Catalytic Enantioselective Aminopalladation–Heck Cascade

• Published in: Angewandte Chemie International Edition Vol. 60; no. 13; pp. 7093 - 7097
• Main Authors: He, Yu‐Ping, Cao, Jian, Wu, Hua, Wang, Qian, Zhu, Jieping
• Format: Journal Article
• Language: English
• Published: Germany Wiley Subscription Services, Inc 22-03-2021
• Edition: International ed. in English
• Subjects: Alkynes; asymmetric synthesis; Chemical synthesis; Cyclopentene; domino reactions; Enantiomers; homogeneous catalysis; Indoles; nucleopalladation; Oxidants; oxidative Heck reactions; Oxidizing agents; asymmetric synthesis; homogeneous catalysis; domino reactions; oxidative Heck reactions; nucleopalladation
• ISSN: 1433-7851; 1521-3773
• DOI: 10.1002/anie.202016001

Domino processes initiated by intramolecular nucleopalladation of alkynes have been developed into powerful synthetic tools for the synthesis of functionalized heterocycles. However, a catalytic enantioselective version of this class of reactions remains scarce. We report herein that reaction of 2‐alkynylanilines with prochiral cyclopentenes in the presence of a catalytic amount of Pd(OAc)2, a chiral bidentate pyrox ligand and O2 as terminal oxidant affords the structurally diverse indole‐cyclopentene conjugates bearing two stereocenters in a highly diastereo‐ and enantio‐selective manner. One of the products is converted to a heavily functionalized tetracyclic indolinone derivative.
Reaction of 2‐alkynylanilines with prochiral cyclopentenes in the presence of a catalytic amount of Pd(OAc)2, a chiral bidentate pyrox ligand and O2 as terminal oxidant affords structurally diverse indole‐cyclopentene conjugates bearing two stereocenters in a highly diastereo‐ and enantio‐selective manner.