The direct magnesiation of highly functionalized aromatics bearing an ester, a nitrile, or a ketone can be readily performed by using an OBoc as a directing group and TMPMgCl.LiCl as a base. It allows, for example, the preparation of a meta-magnesiated benzophenone in >95%. After quenching, highly functionalized and substituted benzenes are obtained. [reaction: see text].

The synthetic potential of arynes can be exploited through a new method for their generation from functionalized aryl magnesium reagents and controlled reaction. Arynes with functional groups such as ester, nitrile, ketone, or nitro groups, or with a quinolyl skeleton, can be formed from polyfunctionalized 2‐iodo aryl 4‐chlorobenezenesulfonates and trapped in 68–93 % yield with furan (see scheme).

Dedicated to Professor Michael Veith on the occasion of his 60th birthdayTransition-metal-catalyzed cross-coupling reactions are very powerful CÀC bond-forming reactions, especially between C(sp 2 ) centers at which typical S N 2 substitutions cannot operate.[1] Palladium(0) catalysts are the most widely and reliably used, [1,2] especially if appropriate ligands such as sterically hindered phosphines are present.[3] Nickel(0) complexes have also found useful applications, but appear to have

Reactive arynes, which are readily generated by the reaction of ortho‐iodoarylsulfonates with iPrMgCl, undergo the smooth addition of various magnesium nucleophiles like magnesium thiolates, selenides, and amides. In all cases the resulting functionalized aryl magnesium species can be trapped by an electrophile leading to highly functionalized aromatic compounds (see scheme).

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