Highly Chemo‐ and Stereoselective Catalyst‐Controlled Allylic C−H Insertion and Cyclopropanation Using Donor/Donor Carbenes

• Published in: Angewandte Chemie International Edition Vol. 57; no. 38; pp. 12405 - 12409
• Main Authors: Zhu, Dong, Chen, Lianfen, Zhang, He, Ma, Zhiqiang, Jiang, Huanfeng, Zhu, Shifa
• Format: Journal Article
• Language: English
• Published: WEINHEIM Wiley 17.09.2018; Wiley Subscription Services, Inc
• Edition: International ed. in English
• Subjects: asymmetric catalysis; Carbenes; Catalysis; Catalysts; Chemistry; Chemistry, Multidisciplinary; cyclopropanation; Cyclopropane; heterocycles; Insertion; Physical Sciences; Rhodium compounds; ruthenium; Science & Technology; Stereoselectivity; ALPHA-DIAZOCARBONYL COMPOUNDS; ORGANIC-SYNTHESIS; PROPARGYLIC ESTERS; ASYMMETRIC-SYNTHESIS; carbenes; DIAZO-COMPOUNDS; asymmetric catalysis; NONDIAZO APPROACH; ruthenium; CHIRAL DIRHODIUM(II) CATALYSTS; cyclopropanation; heterocycles; METAL CARBENE; MIGRATORY INSERTION; ENANTIOSELECTIVE INTRAMOLECULAR CYCLOPROPANATION
• ISSN: 1433-7851; 1521-3773; 1521-3773
• DOI: 10.1002/anie.201805676

The highly chemo‐, enantio‐, and diastereoselective catalyst‐controlled intramolecular allylic C−H insertion and cyclopropanation of donor/donor carbenes are reported. The RuII/Pybox complex selectively catalyzed the intramolecular allylic C−H insertion, providing vinyl‐substituted dihydroindoles with greater than 20:1 chemoselectivity and up to greater than 99 % ee. Chiral dirhodium(II) tetracarboxylates, however, selectively promoted the intramolecular cyclopropanation, giving rise to cyclopropane‐fused tetrahydroquinoline derivatives in excellent yields with greater than 99:1 chemoselectivity and up to 97 % ee. Rh versus Ru: The highly chemo‐, enantio‐ and diastereoselective catalyst‐controlled intramolecular allylic C−H insertion and cyclopropanation of donor/donor carbenes is reported. The RuII/Pybox complex selectively catalyzes the intramolecular allylic C−H insertion, providing vinyl‐substituted dihydroindoles. Chiral dirhodium(II) tetracarboxylates, however, selectively catalyzed the intramolecular cyclopropanation.