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8.1. 36 Organolithium Compounds and Related Reagents in Unconventional Reaction Media
Book
Editors: Li, J. J. ; Luisi, R. ; Wan, Q.
Title: Knowledge Updates 2025/2
Online ISBN: 9783132459823; Book DOI: 10.1055/b000001095
1st edition © 2025 Thieme. All rights reserved.
Georg Thieme Verlag KG, Stuttgart
Subjects: Organic Chemistry;Chemical Reactions, Catalysis;Organometallic Chemistry;Laboratory Techniques, Stoichiometry
Science of Synthesis Knowledge Updates
Parent publication
Title: Science of Synthesis
DOI: 10.1055/b-00000101
Series Editors: Fürstner, A. (Editor-in-Chief); Carreira, E. M.; Faul, M.; Kobayashi, S.; Koch, G.; Nevado, C.; You, S.-L.
Type: Multivolume Edition
Abstract
Challenging the conventional need for inert atmospheres, dry solvents, and strict temperature control when using s-block organometallic reagents (such as Grignard reagents or organolithium/sodium compounds), this Science of Synthesis review highlights recent advances that enable their operation under air, at room temperature, and in the presence of moisture. Success has been driven by using sustainable protic solvents, such as water and deep eutectic solvents (DESs). These protocols have proven versatile for key organic transformations, including nucleophilic additions to unsaturated molecules, ortho- and lateral lithiation of aromatics, and palladium-catalyzed cross-couplings. Additionally, the development of one-pot tandem hybrid transformations is presented, where these polar s-block organometallic species are effectively integrated with organo-, transition-metal, or biocatalysis.
Key words
organolithium reagents - Grignard reagents - organosodium reagents - water - deep eutectic solvents - green chemistry - alcohols - amines - direct ortho-metalation - lateral lithiation - one-pot tandem hybrid transformations- 8 Hansen BB, Spittle S, Chen B, Poe D, Zhang Y, Klein JM, Horton A, Adhikari L, Zelovich T, Doherty BW, Gurkan B, Maginn EJ, Ragauskas A, Dadmun M, Zawodzinski TA, Baker GA, Tuckerman ME, Savinell RF, Sangoro JR. Chem. Rev. 2021; 121: 1232
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