ISSN:
0947-3440
Keywords:
3,7-Dioxa-2-azabicyclo[3.3.0]octanes
;
2,6-Dioxa-3-azatricyclo[5.3.1.04.11]undecanes
;
Amino alcohols
;
Chiral ligands
;
Enantioselective catalysis
;
Homogenous catalysis
;
Chemistry
;
Organic Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
Reduction of the enantiomerically pure allyloxy esters 9 or ent-9 with DIBAH afforded the corresponding aldehydes which were treated in situ with chiral or achiral hydroxylamines 8 to give nitrones 10. These underwent a spontaneous intramolecular 1,3-dipolar cycloaddition, affording the bicyclic compounds 11 and 12, respectively. In an analogous manner, a mixture of the tricyclic compounds 14 and 15 was prepared. Treatment of compound 16 with cyclohexene oxide afforded a mixture of diastereomers 17 and 18. Diastereomers 14 and 15 as well as 17 and 18 could be separated by chromatography. X-ray analyses of compounds 11Ff, 17, and 11Af · HCl were performed. The bicyclic and tricyclic compounds were used as chiral ligands in the reaction of diethylzinc with aldehydes 19, in particular with benzaldehyde (19a). Using bicyclic compounds with a tertiary β-hydroxyalkyl substitutent at the N atom as ligands, ee's in the range of 78 to 95% were found. Whereas for the best ligands 11Ae and Af the enantioselectivity in the reaction of 4-tolualdehyde was only slightly decreased, with the aliphatic aldehydes 19c and d distinctly lower enantioselectivities were determined.
Additional Material:
2 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/jlac.199719970222
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