Journal
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
Volume 57, Issue 47, Pages 15572-15576Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.201809130
Keywords
biomimetic synthesis; cyclization; isotwistane; ortho-benzoquinones; radical reactions
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Funding
- National Health Research Institutes
- Ministry of Science and Technology, Taiwan [MOST-106-2113-M-400-001]
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The first total synthesis of isopalhinine A, as well as unified syntheses of palhinineA and palhinine D, were successfully accomplished by means of a biomimetic strategy that proceeds through a bioinspired 5/6/6/9 tetracyclic intermediate, which mimics the amino ketone form of palhinine D. An early-stage direct SN2 cyclization to construct the nine-membered azonane ring minimized the transannular strain that would otherwise be increased by the twisted nature of the isotwistane skeleton. Then, a diastereoselective Diels-Alder reaction of a masked ortho-benzoquinone using the nine-membered ring as a steric shielding group furnished a functionalized 6/6/9 tricyclic skeleton and established the desired stereochemistry at the C3, C7, C12, and C15 positions in one step. A thiol-mediated acyl radical cyclization gave the bioinspired intermediate bearing three differentiated oxygen-containing functional groups, from which all three total syntheses could be completed in either two or three additional steps.
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