Photoredox/Nickel‐Catalyzed Single‐Electron Tsuji–Trost Reaction: Development and Mechanistic Insights

Matsui, Jennifer K.; Gutiérrez‐Bonet, Álvaro; Rotella, Madeline; Alam, Rauful; Gutiérrez, Osvaldo; Molander, Gary A.

doi:10.1002/ange.201809919

Cited by 27 publications

(7 citation statements)

References 64 publications

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“…7 Nickel/photoredox dualcatalyzed alkylation of vinyl epoxides has also been developed, with strong evidence of an inner-sphere mechanism. 8 Inspired by previous work, a Ni-based radical approach to functionalize allylic electrophiles was sought. Herein, alkylation of allyl alcohol derived motifs has been demonstrated by using 4-alkyl 1,4-dihydropyridines (DHPs) 9 as latent radical precursors.…”

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confidence: 99%

Regioselective Single-Electron Tsuji–Trost Reaction of Allylic Alcohols: A Photoredox/Nickel Dual Catalytic Approach

et al. 2019

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A radical-mediated functionalization of allyl alcohol derived partners with a variety of alkyl 1,4-dihydropyridines via photoredox/nickel dual catalysis is described. This transformation transpires with high linear and E-selectivity, avoiding the requirement of harsh conditions (e.g., strong base, elevated temperature). Additionally, using aryl sulfinate salts as radical precursors, allyl sulfones can also be obtained. Kinetic isotope effect experiments implicated oxidative addition of the nickel catalyst to the allylic electrophile as the turnover-limiting step, supporting previous computational studies.

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confidence: 99%

Regioselective Single-Electron Tsuji–Trost Reaction of Allylic Alcohols: A Photoredox/Nickel Dual Catalytic Approach

et al. 2019

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“…Such a method can emulate CCSD(T) accuracy with the use of a suitable basis set with a low computational cost comparable to DFT methods and thus likely leads to wider application to studying nickel/photoredox dual catalysis 112–116 . In this vein, our group has applied this method to calculating the single‐point energies of the full catalytic cycle of a challenging single‐electron Tsuji–Trost reaction 117 and a three‐component C–H activation/alkene dicarbofunctionalization reaction 118 in photoredox/Ni dual catalytic conditions (vide infra).…”

Section: Methodsmentioning

confidence: 99%

“…More recently, in collaboration with Molander and coworkers, our group studied the mechanism of a photoredox/Ni dual‐catalyzed single‐electron Tsuji‐Trost reaction between trifluoroborate salts and vinyl epoxides using both DFT and DLPNO‐CCSD(T) calculation (Figure 4a). 117 Compared to the alkylation of aryl bromide system (Figure 2), a Ni(0)/Ni(II) oxidative addition with a vinyl epoxide to afford 22 is favorable (via 21‐TS‐22 , barrier of only 3.1 kcal/mol from Ni(0)‐vinyl epoxide complex 21 ), followed by radical addition of benzyl radical 16 (blue; Figure 4b). In this case, the Ni(0) to Ni(I) radical addition transition state 18‐TS‐19 from Ni(0)‐benzyl complex 18 (1.5 kcal/mol) is higher in energy than the Ni(0)/Ni(II) oxidative addition transition state 21‐TS‐22 (−5.8 kcal/mol).…”

Section: Examples Of Mechanistic Studies Of Photoredox and Nickel Dua...mentioning

confidence: 99%

Mechanisms, challenges, and opportunities of dual Ni/photoredox‐catalyzed C(sp²)–C(sp³) cross‐couplings

Yuan

Gutiérrez

2021

WIREs Comput Mol Sci

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The merging of photoredox and nickel catalysis has revolutionized the field of C–C cross‐coupling. However, in comparison to the development of synthetic methods, detailed mechanistic investigations of these catalytic systems are lagging. To improve the mechanistic understanding, computational tools have emerged as powerful tools to elucidate the factors controlling reactivity and selectivity in these complex catalytic transformations. Based on the reported computational studies, it appears that the mechanistic picture of catalytic systems is not generally applicable, but is rather dependent on the specific choice of substrate, ligands, photocatalysts, etc. Given the complexity of these systems, the need for more accurate computational methods, readily available and user‐friendly dynamics simulation tools, and data‐driven approaches is clear in order to understand at the molecular level the mechanisms of these transformations. In particular, we anticipate that such improvement of theoretical methods will become crucial to advance the understanding of excited‐state properties and dynamics of key species, as well as to enable faster and unbiased exploration of reaction pathways. Further, with greater collaboration between computational, experimental, and spectroscopic communities, the mechanistic investigation of photoredox/Ni dual‐catalytic reactions is expected to thrive quickly, facilitating the design of novel catalytic systems and promoting our understanding of the reaction selectivity. This article is categorized under: Structure and Mechanism > Reaction Mechanisms and Catalysis Electronic Structure Theory > Density Functional Theory Molecular and Statistical Mechanics > Molecular Dynamics and Monte‐Carlo Methods

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“…Allyl alcohols 30–3a,b were then formed by inner sphere C(sp 2 )-C(sp 3 ) bond formation from the resulting Ni III complex. 193 …”

Section: Formation Of a C(sp 3 )-C Bondmentioning

confidence: 99%

Generation of Alkyl Radicals: From the Tyranny of Tin to the Photon Democracy

2020

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Alkyl radicals are key intermediates in organic synthesis. Their classic generation from alkyl halides has a severe drawback due to the employment of toxic tin hydrides to the point that “flight from the tyranny of tin” in radical processes was considered for a long time an unavoidable issue. This review summarizes the main alternative approaches for the generation of unstabilized alkyl radicals, using photons as traceless promoters. The recent development in photochemical and photocatalyzed processes enabled the discovery of a plethora of new alkyl radical precursors, opening the world of radical chemistry to a broader community, thus allowing a new era of photon democracy.

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Photoredox/Nickel‐Catalyzed Single‐Electron Tsuji–Trost Reaction: Development and Mechanistic Insights

Cited by 27 publications

References 64 publications

Regioselective Single-Electron Tsuji–Trost Reaction of Allylic Alcohols: A Photoredox/Nickel Dual Catalytic Approach

Regioselective Single-Electron Tsuji–Trost Reaction of Allylic Alcohols: A Photoredox/Nickel Dual Catalytic Approach

Mechanisms, challenges, and opportunities of dual Ni/photoredox‐catalyzed C(sp²)–C(sp³) cross‐couplings

Generation of Alkyl Radicals: From the Tyranny of Tin to the Photon Democracy

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Photoredox/Nickel‐Catalyzed Single‐Electron Tsuji–Trost Reaction: Development and Mechanistic Insights

Cited by 27 publications

References 64 publications

Regioselective Single-Electron Tsuji–Trost Reaction of Allylic Alcohols: A Photoredox/Nickel Dual Catalytic Approach

Regioselective Single-Electron Tsuji–Trost Reaction of Allylic Alcohols: A Photoredox/Nickel Dual Catalytic Approach

Mechanisms, challenges, and opportunities of dual Ni/photoredox‐catalyzed C(sp2)–C(sp3) cross‐couplings

Generation of Alkyl Radicals: From the Tyranny of Tin to the Photon Democracy

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Mechanisms, challenges, and opportunities of dual Ni/photoredox‐catalyzed C(sp²)–C(sp³) cross‐couplings