Copper-Catalyzed C(sp)–C(sp<sup>3</sup>) Coupling of Terminal Alkynes with Alkylsilyl Peroxides via a Radical Mechanism

Sakamoto, Ryu; Kato, Terumasa; Sakurai, S.; Maruoka, Keiji

doi:10.1021/acs.orglett.8b00173

Cited by 42 publications

(14 citation statements)

References 77 publications

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“…In 2018, Maruoka and coworkers developed a fragmentation/alkynylation cascade of larger cycloalkanols using a copper catalyst and preoxidized starting materials (cycloalkylsilylperoxides) (eqn (2)). Interestingly, terminal alkynes could be use in this transformation, and one example of non-cyclic substrate is reported 98…”

Section: Transition Metal Catalyzed Alkynylation Of Alkyl Radicalsmentioning

confidence: 99%

Alkynylation of radicals: spotlight on the “Third Way” to transfer triple bonds

Vaillant

Waser

2019

Chem. Sci.

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Section: Transition Metal Catalyzed Alkynylation Of Alkyl Radicalsmentioning

confidence: 99%

Alkynylation of radicals: spotlight on the “Third Way” to transfer triple bonds

Vaillant

Waser

2019

Chem. Sci.

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“…Thus, the reaction of dimethyl malonate ( 1 a ) with 5‐membered cyclic alkylsilyl peroxide 2 a (1.4 equiv) in THF under the influence of copper(I) iodide (CuI) (5 mol%) with several different bases (K 2 CO 3 , Et 3 N, DIPEA, pyridine, and DMAP), which act as the base and/or ligand, at room temperature for 1 h. The use of K 2 CO 3 , Et 3 N, DIPEA, and pyridine as the base generally gave low yields of the desired monoalkylation product 3 a (Table 1, entries 1–4). In marked contrast, however, the use of DMAP as both a base and ligand afforded exclusively monoalkylation product 3 a in 74% yield (entry 5) [12c] . Here, the corresponding dialkylation product 6 was not formed under these conditions (Scheme 2).…”

Section: Resultsmentioning

confidence: 93%

“…Other commercially available reagents and solvents were purchased from Innochem, Energy Chemical and Bidepharm and used as received. Alkylsilyl peroxides 2 a , [12a] 2 b , [12a] 2 c , [12a] 2 d , [12a] 2 e , [12f] 2 g , [12c] 2 h [12c] and 2 i [12f] were prepared according to the methods in the literature.…”

Section: Methodsmentioning

confidence: 99%

Highly Selective Monoalkylation of Active Methylene and Related Derivatives using Alkylsilyl Peroxides by a Catalytic CuI‐DMAP System

Zhou

Wang

et al. 2021

Asian J Org Chem

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A new approach for highly selective monoalkylation of active methylene and related derivatives using various types of alkylsilyl peroxides in the presence of copper catalysts under mild conditions has been developed to a synthetically useful level. This approach has a wide substrate scope in terms of both active methylene compounds and alkylsilyl peroxides. In addition, nitroalkanes can also be employed for a copper‐catalyzed selective monoalkylation with alkylsilyl peroxides. The participation of radical species was proposed in the present monoalkylation reactions by the mechanistic study.

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“…The observing of acetamido methyl radical in the reaction, was proved by a restrict test with TEMPO (Scheme-XLIV). Ni(cod) Maruoka and co-workers [71] described a suitable method for the synthesis of internal alkynes from the coupling reaction between terminal alkynes C(sp) and alkylsilyl peroxide C(sp 3 ) via copper-catalyzed mediated the radical reaction (Scheme-XLV). Generally, this reaction forwards via generation of alkoxyl radical from alkylsilyl peroxide 173, followed by β-fragmentation and produce the alkyl radical intermediate.…”

Section: Ncmentioning

confidence: 99%

Recent Free-Radical Reactions

Khalid¹,

Mohammed²

2018

Asian J. Chem.

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Free radical reactions are one of the most coveted simulated objectives has been increasingly popular, very versatile and very important method in organic synthesis and due to their considerable and precious applications in different fields are widely used in the past few years. Free radical reactions can be efficient in the preparation of a large number of organic compounds which has been found large applications in many areas of life due to the ease of use of this method, accuracy, selectivity and required mild condition. Free radical reactions have many types of reaction e.g., cyclization, decarboxylation, additions reactions, hydrogen atom abstractions and alkynylation etc. [1a]. Free radicals are very supportive for the synthesis of cycles, atomic relocating permit effective groups to combine and facilely used to generate a number of ligations in one step [1b]. Likewise, the improvement of radicalmediated, C-C bond-forming transmutation has also attracted increasing attention. Usually, these protocols tolerate good selectivity, are highly convenient with collective functional This review highlights the most recent syntheses of free radical reactions, which included numerous processes (photoredox catalysis freeradical reactions, free-radical cascade processes reactions, Minisci-type free radical alkylation reactions and metal-catalysis free radical reactions). A photoredox-catalyzed C-H functioning of aromatic heterocyclic utilizing an assortment of various, alkyltrifluoroborates has been mentioned. Utilizing organo-photocatalyst and a moderate oxidant, conditions malleable for functionalizing complex aromatic heterocyclics are outlined to prepare a oriental agent for late-stage derivatization. Radical alkylations of aromatic heterocyclic (Minisci reactions) appear a more direct functionalization of particular, C-H bonds. For the ground mentioned above, alkylation designing using radical have recently risen to significance for the late-stage functionalization of aromatic heterocyclic framework. Therefore, this issue is the primary point of the present survey, which thinks about work from the most recent five years. The work is ordered by the key procedures associated with the synthesis of free-radical reactions, planning to give researchers a simple comprehension of this free radical-reactions-based science and to give bits of knowledge to provide insights for further investigations.

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Copper-Catalyzed C(sp)–C(sp³) Coupling of Terminal Alkynes with Alkylsilyl Peroxides via a Radical Mechanism

Cited by 42 publications

References 77 publications

Alkynylation of radicals: spotlight on the “Third Way” to transfer triple bonds

Alkynylation of radicals: spotlight on the “Third Way” to transfer triple bonds

Highly Selective Monoalkylation of Active Methylene and Related Derivatives using Alkylsilyl Peroxides by a Catalytic CuI‐DMAP System

Recent Free-Radical Reactions

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Copper-Catalyzed C(sp)–C(sp3) Coupling of Terminal Alkynes with Alkylsilyl Peroxides via a Radical Mechanism

Cited by 42 publications

References 77 publications

Alkynylation of radicals: spotlight on the “Third Way” to transfer triple bonds

Alkynylation of radicals: spotlight on the “Third Way” to transfer triple bonds

Highly Selective Monoalkylation of Active Methylene and Related Derivatives using Alkylsilyl Peroxides by a Catalytic CuI‐DMAP System

Recent Free-Radical Reactions

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Copper-Catalyzed C(sp)–C(sp³) Coupling of Terminal Alkynes with Alkylsilyl Peroxides via a Radical Mechanism