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

Benjamin J. Huffman, Tiffany Chu, Yusuke Hanaki, Jonathan J. Wong, Shuming Chen, K. N. Houk, Ryan A. Shenvi

2021Angewandte Chemie International Edition20 citationsDOIOpen Access PDF

Abstract

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.

Topics & Concepts

DiastereomerRing (chemistry)Covalent bondChemistrySelectivityStereochemistryLewis acids and basesFormal synthesisMichael reactionCombinatorial chemistryOrganic chemistryCatalysisMagnolia and Illicium researchOxidative Organic Chemistry ReactionsPhytochemistry and Bioactive Compounds
Stereodivergent Attached‐Ring Synthesis via Non‐Covalent Interactions: A Short Formal Synthesis of Merrilactone A | Litcius