Nickel-Catalyzed Cross-Coupling of Functionalized Organo­manganese Reagents with Aryl and Heteroaryl Halides Promoted by 4-Fluorostyrene

Abstract

A catalytic system consisting of Ni(acac)2 (5 mol%) and 4-fluorostyrene (20 mol%) allows a convenient cross-coupling of functionalized organomanganese reagents with a variety of aryl and heteroaryl halides leading to polyfunctionalized diaryl- and arylheteroarylmethane derivatives.

Understanding the Chemoselectivity in Palladium-Catalyzed Three-Component Reaction of o-Bromobenzaldehyde, N-Tosylhydrazone, and Methanol

“…2-Benzylbenzoic acid derivatives are synthetically useful building blocks . Traditional approaches to these compounds normally require the employment of air- and moisture-sensitive organometallic reagents. , Therefore, the development of a general method by using abundant feedstock chemicals as reactants is in high demand. In line with our continuous research interest in carbene-bridging C–H activation, we have launched a project on a palladium-catalyzed three-component reaction of o -bromobenzaldehyde, N -tosylhydrazone, and methanol, aiming to prepare 2-benzylbenzoic esters in a modular fashion .…”

Iron-Catalyzed Cross-Coupling of Bis-(aryl)manganese Nucleophiles with Alkenyl Halides: Optimization and Mechanistic Investigations

“…in the presence of MnCl 2 (0.6 equiv.) within 1 h. Titration [31] with iodine led to a yield for 1a of 87%. Cross-coupling methodologies involving those bis-(aryl)manganese species were then investigated (see Supporting Information file for details).…”

“…Recently, we have developed a two-step preparation of functionalized bis-(aryl)manganese reagents by oxidative insertion of magnesium into the C-Br bond of aryl bromides, which is followed by a trans-metalation with MnCl 2 •2LiCl [31]. Herein, we wish to report an effective one-pot preparation of those functionalized bis-(aryl)manganese reagents (Ar 2 Mn•2MgX 2 •4LiCl, denoted as Ar 2 Mn (1), Scheme 1) starting from aryl bromides, which are followed by an iron-catalyzed cross-coupling of 1 with alkenyl iodides and bromides, and provide a range of polyfunctionalized alkenes (4, Scheme 1).…”