Carbon–Carbon Bond Forming Reactions Mediated by Organozinc Reagents

Chemla, Fabrice; Ferreira, Franck; Jackowski, Olivier; Micouin, Laurent; Pérez‐Luna, Alejandro

doi:10.1002/9783527655588.ch4

Cited by 4 publications

(5 citation statements)

References 357 publications

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“…Palladium-catalyzed cross-coupling reactions such as the Kumada–Tamao–Corriu (Mg), Suzuki–Miyaura (B), Stille–Migita–Kosugi (Sn), Hiyama–Denmark (Si), and Negishi (Zn) reactions have fundamentally changed the practice of organic synthesis in both academic and industrial settings alike (Figure ). Among these reactions, the Nobel Prize-sharing Suzuki–Miyaura reaction is the premier cross-coupling process, utilized across all disciplines of chemistry as well as in the industrial synthesis of fine chemicals and pharmaceuticals owing to its demonstrated reliability, broad functional group compatibility, and access to a wide variety of commercially available boron-based reagents.…”

Section: Introductionmentioning

confidence: 99%

Structural, Kinetic, and Computational Characterization of the Elusive Arylpalladium(II)boronate Complexes in the Suzuki–Miyaura Reaction

et al. 2017

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The existence of the oft-invoked intermediates containing the crucial Pd-O-B subunit, the "missing link", has been established in the Suzuki-Miyaura cross-coupling reaction. The use of low-temperature, rapid injection NMR spectroscopy (RI-NMR), kinetic studies, and computational analysis has enabled the generation, observation, and characterization of these highly elusive species. The ability to confirm the intermediacy of Pd-O-B-containing species provided the opportunity to clarify mechanistic aspects of the transfer of the organic moiety from boron to palladium in the key transmetalation step. Specifically, these studies establish the identity of two different intermediates containing Pd-O-B linkages, a tri-coordinate (6-B-3) boronic acid complex and a tetra-coordinate (8-B-4) boronate complex, both of which undergo transmetalation leading to the cross-coupling product. Two distinct mechanistic pathways have been elucidated for stoichiometric reactions of these complexes: (1) transmetalation via an unactivated 6-B-3 intermediate that dominates in the presence of an excess of ligand, and (2) transmetalation via an activated 8-B-4 intermediate that takes place with a deficiency of ligand.

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Section: Introductionmentioning

confidence: 99%

Structural, Kinetic, and Computational Characterization of the Elusive Arylpalladium(II)boronate Complexes in the Suzuki–Miyaura Reaction

et al. 2017

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“…Specifically, the chemical and physical evolution of the PS-750-M and TPGS-750-M systems were investigated in the presence of 1 (1 μM) and 2-iodoethylbenzene (0.5 M) (Figure ). To these systems was added tetramethylethylenediamine (TMEDA), a chelating ligand previously demonstrated to enhance yields of organozinc reagents in aqueous surfactant systems, ,,, and zinc metal powder, previously demonstrated to produce oxidative addition/direct insertion with organohalides (here, represented by 2-iodoethylbenzene) in the presence of TMEDA in aqueous surfactant systems. ,, …”

Section: Resultsmentioning

confidence: 99%

Surfactant Micellar and Vesicle Microenvironments and Structures under Synthetic Organic Conditions

Peacock

Blum

2023

J. Am. Chem. Soc.

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Fluorescence lifetime imaging microscopy (FLIM) reveals vesicle sizes, structures, microenvironments, reagent partitioning, and system evolution with two chemical reactions for widely used surfactant–water systems under conditions relevant to organic synthesis, including during steps of Negishi cross-coupling reactions. In contrast to previous investigations, the present experiments characterize surfactant systems with representative organohalide substrates at high concentrations (0.5 M) that are reflective of the preparative-scale organic reactions performed and reported in water. In the presence of representative organic substrates, 2-iodoethylbenzene and 2-bromo-6-methoxypyridine, micelles swell into emulsion droplets that are up to 20 μm in diameter, which is 3–4 orders of magnitude larger than previously measured in the absence of an organic substrate (5–200 nm). The partitioning of reagents in these systems is imaged through FLIMdemonstrated here with nonpolar, amphiphilic, organic, basic, and oxidative-addition reactive compounds, a reactive zinc metal powder, and a palladium catalyst. FLIM characterizes the chemical species and/or provides microenvironment information inside micelles and vesicles. These data show that surfactants cause surfactant-dictated microenvironments inside smaller micelles (<200 nm) but that addition of a representative organic substrate produces internal microenvironments dictated primarily by the substrate rather than by the surfactant, concurrent with swelling. Addition of a palladium catalyst causes the internal environments to differ between vesiclesinformation that is not available through nor predicted from prior analytical techniques. Together, these data provide immediately actionable information for revising reaction models of surfactant–water systems that underpin the development of sustainable organic chemistry in water.

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“…26–31 We considered that organozinc reagents may participate in catalytic reactions with diazo compounds ( 1 ) by one of two mechanisms (Scheme 1). The diazo compound could initially form carbene A by a Rh-catalyzed process, and carbozincation of this carbene would lead to the enolate C .…”

mentioning

confidence: 99%

“…Organozinc reagents have been employed in a variety of transition-metal catalyzed coupling reactions and have been shown to display a wide range of functional group tolerance. − We considered that organozinc reagents may participate in catalytic reactions with diazo compounds ( 1 ) by one of two mechanisms (Scheme ). The diazo compound could initially form carbene A by a Rh-catalyzed process, and carbozincation of this carbene would lead to the enolate C .…”

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confidence: 99%

Rh(II)-Catalyzed Reactions of Diazoesters with Organozinc Reagents

2015

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Rh(II)-catalyzed reactions of diazoesters with organozinc reagents are described. Diorganozinc reagents participate in reactions with diazo compounds by two distinct, catalyst-dependent mechanisms. With bulky diisopropylethylacetate ligands, the reaction mechanism is proposed to involve initial formation of a Rh-carbene and subsequent carbozincation to give a zinc enolate. With Rh2(OAc)4, it is proposed that initial formation of an azine precedes 1,2-addition by an organozinc reagent. This straightforward route to the hydrazone products provides a useful method for preparing chiral quaternary α-aminoesters or pyrazoles via the Paul-Knorr condensation with 1,3-diketones. Crossover and deuterium labeling experiments provide evidence for the mechanisms proposed.

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Carbon–Carbon Bond Forming Reactions Mediated by Organozinc Reagents

Cited by 4 publications

References 357 publications

Structural, Kinetic, and Computational Characterization of the Elusive Arylpalladium(II)boronate Complexes in the Suzuki–Miyaura Reaction

Structural, Kinetic, and Computational Characterization of the Elusive Arylpalladium(II)boronate Complexes in the Suzuki–Miyaura Reaction

Surfactant Micellar and Vesicle Microenvironments and Structures under Synthetic Organic Conditions

Rh(II)-Catalyzed Reactions of Diazoesters with Organozinc Reagents

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