When all C–C breaks LO–Ose

Trends in Chemistry, Journal Year: 2023, Volume and Issue: 5(3), P. 174 - 200

Published: Feb. 14, 2023

Organic peroxides are becoming popular intermediates for novel chemical transformations. The weak O-O bond is readily reduced by transition metals, including iron and copper, to initiate a radical cascade process that breaks C-C bonds. Great potential exists the rapid generation of complexity, originating from ability couple resulting free radicals with wide range partners. First, this review article discusses history synthesis organic peroxides, providing context necessary understand methodology. Then, it highlights 91 examples recent applications functionalization bonds accessed through metal-mediated reduction peroxides. Finally, we provide some comments about safety when working

Language: Английский

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A cheap metal catalyzed ring expansion/cross-coupling cascade: a new route to functionalized medium-sized and macrolactones

Chemical Science, Journal Year: 2023, Volume and Issue: 14(19), P. 5220 - 5225

Published: Jan. 1, 2023

An efficient alkoxyl radical-triggered ring expansion/cross-coupling cascade was developed under cheap metal catalysis. Through the metal-catalyzed radical relay strategy, a wide range of medium-sized lactones (9-11 membered) and macrolactones (12, 13, 15, 18, 19-membered) were constructed in moderate to good yields, along with diverse functional groups including CN, N3, SCN, X installed concurrently. Density theory (DFT) calculations revealed that reductive elimination cycloalkyl-Cu(iii) species is more favorable reaction pathway for cross-coupling step. Based on results experiments DFT, Cu(i)/Cu(ii)/Cu(iii) catalytic cycle proposed this tandem reaction.

Language: Английский

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Fe-Catalyzed Alkylazidation of α-Trifluoromethylalkenes: An Access to Quaternary Stereocenters Containing CF₃ and N₃ Groups

Organic Letters, Journal Year: 2023, Volume and Issue: 25(8), P. 1336 - 1341

Published: Feb. 23, 2023

A concise Fe-catalyzed alkylazidation of α-trifluoromethylalkenes via a C–C bond cleavage/radical addition/azidation cascade is described. This protocol features broad substrate scope, excellent functional group compatibility, and the ability to be performed on gram scale, thus offering practical step-economic approach synthetically useful tertiary α-trifluoromethyl azides.

Language: Английский

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Exploring the regioselectivity of the cyanoalkylation of 3-aza-1,5-dienes: photoinduced synthesis of 3-cyanoalkyl-4-pyrrolin-2-ones

Organic Chemistry Frontiers, Journal Year: 2022, Volume and Issue: 9(17), P. 4575 - 4582

Published: Jan. 1, 2022

Regioselective cyanoalkylalkenylation of 3-aza-1,5-dienes with oxime esters induced by visible light.

Language: Английский

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Switchable In Situ SO₂ Capture and CF₃ Migration of Enol Triflates with Peroxyl Compounds under Iron Catalysis

Organic Letters, Journal Year: 2022, Volume and Issue: 24(36), P. 6653 - 6657

Published: Sept. 1, 2022

Switchable in situ SO2 capture and CF3 migration of enol triflates with peroxyl compounds under iron catalysis are presented. By regulating the structure peroxides, a variety keto-functionalized dialkyl sulfones α-trifluoromethyl ketones were selectively synthesized good yields mild conditions.

Language: Английский

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Iron-Catalyzed Alkoxyl Radical-Induced C–C Bond Cleavage/gem-Difluoroalkylation Cascade

Organic Letters, Journal Year: 2023, Volume and Issue: 25(23), P. 4329 - 4334

Published: June 1, 2023

An inexpensive iron-catalyzed alkoxyl radical-induced C–C bond cleavage/gem-difluoroalkylation cascade is presented. Regulated by the structure of radical precursors, fluorinated distal diketones were synthesized through a ring-opening strategy and difluoroalkylated medium-sized lactones macrolactones constructed via ring-expansion strategy. Both protocols proceeded under mild redox neutral conditions with broad substrate scope good functional group compatibility.

Language: Английский

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Photoinduced copper-catalyzed alkoxyl radical-triggered ring-expansion/aminocarbonylation cascade

Chinese Chemical Letters, Journal Year: 2023, Volume and Issue: 35(6), P. 109263 - 109263

Published: Oct. 30, 2023

Language: Английский

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Thermo-induced decarboxylative α-C(sp³)–H fluoroalkylation of glycine derivatives with fluorinated peroxy esters

Organic Chemistry Frontiers, Journal Year: 2022, Volume and Issue: 9(13), P. 3546 - 3551

Published: Jan. 1, 2022

A thermo-induced α-C(sp 3 )–H fluoroalkylation of glycine derivatives with a new type fluorinated peroxy ester is described.

Language: Английский

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Nickel-Catalyzed Radical Ring-Opening Phosphorylation of Cycloalkyl Hydroperoxides Leading to Distal Acylphosphine Oxides

Organic Letters, Journal Year: 2023, Volume and Issue: 25(6), P. 928 - 932

Published: Feb. 2, 2023

A facile and efficient nickel-catalyzed C-C bond cleavage/phosphorylation of various cycloalkyl hydroperoxides was developed. This radical ring-opening strategy provided practical access to structurally diverse distal ketophosphine oxides in one pot through concurrent C═O/C-P formation with high atom economy under mild room temperature base-free conditions.

Language: Английский

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Recent Advances in Molecule Synthesis Involving C-C Bond Cleavage of Ketoxime Esters

Molecules, Journal Year: 2023, Volume and Issue: 28(6), P. 2667 - 2667

Published: March 15, 2023

The synthetic strategies of oxime derivatives participating in radical-type reactions have been rapidly developed the last few decades. Among them, N–O bond cleavage esters leading to formation nitrogen-centered radicals triggers adjacent C–C produce carbon-centered free radicals, which has virtually used organic synthesis recent years. Herein, we summarized radical involving and through this special reaction form, including those from acyl ester cyclic ketoxime derivatives. These contents were systematically classified according different types. In review, after 2021 included, with emphasis on substrate scope mechanism.

Language: Английский

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