The Organometallic Approach to Molecular Diversity − Halogens as Helpers

An efficient and mild ortho-zincation of aromatics and heterocycles by using TMP2Mg·2LiCl in the presence of ZnCl2

“…The directed ortho-metalation of aromatics and heterocycles is an efficient method for the functionalization of these compounds [1][2][3][4][5][6][7][8][9][10]. However, deprotonation of some heterocyclic aromatic rings gave unsatisfactory results due to the high reactivity of the generated organometallic intermediates [11,12], and it is already known that the metalation of diazines is challenging since very facile competitive nucleophilic addition reactions occur [13][14][15][16].…”

Synthesis of Complex Organofluorine Compounds

“…Choice of the right combination of base and solvent enables highly selective derivatization of halogenated arenes; this cannot yet be achieved by any other means [112] (Scheme 2.49). Choice of the right combination of base and solvent enables highly selective derivatization of halogenated arenes; this cannot yet be achieved by any other means [112] (Scheme 2.49).…”

A tribute to Prof. Manfred Schlosser

“…More recently, the goal was to attain building blocks with uncommon substituent patterns available for research work in the life science area (fluorine-containing compounds, azines and diazines, azoles…) through selective deprotometalation and subsequent functionalization. [13][14][15] These efforts culminated in the concept of optional site selectivity and the development of a 'toolbox of organometallic methods for regiochemically exhaustive functionalization'. 16 The general goal was to convert simple aromatics, including heterocyclics, into all possible polar organometallic regioisomers, through a judicious choice of base, solvent and possibly ligand, as well as a better knowledge of the factors governing reactivity and regioselectivity, in order to afford a large range of functionalized scaffolds to achieve 'rational and maximal structure proliferation'.…”