Diastereoselective nickel-catalyzed reductive coupling of alkynes and aldehydes and application towards the B-type amphidinolides
Author(s)Ndubaku, Chudi O
Massachusetts Institute of Technology. Dept. of Chemistry.
Timothy F. Jamison.
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The application of recently developed stereoselective nickel-catalyzed reductive coupling reactions of alkynes and aldehydes to the synthesis of complex natural product targets was explored. The "B-Type" amphidinolides were selected as ideal targets owing to their molecular complexity and the paucity of synthetically viable means for their total construction. The diastereoselective nickel-catalyzed reductive coupling of simple aryl-substituted alkynes and a-oxyaldehydes was developed and applied to the construction of the C15-C26 region of amphidinolide H3. ... Alternatively, the nickel-catalyzed reductive coupling reaction of 1,3-enynes and aldehydes was found to be a very effective way of installing the congested 1,3-diene moiety common to all members of this class of natural products. This methodology was further examined as a fragment coupling strategy for the syntheses of amphidinolides G3 and H4. This allowed for a highly convergent and functional group tolerant assembly of these ... molecules and, to date, stands as the most complicated setting for the application of the catalytic reductive coupling reaction.
Thesis (Ph. D.)--Massachusetts Institute of Technology, Dept. of Chemistry, 2006.Vita.Includes bibliographical references.
DepartmentMassachusetts Institute of Technology. Dept. of Chemistry.; Massachusetts Institute of Technology. Department of Chemistry
Massachusetts Institute of Technology