Employing Pd-Catalyzed C–H Arylation in Multicomponent-Multicatalyst Reactions (MC)²R: One-Pot Synthesis of Dihydrobenzoquinolines

Abstract

The one-pot synthesis of a broad variety of dihydrofuroquinolines, dihydrothienoquinolines, and dihydrobenzoquinolines is reported. The combination of the Rh­(I)-catalyzed hydroarylation of vinylpyridines with the Pd(0)/Pd­(II)-catalyzed direct C–H arylation in a Multicomponent-Multicatalyst Reaction (MC)2R could be used to develop an efficient and step-economic protocol for the rapid construction of molecular complexity. A high-yielding synthesis of π-extended heteroarenes through an efficient three-step-one-pot procedure and a highly enantioselective synthesis of 6-alkylsubstituted dihydrobenzoquinolines are shown.

Silber‐katalysierte Hydroarylierung von hochsubstituierten Styrolen

“…[1,2] Andere Transformationen unter Verwendung von vorfunktionalisierten Arylhalogeniden oder Arylnukleophilen, wie Arylboronsäuren, wurden parallel dazu entwickelt (Schema 1 A). [3] Alternativ bilden Funktionalisierungen über Friedel-Crafts-Hydroarylierung oder Hydroheteroarylierung von Styrolen neue C-C-Bindungen mit vollständiger Atomçkonomie. Häufige Herausforderungen sind die Regioselektivität des Aren-Nukleophils, die schlechte Reaktivität von sterisch gehinderten Styrolen und die Stabilität von Heteroaromaten in Gegenwart von Übergangsmetallen, sauren Bedingungen oder erhçhten Temperaturen.…”

Remote Functionalization of α,β-Unsaturated Carbonyls by Multimetallic Sequential Catalysis

“…The economic and environmental benefits associated with sequential multimetallic catalysis has raised strong interest in academia and industry. − The field emulates from Nature’s ability to separate different reactive sites within an enzyme, or different enzymes within a cell to effect a series of orthogonal transformations in a given sequence without the need to isolate unstable reactive intermediates. The implementation of such strategies in synthetic laboratories may ultimately enable chemists to readily convert commodity chemicals into more complex molecular architectures with maximum efficiency, be it in terms of atom-, step-, and redox-economy, and absolute and relative stereocontrol .…”

Silver‐Catalysed Hydroarylation of Highly Substituted Styrenes

“…[1,2] Other transformations using prefunctionalised aryl halides or aryl nucleophiles, such as aryl boronic acids, have been developed in parallel (Scheme 1 A). [3] Alternatively, functionalisation via Friedel-Crafts-type hydroarylation or hydroheteroarylation of styrenes form new CÀC bonds with complete atom economy. Frequently encountered challenges are the regioselectivity of the arene nucleophile, the poor reactivity of sterically hindered styrenes, and the stability of heteroaromatic compounds in the presence of transition metals, acidic conditions, or elevated temperatures.…”