Auto‐Tandem Catalysis: A Single Catalyst Activating Mechanistically Distinct Reactions in a Single Reactor

Abstract

Domino reactions have received great attention as efficient synthetic methodologies for the construction of structurally complex molecules from simple materials in a single operation. Catalysts in domino reactions have also been well studied. In these reactions, a catalyst activates the substrate(s) only once, and the structure of the product is delineated at that time. Recently, the new concept of "tandem catalysis" in domino reactions, in which catalyst(s) sequentially activate more than two mechanistically distinct reactions, has been proposed. Tandem catalysis is categorized into three subclasses: orthogonal-, auto-, and assisted-tandem catalyses. Auto-tandem catalysis is defined as a process in which one catalyst promotes more than two fundamentally different reactions in a single reactor. An overview of recent and significant achievements in auto-tandem catalysis is presented in this paper.

Synthesis of Pyrrolidine Derivatives by a Platinum/Brønsted Acid Relay Catalytic Cascade Reaction

“…As before, we observed that the reaction only occurred with terminal alkynes substituted with electron-rich aromatic rings (Table 1). We also observed that the process gave better results when using the platinum(II)-derived catalyst [PtMe 2 (COD)] instead of the platinum(IV)-derived PtCl 4 . Thus, the reaction of NBoc-protected alkynamines 1 with alkynes 8 c,d in the presence of [PtMe 2 (COD)] (5 mol %) and TfOH (10 mol %) in dichloromethane at À10 8C led to the desired bicyclic pyrrolidine derivatives 9 e-q in very high yield, independently of the starting amine derivative 1 used.…”

“…In this context, relay (tandem) catalysis has emerged as a very powerful tool. [4] In these reactions, one or several catalysts promote two or more mechanistically distinct processes in a single flask circumventing the often labour-and time-intensive, waste-and cost-increasing, and yield-reducing isolation and purification of intermediates in multistep sequences. In this context, we have been involved in recent years in the development of a new methodology in organic synthesis based on catalytic cascade reactions.…”

Formal (3+3) Cycloaddition of Silyl Enol Ethers Catalyzed by Trifric Imide: Domino Michael Addition-Claisen Condensation Accompanied with Isomerization of Silyl Enol Ethers

“…In the domino sequence, the catalyst activates Michael addition, deprotonation of the resulting silyloxonium cation and intramolecular Claisen condensation. 24) We also demonstrated the construction of the clovane skeleton by the intramolecular reaction. Further studies to improve the chemical yield are under investigation.…”

Kinetic models of multi-route reactions in homogeneous catalysis with metal complexes (A Review)

“…Several vari ants of classification were proposed for MCSs and PFCSs (see, e.g., [43,[54][55][56][57][58][59][60][61]. In recent years, systems with several catalysts have been also actively used in the synthetic organic chemistry (see Section 6), including the so called "tandem catalysis" [62] and systems combining metal complexes with acid-base [63] or organic [64] catalysts. Let us consider the KFs of catalysts in MCSs for some processes.…”