Stereodivergent Attached‐Ring Synthesis via Non‐Covalent Interactions: A Short Formal Synthesis of Merrilactone A

A strategy to control the diastereoselectivity of bond formation at a prochiral attached‐ring bridgehead is reported. An unusual stereodivergent Michael reaction relies on basic vs. Lewis acidic conditions and non‐covalent interactions to control re‐ vs. si‐ facial selectivity en route to fully subs...

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Bibliographic Details
Published in:Angewandte Chemie International Edition 2022-01, Vol.61 (3), p.e202114514-n/a
Main Authors: Huffman, Benjamin J., Chu, Tiffany, Hanaki, Yusuke, Wong, Jonathan J., Chen, Shuming, Houk, Kendall N., Shenvi, Ryan A.
Format: Article
Language:English
Subjects:
attached-ring
Cyclization
diastereoselectivity
Divergence
Lactones - chemical synthesis
Lactones - chemistry
Michael addition
Michael reaction
Molecular Structure
natural products
Route selection
Selectivity
Sesquiterpenes - chemical synthesis
Sesquiterpenes - chemistry
Stereoisomerism
Stereoselectivity
Synthesis
synthesis design
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Summary:A strategy to control the diastereoselectivity of bond formation at a prochiral attached‐ring bridgehead is reported. An unusual stereodivergent Michael reaction relies on basic vs. Lewis acidic conditions and non‐covalent interactions to control re‐ vs. si‐ facial selectivity en route to fully substituted attached‐rings. This divergency reflects differential engagement of one rotational isomer of the attached‐ring system. The successful synthesis of an erythro subtarget diastereomer ultimately leads to a short formal synthesis of merrilactone A. An unusual stereodivergent Michael reaction relies on basic vs. Lewis acidic conditions and non‐covalent interactions to control re‐ vs. si‐ facial selectivity en route to fully substituted attached‐rings. This differential engagement of one rotational isomer of an attached‐ring system leads to a short formal synthesis of merrilactone A.
ISSN:1433-7851
1521-3773
DOI:10.1002/anie.202114514