Organotin Reagents in Cross‐Coupling Reactions

Martín‐Matute, Belén; Szabó, Kálmán J.; Mitchell, Terence N.

doi:10.1002/9783527655588.ch6

Cited by 8 publications

(2 citation statements)

References 351 publications

(234 reference statements)

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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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“…Among all tin reagents, trialkyltin hydrides, especially tributyltin hydride, are privileged, as highlighted in a few review articles, ,− as reagents for reductive radical reactions as well as for radical cyclizations. The organotin reagents are also widely used as coupling partners in palladium-catalyzed cross-coupling reactions, mainly for the construction of C sp 2 –C sp 2 bonds according to Stille–Migita cross-coupling. − This reaction allows a good control of the stereochemistry in the resulting vinylic systems and a great functional group tolerance. − Accordingly, some C–C bonds, not that easy to synthesize, as for instance those involving the cross-coupling of “umpolung” organotin reagents with acyl halide, can be obtained, providing for instance highly efficient syntheses of 1,2 or 1,4-dicarbonyl compounds − with possible control of the stereochemistry . Indeed, Stille cross-coupling reactions have found applications in disciplines ranging from natural products and macrolides synthesis , to material sciences for the design of molecules having physical properties …”

Section: Introductionmentioning

confidence: 99%

Methodologies Limiting or Avoiding Contamination by Organotin Residues in Organic Synthesis

et al. 2015

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Photoredox Nickel‐Catalysed Stille Cross‐Coupling Reactions

Zhou,

Yang,

Yang

et al. 2023

Angewandte Chemie

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The Stille cross‐coupling reaction is one of the most common strategies for the construction of C–C bonds. Despite notable strides in the advancement of the Stille reaction, persistent challenges persist in hindering its greener evolution. These challenges encompass multiple facets, such as the high cost of precious metals and ligands, the demand for various additives, and the slow reaction rate. In comparison to the dominant palladium‐catalysed Stille reactions, cost‐effective nickel‐catalysed systems lag behind, and enantioconvergent Stille reactions of racemic stannanes remain undeveloped. Herein, we present a pioneering instance of nickel‐catalysed enantioconvergent Stille cross‐coupling reactions of racemic stannane reagents, resulting in the formation of C–C bonds in good to high yields with excellent stereoselectivity. This strategy provides a practical, scalable, and operationally straightforward method for the synthesis of C(sp3)–C(sp3), C(sp3)–C(sp2), and C(sp3)–C(sp) bonds under exceptionally mild conditions (without additives and bases, ambient temperature). The innovative use of synergistic photoredox/nickel catalysis enables a novel single‐electron transmetalation process of stannane reagents, providing a new research paradigm of Stille reactions.

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Organotin Reagents in Cross‐Coupling Reactions

Cited by 8 publications

References 351 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

Methodologies Limiting or Avoiding Contamination by Organotin Residues in Organic Synthesis

Photoredox Nickel‐Catalysed Stille Cross‐Coupling Reactions

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