Enantioselective Synthesis of the Spirotropanyl Oxindole Scaffold through Bimetallic Relay Catalysis
Dr. Zhi-Jun Jia
Max-Planck-Institut für Molekulare Physiologie, Abteilung Chemische Biologie, Otto-Hahn-Strasse 11, 44227 Dortmund, Germany
Technische Universität Dortmund, Fakultät Chemie, Chemische Biologie, Chemische Biologie, Otto-Hahn-Strasse 4a, 44227 Dortmund, Germany
Search for more papers by this authorDr. Gang Shan
Max-Planck-Institut für Molekulare Physiologie, Abteilung Chemische Biologie, Otto-Hahn-Strasse 11, 44227 Dortmund, Germany
Search for more papers by this authorDr. Constantin G. Daniliuc
Westfälische Wilhelms-Universität Münster, Organisch-Chemisches Institut, Corrensstrasse 40, 48149 Münster, Germany
Search for more papers by this authorCorresponding Author
Dr. Andrey P. Antonchick
Max-Planck-Institut für Molekulare Physiologie, Abteilung Chemische Biologie, Otto-Hahn-Strasse 11, 44227 Dortmund, Germany
Technische Universität Dortmund, Fakultät Chemie, Chemische Biologie, Chemische Biologie, Otto-Hahn-Strasse 4a, 44227 Dortmund, Germany
Search for more papers by this authorCorresponding Author
Prof. Dr. Herbert Waldmann
Max-Planck-Institut für Molekulare Physiologie, Abteilung Chemische Biologie, Otto-Hahn-Strasse 11, 44227 Dortmund, Germany
Technische Universität Dortmund, Fakultät Chemie, Chemische Biologie, Chemische Biologie, Otto-Hahn-Strasse 4a, 44227 Dortmund, Germany
Search for more papers by this authorDr. Zhi-Jun Jia
Max-Planck-Institut für Molekulare Physiologie, Abteilung Chemische Biologie, Otto-Hahn-Strasse 11, 44227 Dortmund, Germany
Technische Universität Dortmund, Fakultät Chemie, Chemische Biologie, Chemische Biologie, Otto-Hahn-Strasse 4a, 44227 Dortmund, Germany
Search for more papers by this authorDr. Gang Shan
Max-Planck-Institut für Molekulare Physiologie, Abteilung Chemische Biologie, Otto-Hahn-Strasse 11, 44227 Dortmund, Germany
Search for more papers by this authorDr. Constantin G. Daniliuc
Westfälische Wilhelms-Universität Münster, Organisch-Chemisches Institut, Corrensstrasse 40, 48149 Münster, Germany
Search for more papers by this authorCorresponding Author
Dr. Andrey P. Antonchick
Max-Planck-Institut für Molekulare Physiologie, Abteilung Chemische Biologie, Otto-Hahn-Strasse 11, 44227 Dortmund, Germany
Technische Universität Dortmund, Fakultät Chemie, Chemische Biologie, Chemische Biologie, Otto-Hahn-Strasse 4a, 44227 Dortmund, Germany
Search for more papers by this authorCorresponding Author
Prof. Dr. Herbert Waldmann
Max-Planck-Institut für Molekulare Physiologie, Abteilung Chemische Biologie, Otto-Hahn-Strasse 11, 44227 Dortmund, Germany
Technische Universität Dortmund, Fakultät Chemie, Chemische Biologie, Chemische Biologie, Otto-Hahn-Strasse 4a, 44227 Dortmund, Germany
Search for more papers by this authorGraphical Abstract
Ring, ring: The first enantioselectively catalyzed synthesis of the spirotropanyl oxindole scaffold, which is characteristic of bioactive alkaloids like alstonisine and chitosenine, was developed. The method involves a bimetallic relay catalysis strategy, with a highly enantioselective 1,3-dipolar cycloaddition as the key step.
Abstract
Spirotropanyl oxindole alkaloids like alstonisine and chitosenine show a wide range of bioactivites. We report the first enantioselective synthesis of the spirotropanyl oxindole scaffold by means of a bimetallic relay catalysis strategy. A new class of E-oximino α-diazo ketones was developed for the intramolecular generation of transient azomethine ylides catalyzed by an achiral RhII complex and a subsequent intermolecular 1,3-dipolar cycloaddition catalyzed by a chiral N,N′-dioxide NdIII Lewis acid complex. The enantioselectively catalyzed transformation has broad scope and yields the desired spirotropanyl oxindole cycloadducts in high yields and with very high enantio- and diastereoselectivity.
Supporting Information
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