Dual Ni/Organophotoredox Catalyzed Allylative Ring Opening Reaction of Oxabenzonorbornadienes and Analogs

Diallo, Abdoul G.; Paris, Déborah; Faye, Djiby; Gaillard, Sylvain; Lautens, Mark; Renaud, Jean‐Luc

doi:10.1021/acscatal.2c00512

Cited by 5 publications

(2 citation statements)

References 55 publications

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“…Transition metal-catalyzed allylation-type reactions are a powerful method to construct new carbon–carbon and carbon–heteroatom bonds . This class of reactions spans from palladium-catalyzed Tsuji–Trost reactions (Scheme a) to more recent reductive allylation processes with first-row transition metals (Scheme b). − A common feature in all these transformations is the formation of a π-allyl-metal intermediate. Typically, a low-valent metal species undergoes oxidative addition across an allyl electrophile to generate a π-allyl-metal intermediate.…”

Section: Introductionmentioning

confidence: 99%

Investigating Oxidative Addition Mechanisms of Allylic Electrophiles with Low-Valent Ni/Co Catalysts Using Electroanalytical and Data Science Techniques

et al. 2022

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The catalysis by a π-allyl-Co/Ni complex has drawn significant attention recently due to its distinct reactivity in reductive Co/Ni-catalyzed allylation reactions. Despite significant success in reaction development, the critical oxidative addition mechanism to form the π-allyl-Co/Ni complex remains unclear. Herein, we present a study to investigate this process with four catalysis-relevant complexes: Co(MeBPy)Br2, Co(MePhen)Br2, Ni(MeBPy)Br2, and Ni(MePhen)Br2. Enabled by an electroanalytical platform, Co(I)/Ni(I) species were found responsible for the oxidative addition of allyl acetate. Kinetic features of different substrates were characterized through linear free-energy relationship (Hammett-type) studies, statistical modeling, and a DFT computational study. In this process, a coordination-ionization-type transition state was proposed, sharing a similar feature with Pd(0)-mediated oxidative addition in Tsuji–Trost reactions. Computational and ligand structural analysis studies support this mechanism, which should provide key information for next-generation catalyst development.

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Section: Introductionmentioning

confidence: 99%

Investigating Oxidative Addition Mechanisms of Allylic Electrophiles with Low-Valent Ni/Co Catalysts Using Electroanalytical and Data Science Techniques

et al. 2022

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“…Along this line, dual photoredox and nickel catalysis has shown great potential in the design of co-catalysis strategies for the construction of challenging chemical bonds starting from inexpensive substrates under very mild conditions [32][33][34][35][36][37][38][39][40][41][42][43][44][45][46][47] . Inspired by elegant reports on nickel/photoredox dual catalysis [48][49][50][51][52][53][54][55][56][57][58][59][60][61][62][63][64] and our recent work 65 , we envisioned an unprecedented triple catalysis process comprising cooperative nickel, photoredox and sulfinate catalysis to accomplish the challenging intermolecular α-arylation of electron-deficient alkenes and styrenes using commercially available aryl bromides (Fig. 1d).…”

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confidence: 99%

Cooperative triple catalysis enables regioirregular formal Mizoroki–Heck reactions

2022

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The Mizoroki–Heck reaction between alkenes and aryl halides represents one of the most important methods for C−C bond formation in synthetic chemistry. Governed by their electronic and steric nature, alkenes are generally arylated with high regioselectivity, which conversely hampers diversity, in particular, if the regioirregular isomer is targeted. Usually, electron-poor alkenes selectively afford the corresponding β-coupled products, and achieving the opposite regioselectivity to obtain their α-arylated congeners is highly challenging. It would be desirable to access the irregular α-regioisomer by simple variation of the reaction conditions, keeping the standard substrates, thereby significantly enlarging the product space. Herein, we describe an intermolecular α-arylation of electron-poor alkenes through cooperative nickel, photoredox and sulfinate catalysis. This triple catalysis system operates under mild conditions and features excellent functional group tolerance. The orchestration of radical, transition metal and ionic bond-forming and -cleaving reactions in a single process is highly challenging, but certainly opens valuable doors in terms of reactivity. Moreover, the intermolecular α-arylation, α-alkenylation and α-alkynylation of styrenes could also be achieved through a one-pot process.

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Rhodium-catalyzed ring-opening reactions of heterobicyclic alkenes with heteroarene nucleophiles

Neufeld¹,

Pounder²,

Tam³

2023

Tetrahedron Letters

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Dual Ni/Organophotoredox Catalyzed Allylative Ring Opening Reaction of Oxabenzonorbornadienes and Analogs

Cited by 5 publications

References 55 publications

Investigating Oxidative Addition Mechanisms of Allylic Electrophiles with Low-Valent Ni/Co Catalysts Using Electroanalytical and Data Science Techniques

Investigating Oxidative Addition Mechanisms of Allylic Electrophiles with Low-Valent Ni/Co Catalysts Using Electroanalytical and Data Science Techniques

Cooperative triple catalysis enables regioirregular formal Mizoroki–Heck reactions

Rhodium-catalyzed ring-opening reactions of heterobicyclic alkenes with heteroarene nucleophiles

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