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    Synthesis of a 4-Vinyltetrahydrocarbazole by Palladium-Catalyzed Asymmetric Allylic Alkylation of Indole-Containing Allylic Carbonates

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    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 → (S)-3, (Z)-substrate → (R)-3]

    Sequential unsymmetrical aryl coupling of o-substituited aryl iodides with o-bromophenols and reaction with olefins: palladium-catalyzed synthesis of 6H-dibenzopyran derivatives

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    Dibenzopyran derivatives are prepared by palladium- and norbornene-catalyzed reaction of aryl iodides, o-substituted with electron-releasing substituents, o-bromophenols, and activated alkenes
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