The preparation of organolithium reagents and intermediates

Leroux, Frédéric R.; Schlosser, Manfred; Zohar, Elinor; Marek, Ilan

doi:10.1002/047002111x.ch9

Cited by 46 publications

(24 citation statements)

References 319 publications

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“…The “superbase” designation associated with LIC-KOR originates from its enhanced reactivity compared to n -butyllithium, and though it is less reactive than n -butylpotassium, its reactivity is generally more controllable kinetically, and thus LIC-KOR is more utilizable than the separated alkylpotassium compound. Expressing the synergistic effect of LIC-KOR in broad terms, Schlosser notes, “the symbiotic action of two different metals (lithium and potassium) suppresses erratic side reactions” …”

Section: Heterometallic Synergistic Main Group Complexesmentioning

confidence: 99%

Alkali-Metal-Mediated Synergistic Effects in Polar Main Group Organometallic Chemistry

2019

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The development of synthetic chemistry since the early 1900s owes much to the service of organolithium reagents. Brilliant bases (e.g., deprotonating C−H bonds), nucleophiles (e.g., adding to unsaturated molecules), and transfer agents (e.g., delivering ligands to other metals), these versatile virtuosi and to a lesser extent the organic derivatives of the other common alkali metals sodium and potassium have proved indispensable in both academia and technology. Today these monometallic compounds are still utilized widely in synthetic campaigns, but in recent years they have been joined by an assortment of bimetallic formulations that also contain an alkali metal but in company with another metal. These bimetallic formulations often exhibit unique chemistry that can be interpreted in terms of synergistic effects, for which the alkali metal is essential, though it is often the second metal that performs the synthetic transformation. Here, this "alkali-metal-mediated" chemistry is surveyed focusing mainly on bimetallic formulations containing two alkali metals or an alkali metal paired with magnesium, calcium, zinc, aluminum, or gallium. In this International Year of the Periodic Table (IYPT), we ponder whether a Pairiodic Table of Element Pairs will emerge in the future.

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Section: Heterometallic Synergistic Main Group Complexesmentioning

confidence: 99%

Alkali-Metal-Mediated Synergistic Effects in Polar Main Group Organometallic Chemistry

2019

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“…The most impressive application of this methodology has been the preparation by Milne and Buchwald of one of the most versatile ligands (S-Phos) for the Suzuki-Miyaura coupling reaction. [14] The advantage of these ortho-bromobiphenyls lies in the possibility of functionalizing common precursors by regioselective bromine/lithium permutations [15] to give a large family of target ligands. [16] Unfortunately, the use of this protocol had been restricted to accessing suitable "aryne precursors".…”

Section: Introductionmentioning

confidence: 99%

Regioselectivity in the Aryne Cross‐Coupling of Aryllithiums with Functionalized 1,2‐Dibromobenzenes

et al. 2010

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Tri‐ and tetrasubstituted ortho‐bromobiaryls have been synthesized in good‐to‐excellent yields by aryne cross‐coupling reactions starting from 1,3‐dimethoxybenzene and functionalized 1,2‐dibromobenzenes. This study outlines the influence of the 1,2‐dibromobenzene precursor as well as the reaction temperature on the outcome of the aryl–aryl bond formation and indicates, in the case of dissymmetrical benzyne precursors, how structural parameters (electronic effects, steric hindrance, temperature, etc.) control the regioselectivity of the aryne cross‐coupling reactions.

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“…An effective discrimination between two bromine atoms as a function of their chemical environment has so far been observed only sporadically in such processes [30,34–35 51–52 70–72]. …”

Section: Resultsmentioning

confidence: 99%

“…Polar organometallic chemistry [33–35] allows the performance of highly selective reactions. Therefore, it seemed to us the ideal tool to reaching this goal.…”

Section: Introductionmentioning

confidence: 99%

Bromine–lithium exchange: An efficient tool in the modular construction of biaryl ligands

Bonnafoux¹,

Leroux²,

Colobert³

2011

Beilstein J. Org. Chem.

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SummaryRegioselective bromine–lithium exchange reactions on polybrominated biaryls enable the modular synthesis of various polysubstituted biphenyls such as bis(dialkylphosphino)-, bis(diarylphosphino)- and dialkyl(diaryl)phosphinobiphenyls. All permutations of substituents at the ortho positions of the biphenyls are possible. In a similar manner, one can gain access to monophosphine analogues. So far, such a process, based on the effective discrimination between bromine atoms as a function of their chemical environment, has been observed only sporadically.

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The preparation of organolithium reagents and intermediates

Cited by 46 publications

References 319 publications

Alkali-Metal-Mediated Synergistic Effects in Polar Main Group Organometallic Chemistry

Alkali-Metal-Mediated Synergistic Effects in Polar Main Group Organometallic Chemistry

Regioselectivity in the Aryne Cross‐Coupling of Aryllithiums with Functionalized 1,2‐Dibromobenzenes

Bromine–lithium exchange: An efficient tool in the modular construction of biaryl ligands

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