Cascade radical reaction of substrates with a carbon–carbon triple bond as a radical acceptor

Miyabe, Hideto; Asada, Ryuta; Takemoto, Yoshiji

doi:10.3762/bjoc.9.128

Cited by 20 publications

(9 citation statements)

References 72 publications

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“…A 5 M hydrochloric acid solution in a water/methanol mixture (obtained by diluting 3.2 mL of 37% aqueous hydrochloric acid in 4.4 mL of methanol, 7.6 mL, 38 mmol, 10 equiv) was slowly added to tert-butyl (benzyloxy)(prop-2-yn-1-yl)carbamate (1.00 g, 3.83 mmol, prepared according to literature procedure) 31 General procedure C for the aza-Michael reaction to 3-vinyl-1,2,4-triazine. The alkoxyamine derivative 2 (1.5 equiv) was added to a solution of 3-vinyl-1,2,4-triazines 1 (0.1-1 mmol, 0.1 M) and trifluoromethanesulfonimide E (20 mol%) in toluene.…”

Section: O-benzyl-n-(prop-2-yn-1-yl)hydroxylamine (2h)mentioning

confidence: 99%

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Organocatalytic aza-Michael Reaction to 3-Vinyl-1,2,4-triazines as a Valuable Bifunctional Platform

et al. 2019

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An unprecedented catalytic aza-Michael addition to substituted 3-vinyl-1,2,4-triazines, as original bifunctional platforms for domino conjugate addition-ihDA/rDA reaction, was achieved using the highly acidic triflimide as organocatalyst. Based on the use of alkoxyamine nucleophiles, this sequence not only highlights a rare example of catalytic aza-Michael reaction to alkenylazaarenes but proved to be useful for the elaboration of an array of biorelevant tetrahydro-[1,6]-naphthyridines. Medicinal chemistry and chemical biology are currently seeking original heterocyclic scaffolds as biological tools. Accordingly, the development of new synthetic methodologies aiming at exploring chemical space, while increasing molecular diversity and complexity, is a current concern in organic synthesis. 1 The construction of fused non-aromatic/heteroaromatic bicycles has emerged as a promising strategy furnishing unprecedented potent bioactive

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Section: O-benzyl-n-(prop-2-yn-1-yl)hydroxylamine (2h)mentioning

confidence: 99%

“…d6, 80 °C): δC 153.7 (C), 153.6 (C), 138.6 (C), 134.9 (CH), 128.1 (CH), 128.0 (2 CH), 127.0 (C), 125.9 (2 CH), 117.2 (CH), 60.3 (CH), 59.4 (CH3), 53.6 (CH2), 33.3 (CH2), 32.1 (CH2),31.0 (CH2), 24.8 (CH2), 21.6 (CH2), 13.3 (CH3). ESI+ -HRAM: m/z calculated for [C20H27N2O] + ([M+H] + ) 311.211790, found 311.211662.…”

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confidence: 99%

Organocatalytic aza-Michael Reaction to 3-Vinyl-1,2,4-triazines as a Valuable Bifunctional Platform

et al. 2019

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“…Compared with the stereocontrol studies on intermolecular radical reactions, the enantiocontrol in radical cyclizations still remains a major challenge [45][46][47][48][49][50][51][52]. Therefore, we have started investigating the new type of chiral Lewis acid-mediated cyclization approach [53][54][55]. The radical addition-cyclizationtrapping reaction of substrate 7 having methacryloyl moiety and the C-C triple bond was studied by using radical initiator Et 3 B (Scheme 4) [56,57].…”

Section: Cascade Reactions Via Radical-radical Processmentioning

confidence: 99%

Cascade radical reactions via carbon-carbon/heteroatom bond-forming process

Miyabe¹,

Takemoto²

2014

Univers Org Chem

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This article highlights our recent efforts toward developing the cascade reactions constructing the carbon-carbon and carbonheteroatom bond based on radical chemistry. The diethylzinc-promoted reaction of dehydroamino acid derivatives with acid anhydride or π-allyl palladium complex gave α,α-disubstituted amino acids via the radical and anionic carbon-carbon bond-forming process. This reaction was successfully expanded into the reductive transformation of N-phthaloyl dehydroalanine using Bu 3 SnH and Pd(PPh 3) 4. The chiral Lewis acid-mediated cascade radical addition-cyclization-trapping reaction proceeded smoothly with good enantioselectivities by using hydroxamate ester functionality as a chiral Lewis acid-coordinating tether between two radical acceptors. This method was applied into cascade reaction involving the unfavorable polarity-mismatched addition of electrophilic perfluoroalkyl radicals to electron-deficient acceptors. Additionally, cascade sequence terminated by radical-radical coupling was also reported.

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“…Recent decades have seen a renaissance in radical chemistry [ 13 , 14 , 15 , 16 , 17 , 18 , 19 , 20 , 21 ]. In practical applications, radical and photochemical reactions play a pivotal role in the synthesis of various organic compounds and drugs [ 22 , 23 , 24 , 25 , 26 , 27 , 28 , 29 ], functionalization of heterocyclic systems [ 30 ], photoredox catalysis [ 31 , 32 , 33 ], and materials science [ 34 ].…”

Section: Introductionmentioning

confidence: 99%

Computational Design of Radical Recognition Assay with the Possible Application of Cyclopropyl Vinyl Sulfides as Tunable Sensors

Sahharova¹,

Gordeev²,

Eremin³

et al. 2021

IJMS

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The processes involving the capture of free radicals were explored by performing DFT molecular dynamics simulations and modeling of reaction energy profiles. We describe the idea of a radical recognition assay, where not only the presence of a radical but also the nature/reactivity of a radical may be assessed. The idea is to utilize a set of radical-sensitive molecules as tunable sensors, followed by insight into the studied radical species based on the observed reactivity/selectivity. We utilize this approach for selective recognition of common radicals—alkyl, phenyl, and iodine. By matching quantum chemical calculations with experimental data, we show that components of a system react differently with the studied radicals. Possible radical generation processes were studied involving model reactions under UV light and metal-catalyzed conditions.

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Cascade radical reaction of substrates with a carbon–carbon triple bond as a radical acceptor

Cited by 20 publications

References 72 publications

Organocatalytic aza-Michael Reaction to 3-Vinyl-1,2,4-triazines as a Valuable Bifunctional Platform

Organocatalytic aza-Michael Reaction to 3-Vinyl-1,2,4-triazines as a Valuable Bifunctional Platform

Cascade radical reactions via carbon-carbon/heteroatom bond-forming process

Computational Design of Radical Recognition Assay with the Possible Application of Cyclopropyl Vinyl Sulfides as Tunable Sensors

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