The stereocontrolled synthesis of a C15 C24 fragment of dolabelides is reported. The C19 and C21 hydroxyl-bearing stereocenters were installed using ruthenium-mediated asymmetric hydrogenations of cyclic hemiketal 4 and b-keto ester 7. The C25 C30 portion of dolabelides was prepared as well by ring
Synthesis of C1C8 and C9C24 fragments of (−)-discodermolide: use of asymmetric alkylation and stereoselective aldol reactions
✍ Scribed by Sandra A. Filla; Jinhua J. Song; Lihren Chen; Satoru Masamune
- Publisher
- Elsevier Science
- Year
- 1999
- Tongue
- French
- Weight
- 301 KB
- Volume
- 40
- Category
- Article
- ISSN
- 0040-4039
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✦ Synopsis
The C1-C8 and C9--C24 fragments of (-)-discodermolide, the antipode of the marine natural product (+)discodermolide, have been synthesized with excellent stereoselectivities. These syntheses feature the utilization of the isoxazolidine-mediated asymmetric alkylation methodology and fragment-fragment coupling aldol reactions.
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Two chiral intenediates, C(l)-C( 9) and C(llI-Cc171 portions of protomycinolide IV, were synthesized both from (Sl-ethyl lactate via asymmetric pinacoZ-type rearrangement folZowed b2 diastereoselective reactions on cc-methyl-B,y-unsaturated carbonyl compounds.
The synthesis of the C 7 C 21 fragment of epothilone A involving asymmetric alkoxyallyl-and crotylboration using a-pinene-derived reagents is described.