Four-component radical-dual-difunctionalization (RDD) and decarbonylative alkylative peroxidation of two different alkenes with aliphatic aldehydes and TBHP

2019 ◽  
Vol 55 (80) ◽  
pp. 12080-12083 ◽  
Author(s):  
Ren-Xiang Liu ◽  
Feng Zhang ◽  
Yong Peng ◽  
Luo Yang
Keyword(s):  
Alkyl Radical ◽  
Cross Coupling ◽  
Aliphatic Aldehydes

From difunctionalization of a single alkene to radical-dual-difunctionalization of two different alkenes! A alkylative peroxidation and cross-coupling of two alkenes was established with the aliphatic aldehydes as the alkyl radical source.

Copper-catalyzed decarboxylative and oxidative decarbonylative cross-coupling between cinnamic acids and aliphatic aldehydes

2018 ◽  
Vol 5 (22) ◽  
pp. 3299-3305 ◽  
Author(s):  
Zaigang Luo ◽  
Xinxin Han ◽  
Yuyu Fang ◽  
Peng Liu ◽  
Chengtao Feng ◽  
...  
Keyword(s):  
Cross Coupling ◽  
Cinnamic Acids ◽  
Aliphatic Aldehydes

A convenient copper-catalyzed decarboxylative and oxidative decarbonylative cross-coupling of cinnamic acids with aliphatic aldehydes was achieved, which provides a useful strategy of C(sp3)–C(sp2) bonds construction for the synthesis of alkyl-substituted E-alkenes.

Radical alkylation of C(sp3)–H bonds with diacyl peroxides under catalyst-free conditions

2019 ◽  
Vol 55 (98) ◽  
pp. 14813-14816 ◽  
Author(s):  
Hao Tian ◽  
Wentao Xu ◽  
Yuxiu Liu ◽  
Qingmin Wang
Keyword(s):  
Alkyl Radical ◽  
Cross Coupling ◽  
Catalyst Free ◽  
Alkylation Reactions

Herein, we describe a protocol for alkylation reactions of C(sp3)–H bonds with diacyl peroxides by means of a process involving cross-coupling between an alkyl radical and an α-aminoalkyl radical.

1,2-Arylalkylation of N-(arylsulfonyl)acrylamides using aliphatic aldehydes as the alkyl source

2017 ◽  
Vol 15 (26) ◽  
pp. 5476-5479 ◽  
Author(s):  
Jin-Tao Yu ◽  
Rongzhen Chen ◽  
Jiawei Zhu ◽  
Jiang Cheng
Keyword(s):  
Alkyl Radical ◽  
Aliphatic Aldehydes ◽  
Metal Free

A metal-free decarbonylative arylalkylation of N-(arylsulfonyl)acrylamides using aliphatic aldehydes as the alkyl radical source was developed.

scholarly journals Nickel-Catalyzed Reductive Coupling of Unactivated Alkyl Bromides and Aliphatic Aldehydes

2021 ◽  
Author(s):  
Cole Cruz ◽  
John Montgomery
Keyword(s):  
Functional Groups ◽  
Catalytic System ◽  
Cross Coupling ◽  
Secondary Alcohols ◽  
Reductive Coupling ◽  
Aliphatic Aldehydes ◽  
Alkyl Bromide ◽  
Alkyl Bromides ◽  
Wide Range ◽  
Ni Species

We report the development of a mild, convenient coupling of aliphatic aldehydes and unactivated alkyl bromides. The catalytic system features the use of a common Ni(II) precatalyst and a readily available bisoxazoline ligand and affords silyl-protected secondary alcohols. The reaction is operationally simple, utilizing Mn as a stoichiometric reductant, and tolerates a wide range of functional groups. Initial mechanistic experiments support a mechanism featuring an alpha-silyloxy Ni species which undergoes formal oxidative addition of the alkyl bromide species via a reductive cross-coupling pathway.

scholarly journals Unexpected Nickel Complex Speciation Unlocks Alternative Pathways for the Reactions of Alkyl Halides with dppf-Nickel(0)

2020 ◽  
Author(s):  
Megan Greaves ◽  
Thomas O. Ronson ◽  
Guy Lloyd-Jones ◽  
Feliu Maseras ◽  
Stephen Sproules ◽  
...  
Keyword(s):  
Alkyl Radical ◽  
Nickel Complex ◽  
Cross Coupling ◽  
Active Species ◽  
Alkyl Halides ◽  
Phosphine Ligands ◽  
Coupling Reactions ◽  
Alternative Pathways ◽  
Cross Coupling Reactions ◽  
Abstraction Reaction

The mechanism of the reactions between dppf-Ni0 complexes and alkyl halides has been investigated using kinetic and mechanistic experiments and DFT calculations. The active species is [Ni(dppf)2], which undergoes a halide abstraction reaction with alkyl halides and rapidly captures the alkyl radical that is formed. The yields in prototypical nickel-catalysed Kumada cross-coupling reactions are shown to be improved by the addition of free phosphine ligands<br>

A Synergistic LUMO Lowering Strategy Using Lewis Acid Catalysis in Water to Enable Photoredox Catalytic, Functionalizing C-C Cross-Coupling of Styrenes

2018 ◽  
Author(s):  
Elisabeth Speckmeier ◽  
Patrick J. W. Fuchs ◽  
Kirsten Zeitler
Keyword(s):  
Cyclic Voltammetry ◽  
Lewis Acid ◽  
Lewis Acids ◽  
Alkyl Radical ◽  
Acid Catalysis ◽  
Coupling Reaction ◽  
Cross Coupling ◽  
Catalytic Activation ◽  
Type Transformation ◽  
Acetophenone Derivatives

Easy available alpha-carbonyl acetates serve as convenient alkyl radical source for an efficient, photocatalytic crosscoupling with a great variety of styrenes. Activation of electronically different alpha-acetylated acetophenone derivatives could be effected via LUMO lowering catalysis using a superior, synergistic combination of water and (water-compatible) Lewis acids. Deliberate application of <i>fac</i>-Ir(ppy)<sub>3</sub> as photocatalyst to enforce an oxidative quenching cycle is crucial to the success of this (umpolung type) transformation. Mechanistic particulars of this dual catalytic coupling reaction have been studied in detail using both Stern-Volmer and cyclic voltammetry experiments. As demonstrated in more than 30 examples, our waterassisted<br>LA/photoredox catalytic activation strategy allows for excess-free, equimolar radical cross-coupling and subsequent formal Markovnikov hydroxylation to versatile 1,4-difunctionalized products in good to excellent yields.

A Synergistic LUMO Lowering Strategy Using Lewis Acid Catalysis in Water to Enable Photoredox Catalytic, Functionalizing C-C Cross-Coupling of Styrenes

2018 ◽  
Author(s):  
Elisabeth Speckmeier ◽  
Patrick J. W. Fuchs ◽  
Kirsten Zeitler
Keyword(s):  
Cyclic Voltammetry ◽  
Lewis Acid ◽  
Lewis Acids ◽  
Alkyl Radical ◽  
Acid Catalysis ◽  
Coupling Reaction ◽  
Cross Coupling ◽  
Catalytic Activation ◽  
Type Transformation ◽  
Acetophenone Derivatives

Easy available alpha-carbonyl acetates serve as convenient alkyl radical source for an efficient, photocatalytic crosscoupling with a great variety of styrenes. Activation of electronically different alpha-acetylated acetophenone derivatives could be effected via LUMO lowering catalysis using a superior, synergistic combination of water and (water-compatible) Lewis acids. Deliberate application of <i>fac</i>-Ir(ppy)<sub>3</sub> as photocatalyst to enforce an oxidative quenching cycle is crucial to the success of this (umpolung type) transformation. Mechanistic particulars of this dual catalytic coupling reaction have been studied in detail using both Stern-Volmer and cyclic voltammetry experiments. As demonstrated in more than 30 examples, our waterassisted<br>LA/photoredox catalytic activation strategy allows for excess-free, equimolar radical cross-coupling and subsequent formal Markovnikov hydroxylation to versatile 1,4-difunctionalized products in good to excellent yields.

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