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Advances in transition metal (Pd, Ni, Fe)-catalyzed cross-coupling reactions using alkyl-organometallics as reaction partners.

Recent Advances in the Baylis−Hillman Reaction and Applications

Transition metal chemistry of cyclopropenes and cyclopropanes.

Beijing National Laboratory of Molecular Sciences (BNLMS) and Key Laboratory of Bioorganic Chemistry and Molecular Engineering of Ministry of Education, College of Chemistry and Green Chemistry Center, Peking University, 202 Chengfu Road, 098#, Beijing 100871, China State Key Laboratory of Organometallic Chemistry, Chinese Academy of Sciences, 345 Lingling Road, Shanghai 200032, China State Key Laboratory of Elemento-Organic Chemistry, Nankai University, Tianjin 200060, China

Transition-Metal-Free Coupling Reactions

Organomagnesium reagents occupy a central position in synthetic organic and organometallic chemistry. Recently, the halogen-magnesium exchange has considerably extended the range of functionalized Grignard reagents available for synthetic purposes. Functional groups such as esters, nitriles, iodides, imines, or even nitro groups can be present in a wide range of aromatic and heterocyclic organomagnesium reagents. Also various highly functionalized alkenyl magnesium species can be prepared. These recent developments as well as new applications of organomagnesium reagents in cross-coupling reactions and amination reactions will be covered in this Review.

Highly functionalized organomagnesium reagents prepared through halogen-metal exchange.

Magnesiumverbindungen spielen eine zentrale Rolle in der praparativen organischen und metallorganischen Chemie. Seit kurzem ermoglicht der Halogen-Magnesium-Austausch den Zugang zu einer Reihe funktionalisierter Grignard-Reagentien. Ester-, Nitril-, Iod- und Iminfunktionen und sogar Nitrogruppen konnen in einer breiten Reihe aromatischer und heterocyclischer Organomagnesiumverbindungen vorhanden sein. Auch hoch funktionalisierte Alkenylmagnesiumspezies konnen auf diese Weise generiert werden. Diese neuen Entwicklungen sowie die Anwendung von Organomagnesiumreagentien in Kreuzkupplungen und Aminierungsreaktionen werden in diesem Aufsatz eingehend beschrieben.

Synthese hoch funktionalisierter Organomagnesiumreagentien durch Halogen-Metall-Austausch

Functionalized magnesium reagents have been prepared via an iodine-magnesium exchange. These reagents can be either trapped directly with aldehydes or transmetallated to copper or zinc to participate in cross-coupling reactions. The iodine-magnesium exchange, represent a unique method for the preparation of aryl and heteroaryl magnesium reagents.

Preparation and Reactions of Functionalized Arylmagnesium Reagents

A dry two-necked flask equipped with a magnetic stirring bar and a septum was charged with the cis-2-iodo-cyclopropanecarboxylic acid ethyl ester 1 (1 mmol) in dry THF (4 mL) under argon. The reaction mixture was cooled to —40 C and a solution of iPrMgCl (0.67 mL, 1.62 M in THF, 1.1 mmol) was slowly added. After 15 min of stirring, the exchange was complete (checked by GC analysis). Electrophile (1.5 mmol) was added and the reaction mixture was allowed to warm up to rt. After 2 h, the reaction mixture was quenched with sat. NH4Cl-solution (10 mL) and extract with ether. The organic layer was washed with brine, dried over MgSO4 and concentrated under vacuum. The crude residue was purified by flash chromatography using the specified solvent system.

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Viet Anh Vu

Papers

Highly functionalized organomagnesium reagents prepared through halogen-metal exchange.

Synthese hoch funktionalisierter Organomagnesiumreagentien durch Halogen-Metall-Austausch

Preparation and Reactions of Functionalized Arylmagnesium Reagents

Preparation of new functionalized cyclopropylmagnesium reagents.

Preparation of α-functionalized alkenylmagnesium reagents via a halide–magnesium exchange