Scheme 4. Proposed reaction mechanism.Scheme 5. Derivatization of 2 a and 3 a. mCBPA = meta-chloroperbenzoic acid, PMHS = poly(methylhydroxysilane).Scheme 6. The mode of oxidative addition.
The first enantioselective total synthesis of tangutorine has been achieved, wherein a Pd-catalyzed asymmetric allylic amination using a chiral diaminophosphine oxide (DIAPHOX) preligand was the key step.
Inspiroierend: Eine neuartige Synthese von Spirocyclen basierend auf einer Palladium‐katalysierten intramolekularen ipso‐Friedel‐Crafts‐Alkylierung von Phenolen (siehe Schema; dba=Dibenzylidenaceton) und Indolen wird beschrieben. Mechanistische Studien belegen, dass die Reaktion über eine präzedenzlose Rearomatisierungs‐unterstützte oxidative Addition verläuft.
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