Nickel‐Catalyzed Reductive C(sp<sup>2</sup>)−Si Coupling of Chlorohydrosilanes via Si−Cl Cleavage

Zhao, Zhenzhen; Pang, Xiaoyang; Wei, Xiao‐Xue; Liu, Xueyuan; Shu, Xing‐Zhong

doi:10.1002/anie.202200215

Cited by 37 publications

(32 citation statements)

References 89 publications

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“…The initial studies were disappointing, with no desired product being observed when the reactions were conducted under various conditions in the presence of a nitrogen ligand such as 5,5′-dmbpy ( L1 ) or 3,4,7,8-Me 4 Phen ( L2 ) (Table ). These ligands have been effective at reductive C–Si couplings . Our recent finding and other reports revealed that chlorosilanes might be activated by nickel through an S N 2 oxidative addition.…”

supporting

confidence: 56%

Nickel-Catalyzed Reductive [4 + 1] Sila-Cycloaddition of 1,3-Dienes with Dichlorosilanes

Pan

Wei

et al. 2023

J. Am. Chem. Soc.

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Transition-metal-catalyzed sila-cycloaddition has been a promising tool for accessing silacarbocycle derivatives, but the approach has been limited to a selection of well-defined sila-synthons. Herein, we demonstrate the potential of chlorosilanes, which are industrial feedstock chemicals, for this type of reaction under reductive nickel catalysis. This work extends the scope of reductive coupling from carbocycle to silacarbocycle synthesis and from single C–Si bond formation to sila-cycloaddition reactions. The reaction proceeds under mild conditions and shows good substrate scope and functionality tolerance, and it offers new access to silacyclopent-3-enes and spiro silacarbocycles. The optical properties of several spiro dithienosiloles as well as structural variations of the products are demonstrated.

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confidence: 56%

Nickel-Catalyzed Reductive [4 + 1] Sila-Cycloaddition of 1,3-Dienes with Dichlorosilanes

Pan

Wei

et al. 2023

J. Am. Chem. Soc.

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“…Shu and co-workers reported an innovative approach to their synthesis via a Ni-catalyzed reductive coupling of triflates with chlorohydrosilanes (R 2 Si(H)Cl) (Scheme 14). 26 Their method apparently takes advantage of the polarization of the Si−Cl bond, which allows it to react via oxidative addition even though its bond dissociation energy (BDE) is much higher than that of the Si−H bond. For aryl triflates, Me 4 phen/Ni(COD) 2 was found to be optimal.…”

Section: ■ Recent Reports On Ni-catalyzed Reactionsmentioning

confidence: 99%

Recent Advances in Nonprecious Metal Catalysis

Haibach

Shekhar

Ahmed

et al. 2023

Org. Process Res. Dev.

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Nonprecious-metal-catalyzed alternatives to powerful precious metal transformations are of increasing interest in academia and the pharmaceutical industry due to the lower cost, better sustainability, and lower toxicity. With the continual growth in the broad field of nonprecious metal catalysis (NPMC), we have chosen to highlight selected articles published from March to June 2022 which are intended to highlight examples of NPMC that we feel may be especially relevant to pharmaceutical development. We aim to inspire academic and industrial innovation in NPMC through the discussion herein.

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“…Very recently, we reported a nickel-catalyzed cross-electrophile coupling of alkenyl and aryl electrophiles with hydrochlorosilanes (Scheme 22). 46 Conventionally, H−Si(R) 2 −Cl is activated by low-valenttransition metals through Si−H cleavage, because the bonddissociation energy of Si−H (ca. 77 kcal/mol) is much lower than that of Si−Cl (ca.…”

Section: Reductive Coupling Of Chlorosilanesmentioning

confidence: 99%

Reductive Cross-Coupling of Unreactive Electrophiles

2022

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Metrics & MoreArticle Recommendations CONSPECTUS: Transition-metal-catalyzed reductive coupling of electrophiles has emerged as a powerful tool for the construction of molecules. While major achievements have been made in the field of cross-couplings between organic halides and pseudohalides, an increasing number of reports demonstrates reactions involving more readily available, low-cost, and stable, but unreactive electrophiles. This account summarizes the recent results in our laboratory focusing on this topic. These findings typically include deoxygenative C−C coupling of alcohols, reductive alkylation of alkenyl acetates, reductive C−Si coupling of chlorosilanes, and reductive C−Ge coupling of chlorogermanes.The reductive deoxygenative coupling of alcohols with electrophiles is synthetically appealing, but the potential of this chemistry remains to be disclosed. Our initial study focused on the reaction of allylic alcohols and aryl bromides by the combination of nickel and Lewis acid catalysis. This method offers a selectivity that is opposite to that of the classic Tsuji−Trost reactions. Further investigation on the reaction of benzylic alcohols led to the foundation of a dynamic kinetic cross-coupling strategy with applications in the nickelcatalyzed reductive arylation of benzylic alcohols and cobalt-catalyzed enantiospecific reductive alkenylation of allylic alcohols. The titanium catalysis was later established to produce carbon radicals directly from unactivated tertiary alcohols via C−OH cleavage.The development of their coupling reactions with carbon fragments delivers new methods for the construction of all-carbon quaternary centers. These reactions have shown high selectivity for the functionalization of tertiary alcohols, leaving primary and secondary alcohols intact. Alkenyl acetates are inexpensive, stable, and environmentally friendly and are considered the most attractive alkenyl reagents. The development of reductive alkylation of alkenyl acetates with benzyl ammoniums and alkyl bromides offers mild approaches for the conversion of ketones into aliphatic alkenes. Extensive studies in this field have enabled us to extend the cross-electrophile coupling from carbon to silicon and germanium chemistry. These reactions harness the ready availability of chlorosilanes and chlorogermanes but suffer from the challenge of their low reactivity toward transition metals. Under reductive nickel catalysis, a broad range of alkenyl and aryl electrophiles couple well with vinyl-and hydrochlorosilanes. The use of alkyl halides as coupling partners led to the formation of functionalized alkylsilanes. The C−Ge coupling seems less substrate-dependent, and various common chlorogermanes couple well with aryl, alkenyl, and alkyl electrophiles. In general, functionalities such as Grignard-sensitive groups (e.g., acid, amide, alcohol, ketone, and ester), acid-sensitive groups (e.g., ketal and THP protection), alkyl fluoride and chloride, aryl bromide, alkyl tosylate and mesylate, silyl ether, and amine are tolerated. ...

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Nickel‐Catalyzed Reductive C(sp²)−Si Coupling of Chlorohydrosilanes via Si−Cl Cleavage

Cited by 37 publications

References 89 publications

Nickel-Catalyzed Reductive [4 + 1] Sila-Cycloaddition of 1,3-Dienes with Dichlorosilanes

Nickel-Catalyzed Reductive [4 + 1] Sila-Cycloaddition of 1,3-Dienes with Dichlorosilanes

Recent Advances in Nonprecious Metal Catalysis

Reductive Cross-Coupling of Unreactive Electrophiles

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Nickel‐Catalyzed Reductive C(sp2)−Si Coupling of Chlorohydrosilanes via Si−Cl Cleavage

Cited by 37 publications

References 89 publications

Nickel-Catalyzed Reductive [4 + 1] Sila-Cycloaddition of 1,3-Dienes with Dichlorosilanes

Nickel-Catalyzed Reductive [4 + 1] Sila-Cycloaddition of 1,3-Dienes with Dichlorosilanes

Recent Advances in Nonprecious Metal Catalysis

Reductive Cross-Coupling of Unreactive Electrophiles

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Nickel‐Catalyzed Reductive C(sp²)−Si Coupling of Chlorohydrosilanes via Si−Cl Cleavage