Enantioselective Total Synthesis of (+)-Peniciketals A and B: Two Architecturally Complex Spiroketals.

Abstract

The enantioselective total syntheses of (+)-peniciketals A and B, two members of a family of architecturally complex spiroketals, have been achieved. Key synthetic transformations comprise Type I Anion Relay Chemistry (ARC) to construct the benzannulated [6,6]-spiroketal skeleton, a Negishi cross-coupling/olefin cross-metathesis reaction sequence to generate the trans-enone structure, and a late-stage large fragment union exploiting our recently developed photoisomerization/cyclization tactic.

• Authors: Yifan Deng, Chia-Ping H Yang, Amos B Smith Iii
• Journal: Journal of the American Chemical Society (J Am Chem Soc) Vol. 143 Issue 4 Pg. 1740-1744 (02 03 2021) ISSN: 1520-5126 [Electronic] United States
• PMID: 33496178 (Publication Type: Journal Article, Research Support, N.I.H., Extramural, Research Support, Non-U.S. Gov't)

Chemical References

• Pyrans
• Spiro Compounds
• peniciketal A
• peniciketal B

Topics

• Molecular Structure
• Pyrans (chemical synthesis)
• Spiro Compounds (chemical synthesis)
• Stereoisomerism