Base‐Mediated Defluorosilylation of C(sp<sup>2</sup>)−F and C(sp<sup>3</sup>)−F Bonds

Liu, Xiang‐Wei; Zárate, Cayetana; Martı́n, Rubén

doi:10.1002/ange.201813294

Cited by 20 publications

(5 citation statements)

References 96 publications

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“…Cobalt particles were homogeneously dispersed on both Co/CÀ X catalysts, indicating that the worm-like mesoporous structure of CÀ X was beneficial for the anchoring of cobalt crystallites. Much higher cobalt dispersion was found on the plasma treated sample, the average cobalt particle size on Co/CÀ X-C was around 13 nm, while that on Co/CÀ X-P was in the range of 5-6 nm, consistent with our previous findings, [11,25,26] glow discharge plasma is an effective technique for the preparation of highly dispersed cobalt-based catalysts. As to the other two carbon material supported catalysts, a very high cobalt dispersion was illustrated on Co/ACÀ C, cobalt particles with size of 2-5 nm were well dispersed in AC support.…”

Section: Morphology and Porous Propertiessupporting

confidence: 90%

Properties of Carbon Xerogels Supported Cobalt‐Based Catalysts and Their Performance in CO Hydrogenation Reaction

et al. 2019

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Carbon xerogels (C−X), which synthesized by a convenient method with moderate porous texture and high surface area, was used as potential support for cobalt‐based catalysts, and the catalytic performance was studied by CO hydrogenation. The use of activated carbon (AC) and carbon nanotubes (CNTs) as supports was also investigated for comparison. The catalysts were prepared by incipient wetness impregnation method, and adjustment of cobalt dispersion on Co/C−X was achieved by variation of the decomposition approaches of cobalt nitrate. Characterization and CO hydrogenation results showed that C−X is a good candidate as catalyst support, it could homogeneously disperse both big cobalt particles and small ones. And the supported Co/C−X catalysts had either higher catalytic activity or better reaction stability, in comparison with CNTs and AC supported counterparts. Glow discharge plasma assisted decomposition of cobalt nitrate led to the formation of much smaller cobalt particles, and due to the inert properties of carbon materials, the Co/C−X‐P catalyst showed both higher cobalt dispersion and cobalt reducibility than the calcined counterpart, and thus presented a much higher CO hydrogenation activity with good reaction stability as well.

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Section: Morphology and Porous Propertiessupporting

confidence: 90%

Properties of Carbon Xerogels Supported Cobalt‐Based Catalysts and Their Performance in CO Hydrogenation Reaction

et al. 2019

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“…However, the chemical transformation of fluoro-organic compounds via C–F bond cleavage under very mild conditions is still rare. For example, aryl fluorides have rarely been functionalized due to the difficulty of oxidative addition of low-valent transition metals to C( sp 2 )-F bonds, whereas the field of C( sp 2 )-F cleavage using silyl cooperativity and/or transition-metal catalysis has also benefited from a wide breadth of research, especially in the last decade 24 – 30 . Activation of C( sp 3 )-F bonds in aliphatic fluorocarbons is mostly limited to reactive benzyl or allylic fluorides where p -block-based Lewis acids with high fluoride affinity are usually required 31 – 33 .…”

Section: Introductionmentioning

confidence: 99%

Catalyst-free carbosilylation of alkenes using silyl boronates and organic fluorides via selective C-F bond activation

et al. 2021

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A regioselective carbosilylation of alkenes has emerged as a powerful strategy to access molecules with functionalized silylated alkanes, by incorporating silyl and carbon groups across an alkene double bond. However, to the best of our knowledge, organic fluorides have never been used in this protocol. Here we disclose the catalyst-free carbosilylation of alkenes using silyl boronates and organic fluorides mediated by tBuOK. The main feature of this transformation is the selective activation of the C-F bond of an organic fluoride by the silyl boronate without undergoing potential side-reactions involving C-O, C-Cl, heteroaryl-CH, and even CF3 groups. Various silylated alkanes with tertiary or quaternary carbon centers that have aromatic, hetero-aromatic, and/or aliphatic groups at the β-position are synthesized in a single step from substituted or non-substituted aryl alkenes. An intramolecular variant of this carbosilylation is also achieved via the reaction of a fluoroarene with a ω-alkenyl side chain and a silyl boronate.

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“…Meanwhile, Martin et al . developed a base‐promoted defluorosilylation of unactivated fluoroarenes and fluoroalkanes by C—F bond cleavage . Despite these advances, transition‐metal‐free defluorosilylation of fluoroalkenes to build silylated fluoroalkenes remains elusive …”

Section: Background and Originality Contentmentioning

confidence: 99%

Transition‐Metal‐Free Defluorosilylation of Fluoroalkenes with Silylboronates

Gao

Wang

et al. 2019

Chin. J. Chem.

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of main observation and conclusion Silylated fluoroalkenes are important synthetic intermediates with complementary reactivity, which play a key role in the construction of natural products, pharmaceuticals, and manmade materials. Converting the normally highly stable fluoroalkenes into silylated fluoroalkenes by selective defluorosilylation is a challenging task. Herein, we report a simple, inexpensive and robust defluorosilylation of a variety of fluoroalkenes with silylboronates in the presence of alkoxy base to directly synthesize various silylated fluoroalkenes. The protocol features mild and safe reaction conditions that avoid a catalyst, a transition metal, a ligand, and high reaction temperature and tolerates a wide scope of fluoroalkene substrates without compromising the efficiency. Density functional theory calculations show that transient silyl anion complex undergoes an S N 2' or S N V substitution, which is responsible for this base-mediated defluorosilylation.1010 www.cjc.wiley-vch.de

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Base‐Mediated Defluorosilylation of C(sp²)−F and C(sp³)−F Bonds

Cited by 20 publications

References 96 publications

Properties of Carbon Xerogels Supported Cobalt‐Based Catalysts and Their Performance in CO Hydrogenation Reaction

Properties of Carbon Xerogels Supported Cobalt‐Based Catalysts and Their Performance in CO Hydrogenation Reaction

Catalyst-free carbosilylation of alkenes using silyl boronates and organic fluorides via selective C-F bond activation

Transition‐Metal‐Free Defluorosilylation of Fluoroalkenes with Silylboronates

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Base‐Mediated Defluorosilylation of C(sp2)−F and C(sp3)−F Bonds

Cited by 20 publications

References 96 publications

Properties of Carbon Xerogels Supported Cobalt‐Based Catalysts and Their Performance in CO Hydrogenation Reaction

Properties of Carbon Xerogels Supported Cobalt‐Based Catalysts and Their Performance in CO Hydrogenation Reaction

Catalyst-free carbosilylation of alkenes using silyl boronates and organic fluorides via selective C-F bond activation

Transition‐Metal‐Free Defluorosilylation of Fluoroalkenes with Silylboronates

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Base‐Mediated Defluorosilylation of C(sp²)−F and C(sp³)−F Bonds