Palladium-catalyzed intramolecular asymmetric allylic alkylation was used for the first time to prepare 4-vinyltetrahydrocarbazole 3. Suitable indole-containing allylic carbonates were synthesized and cyclized in the presence of a chiral catalyst formed in situ from Pd(OAc)2 and members of the PhthalaPhos ligand library (i.e., 1,1′-bi-2-naphthol-monophosphites possessing a phthalic acid diamide group). The use of a stable and readily available palladium source such as Pd(OAc)2―reduced in situ by the phosphite to form the Pd0 catalyst―allowed better and more reproducible results to be obtained relative to the results achieved by using [Pd2(dba)3·CHCl3] (dba = dibenzylideneacetone) and [Pd(allyl)Cl]2. A ligand screening led to identification of the best ligand [(S)-L1], which, after optimization of the reaction parameters, gave product 3 with 75 % ee. Remarkably, the reaction turned out to be stereodivergent: by using ligand (S)-L1, the absolute configuration of product 3 was found to depend on the geometry of the substrate's double bond [(E)-substrate [RIGHTWARDS ARROW] (S)-3, (Z)-substrate [RIGHTWARDS ARROW] (R)-3].
|Titolo:||Synthesis of a 4-Vinyltetrahydrocarbazole by palladium-catalyzed asymmetric allylic alkylation of indole-containing allylic carbonates|
|Parole Chiave:||Asymmetric catalysis; Nitrogen heterocycles; Alkylation; Palladium; Phosphites|
|Settore Scientifico Disciplinare:||Settore CHIM/06 - Chimica Organica|
|Data di pubblicazione:||ott-2015|
|Data ahead of print / Data di stampa:||18-set-2015|
|Digital Object Identifier (DOI):||10.1002/ejoc.201500979|
|Appare nelle tipologie:||01 - Articolo su periodico|