Nickel-catalyzed cross-coupling reaction of carbamates with silylmagnesium reagents

Murugesan, Vetrivelan; Balakrishnan, Venkadesh; Rasappan, Ramesh

doi:10.1016/j.jcat.2019.07.026

Cited by 33 publications

(24 citation statements)

References 111 publications

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“…In accordance with our interest in nickel-mediated cross-coupling reactions, , we were further interested in capitalizing on the application of Me 3 SiMgI in enantiospecific cross-coupling reactions via C(sp 3 )–O bond cleavage. We were optimistic that the methodology developed by Shi, Jarvo, ,− and others ,, (Scheme a) could be borrowed for the use of Me 3 SiMgI as the coupling partner; however, these literature protocols were not amenable to Me 3 SiMgI, and traces of the cross-coupled product were observed (Scheme c), highlighting the limitation of these literature strategies.…”

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confidence: 99%

“…Despite the success of Grignard reagents (unhindered) as a coupling partner in C(sp 3 )–OMe bond cleavage, the cross-coupling reactions of ethers remain essentially limited to C–C bond-forming reactions. On the contrary, organosilicons (C–Si bond) have widespread applications across various disciplines − and are versatile intermediates in organic synthesis. − Consequently, considerable effort in cross-coupling reactions has been spent to contribute to the synthesis of organosilanes, including silylation via C–N bond cleavage (Scheme b). − Recently, for the first time, we introduced an economical Me 3 SiMgI (directly synthesized from TMSI) in cross-coupling reactions [C(sp 2 )–OCb bond cleavage] for the synthesis of ArSiMe 3 , a useful organosilane for further synthetic transformations (Scheme b).…”

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confidence: 99%

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Nickel-Mediated Enantiospecific Silylation via Benzylic C–OMe Bond Cleavage

et al. 2021

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Benzylic stereocenters are found in bioactive and drug molecules, as enantiopure benzylic alcohols have been used to build such a stereogenic center, but are limited to the construction of a C–C bond. Silylation of alkyl alcohols has the potential to build bioactive molecules and building blocks; however, the development of such a process is challenging and unknown. Herein, we describe an unprecedented AgF-assisted nickel catalysis in the enantiospecific silylation of benzylic ethers.

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Nickel-Mediated Enantiospecific Silylation via Benzylic C–OMe Bond Cleavage

et al. 2021

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“…The streamlined synthetic approaches to these compounds involve treating alkyl Grignard/lithium reagents with chlorosilanes and catalytic hydrosilylation of alkenes . As an attractive alternative, transition-metal-catalyzed C–Si coupling offers a regio-defined approach to this class of compounds. − These methods typically involve the coupling of alkyl–I with R 3 Si–H, the coupling of alkyl electrophiles with R 3 Si–M (e.g., M = Li, B, Mg, or Zn), and the coupling of alkyl Grignard and zinc reagents with R 3 Si–X (mostly X = Br or I) . Alternatively, the reaction of alkyl and silyl electrophiles may deliver the same compounds by using more readily available chemicals; however, its potential remains largely unexplored.…”

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Nickel-Catalyzed Cross-Electrophile C(sp³)–Si Coupling of Unactivated Alkyl Bromides with Vinyl Chlorosilanes

Duan

Wang

et al. 2021

Org. Lett.

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Cross-electrophile C–Si coupling has emerged as a promising tool for the construction of organosilanes, but the potential of this method remains largely unexplored. Herein, we report a C(sp3)–Si coupling of unactivated alkyl bromides with vinyl chlorosilanes. The reaction proceeds under mild conditions, and it offers a new approach to alkylsilanes. 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 were tolerated. Incorporation of the −Si(vinyl)R2 moiety into complex molecules and the immobilization of a glass surface by formed organosilanes were demonstrated.

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“…In the backdrop of our recent findings on the preparation of Me 3 SiMgI from Me 3 SiI 30 and the literature reports on polar solvents such as dimethylacetamide, 26,31 hexamethylphosphoramide, 32 N , N -dimethylformamide, 26,27,31 dimethylsulfoxide, 32 acetonitrile, 33 tetramethylurea, 27 a CH 3 CN–pyridine 33 and N -methyl-2-pyrrolidone (NMP 27 a ) favoring the generation of organozinc reagents, we envisioned that amine additives may assist the formation of silylzinc reagents. Pleasingly, we observed a successful reductive metalation of zinc when an industrially friendly solvent, 34 toluene, along with 1.1 eq.…”

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confidence: 96%