ChemInform Abstract: Preparation of Functionalized Lithium, Magnesium, Aluminum, Zinc, Manganese~, and Indium Organometallics from Functionalized Organic Halides.

Abstract

Preparation of Functionalized Lithium, Magnesium, Aluminum, Zinc, Manganese-, and Indium Organometallics from Functionalized Organic Halides. -[149 refs. + subrefs.]. -(DAGOUSSET, G.; FRANCOIS, C.; LEON, T.; BLANC, R.; SANSIAUME-DAGOUSSET, E.; KNOCHEL*, P.; Synthesis 46 (2014) 23, 3133-3171, http://dx.

Microscopy Reveals: Impact of Lithium Salts on Elementary Steps Predicts Organozinc Reagent Synthesis and Structure

“…2 Whereas only organomagnesium (Grignard) reagents used to be widely accessible by direct insertion of metals into organohalides, 3,4 the organometallic toolbox was expanded to zinc, 1 indium, 5−7 manganese, 8 and aluminum 9 through the addition of lithium chloride, sometimes in combination with transition metal additives. 10 Yet the mechanistic role of LiCl and the impact of the presence of additives on the structure of the resulting organozinc reagents remains poorly understood, limiting the expansion of salt effects that promote oxidative addition to other metals. The nature of the organometallic reagents that form from these reactions is of the utmost importance to understand, as the presence of salts left over is known to alter reactivity, often favorably.…”

“…The resulting reagents are useful, for example, as transmetalation partners in Negishi cross-coupling reactions . Whereas only organomagnesium (Grignard) reagents used to be widely accessible by direct insertion of metals into organohalides, , the organometallic toolbox was expanded to zinc, indium, − manganese, and aluminum through the addition of lithium chloride, sometimes in combination with transition metal additives . Yet the mechanistic role of LiCl and the impact of the presence of additives on the structure of the resulting organozinc reagents remains poorly understood, limiting the expansion of salt effects that promote oxidative addition to other metals.…”

Access to Functionalized Quaternary Stereocenters via the Copper-Catalyzed Conjugate Addition of Monoorganozinc Bromide Reagents Enabled by N,N-Dimethylacetamide

“…The metal-catalyzed formation of C–C bonds with organometallics represents a versatile technology in organic synthesis. Organozinc reagents comprise an important class of organometallics that have earned widespread use due to their outstanding functional group compatibility while maintaining sufficient reactivity. − This enhanced chemoselectivity coupled with reagent accessibility facilitates applications in the construction of highly functionalized organics for complex molecule synthesis. Strategies have been developed to modulate the reactivity of mild organozinc species when engaged with challenging substrates, as demonstrated in their conjugate addition to β,β-disubstituted α,β-unsaturated carbonyls.…”

Aplicação de reagentes organometálicos na funcionalização de imidazo[1,2-ɑ)piridinas e estudo de ressonância magnética nuclear dinâmica da 4-formil-aminoantipirina

“…As estratégias que permitem preparar esses reagentes podem envolver reações de transmetalação (um metal é trocado por outro menos eletropositivo, normalmente formando compostos mais estáveis), troca halogênio/metal (a interação de um halogênio com o composto organometálico, formando um segundo composto organometálico mais estável), inserção oxidativa (uma inserção de um metal, como magnésio ou zinco, entre uma ligação carbono-halogênio) e metalação dirigida (um composto orgânico sofre uma desprotonação por ação de uma base organometálica, formando um novo reagente organometálico (Dagousset, François et al 2014).…”