substitution of
7-oxabicyclo[2.2.l]hept-2-yl derivatives by protected amino group at C(S-exo) and hydroxy group at C(6-endo).
The 7-oxabicyclo[2.2.1]hept-S-en-2-yl derivatives 1 -6 can be obtained optically pure.' Because of their bicyclic structure, the double-bond at C(5)-C(6) reacts with high exo face selectivity.2 The rtgioselectivity of electrophilic additions of these systems depends on the nature of the substituents at C(2).h3 For instance, while the CN and camphanyloxy groups in 1, or CN and OAc group in 7, play the role of electron-withdrawing substituents, giving exclusively adducts of type 8, the carbonyl group iu 4 acts as an electron&mating substituent and leads to the formation of adducts 9.3 Adducts 8 can be transformed into ketones 10, regioisorneric with 9. &tones 9 and 10 can be substituted stereoselectively at C(3) and then traosfomed into a variety of compounds, including sugar derivatives of biological iuterest.4