We found a match
Your institution may have access to this item. Find your institution then sign in to continue.
- Title
Further Explorations into the Synthesis of Dehydro -Hedione<sup>®</sup>.
- Authors
Winter, Béat; Chapuis, Christian; Brauchli, Robert; de Saint Laumer, Jean-Yves
- Abstract
Dehydrohedione (DHH) 1 may be obtained in 20% overall yield by a Reformatsky reaction with enone methyl ether 3b, followed by acidic workup of the crude reaction mixture. Alternatively, epoxidation (3-chloroperbenzoic acid, CH2Cl2, 84% yield) of the tertiary allyl alcohol derivative 4 affords a 1 : 2 mixture of 8a and 8b. The latter epoxy ester 8b may also be obtained stereoselectively either from 4 ( tBuO2H, [Mo(CO)6], 1,2-dichloroethane, 70°, 62% yield; or tBuO2H, [VO(acac)2], decane, 20°, 92% yield), or from 5 (AcOMe, LiN(SiMe3)2, THF, −78°, 84-87%). BF3⋅Et2O-Catalyzed cascade rearrangement and OH elimination of 8a afford selectively DHH 1 in 88% yield. The cis disposition of the side chains of the weakly odoriferous hedione-like analogues 2b and 2c was maintained by means of either an epoxy or a cyclopropane moiety.
- Subjects
REFORMATSKY reaction; CARBONYL compounds; EPOXIDATION; ALLYL alcohol derivatives; CYCLOPROPANE
- Publication
Helvetica Chimica Acta, 2013, Vol 96, Issue 2, p246
- ISSN
0018-019X
- Publication type
Article
- DOI
10.1002/hlca.201200440