ISSN:
0947-3440
Keywords:
Epoxidations
;
Diastereoselectivity
;
Hydrogen bonding
;
1-Methylgeraniol
;
Chemoselectivity
;
Peroxides
;
Chemistry
;
Organic Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
The chiral 1-methylgeraniol has been designed and applied for epoxidation reactions as a mechanistic probe, which allows to assess simultaneously in one and the same molecule regio- and stereochemical information. Of the two trisubstituted double bonds, the terminal 7,8 one reflects kinetic preferences on account of its greater π nucleophilicity, the 3,4 one with the chiral allylic hydroxy functionality expresses diastereoselective directivity through hydrogen bonding. The combination of regio- and stereoselectivity provides a novel and powerful mechanistic tool to differentiate electronic and steric effects of oxidants. Thus, various epoxidizing agents have been employed and the mechanistic implications derived from the product ratios are well in line with those reported, which exemplifies the validity of the probe.
Additional Material:
1 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/jlac.199719970713
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