A tricyclic phosphine has been generated that has a rigid molecular backbone with the P atoms exclusively bound to C(sp ) atoms as well as a very large Tolman angle and buried volume. It is an interesting new ligand in coordination chemistry (Au, Pd complexes) and shows unusual insertion reactions into its endocyclic P-C bonds facilitated by its inherent molecular strain.
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Phosphine-Catalyzed Crossed Rauhut-Currier-Type Coupling and [3 + 2]-Cycloaddition of 2-Alkylidene-3-oxindoles with Alkenes and Allenes to Access β,γ-Unsaturated Enones and Polycyclic Oxindoles.
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University of Rostock, Institute of Chemistry, Albert-Einstein-Str. 3a, Rostock 18059, Germany.
Dihydroazepino[1,2-]indole diones are tricyclic -acyl-2-alkylidene-3-oxindole enones that readily engage in tertiary phosphine-catalyzed intermolecular coupling reactions with acceptor-substituted alkenes. In these reactions, the tricyclic α-substituted enones undergo an α-alkylation with concomitant formation of a quaternary stereocenter, as well as the installation of a new double bond within the seven-membered azepane ring. The organocatalytic reaction constitutes a special case of the crossed intermolecular Rauhut-Currier reaction as the presence of the α-substituent in the enones prohibits the formation of an α,β-unsaturated product, but instead, skipped β,γ-unsaturated enones are obtained.
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Anorganische und Allgemeine Chemie, Department Chemie und Pharmazie, Friedrich-Alexander-Universität Erlangen-Nürnberg, Egerlandstraße 1, 91058 Erlangen, Germany.
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State Key Laboratory of Elemento-Organic Chemistry and College of Chemistry, Nankai University, Tianjin 300071, People's Republic of China.
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Chem Sci
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Department of Chemistry and State Key Laboratory of Synthetic Chemistry, The Chinese University of Hong Kong Shatin New Territories Hong Kong China
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