Multicomponent Coupling Reaction of Perfluoroarenes with 1,3-Butadiene and Aryl Grignard Reagents Promoted by an Anionic Ni(II) Complex

The crystal structures of different perfluoroorganyl iodanes are described, including those of four new benziodoxole derivatives with RF = n‐C3F7, n‐C4F9, n‐C8F17, and C6F5. In all of the compounds, the iodine atom shows significant Lewis acidity, and the fourth coordination site is readily filled by secondary bonding interactions to produce square‐planar coordination. Although this geometry is a good model for benziodoxoles, benziodoxolone derivatives tend to aggregate further through additional weak I···O or I···aryl contacts. The different interactions lead to the formation of various assemblies with different dimensions in the solid state. The protonation of the reagents results in the formation of entirely different supramolecular structures, which are supported by hydrogen bonding. The structural features of the reagents in the solid state reflect well their behavior in solution, and the I–C(RF) bond is influenced by the coordination of Lewis basic solvents to the iodine atom and by hydrogen bonding with protic solvents. These solvent effects are more pronounced for reagents containing the trifluoromethyl fragment than for derivatives with longer RF chains.

show abstract

“…Yield: 1.36 g (48 %). The identity of the compound was established by comparison of the NMR spectroscopic data with reference data …”

Section: Methodsmentioning

confidence: 99%

Supramolecular Aggregation of Perfluoroorganyl Iodane Reagents in the Solid State and in Solution

et al. 2018

View full text Add to dashboard Cite

show abstract

“…A nickel‐catalyzed dimerization and difunctionalization of 1,3‐butadienes were also reported by Kambe and coworkers in 2003 (Scheme 5). [ 53‐56 ] Alkyl/aryl Grignard reagents as well as electrophiles such as chlorosilanes, alkyl fluorides and perfluoroarenes were used in this nickel‐catalyzed process. The authors proposed that [Ni 0 ] species participated in the oxidative dimerization of 1,3‐butadiene to generate bis(π‐allyl)nickel intermediate A , which readily reacted with the Grignard reagent to form an anionic complex B with a nucleophilic σ‐allyl bond.…”

Section: Intermolecular Dicarbofunctionalization Of Alkenesmentioning

confidence: 99%

Nickel‐CatalyzedDicarbofunctionalization of Alkenes^†

2020

View full text Add to dashboard Cite

As a straightforward strategy for rapidly increasing molecular complexity, dicarbofunctionalization of alkenes has attracted substantial interests of organic synthesis, medicine chemistry, and materials science. Nickel-catalyzed cascade dicarbofunctionalizations have been flourished in this area recently, and nickel-mediated radical pathways particularly offer new opportunities in conjunctive cross-couplings with alkyl coupling partners. Herein, we give a comprehensive review of nickel-catalyzed dicarbofunctionalization of alkenes through a historical perspective, including intermolecular three-component reactions and intramolecular cascade reactions. Among the pathways discussed in this review, the carbometallation/cross-coupling process and the radical addition/cross-coupling process are the two major pathways for the nickel-catalyzed dicarbofunctionalization of alkenes. The oxidative cyclization and 1,2-metallate shift processes are also selectively discussed. These methods overcome the limitations associated with the reactions using noble metals in the field, providing an efficient and straightforward access to structurally diversified molecules. Yun-Cheng Luo (right) received his BSc degree in 2016 and master degree in 2019 from University of Science and Technology of China. Then he joined Professor Xingang Zhang's group at Shanghai Institute of Organic Chemistry, University of Chinese Academy of Sciences to pursue his doctorate in organic chemistry. His research interests are focused on the activation of inert C-H or C-X bonds of bulky chemicals and their applications in the synthesis of fluorine-containing compounds. Chang Xu (middle) obtained his BSc degree in basic pharmacy from China Pharmaceutical University (China) in 2015. With an interest in organic chemistry and medicinal chemistry, he then began his graduate studies at Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences under the supervision of Professor Xingang Zhang. His research interests are focused on the activation and transformations of fluoroalkylanes and their applications in medicinal chemistry. Xingang Zhang (left) obtained his BSc degree in 1998 from Sichuan University (China) and received the Ph.D. in 2003 at Shanghai Institute of Organic Chemistry (SIOC), Chinese Academy of Sciences. After his postdoctoral work at University of Illinois at Urbana Champaign (USA), he joined the faculty team of SIOC as a research associate professor in 2008, and became research professor in 2012. His current research interests are focused on organofluorine chemistry and chemical biology.

show abstract

“…The corresponding allylsilanes were generated in good yields under the reaction conditions. Recently, the same group extended the electrophiles from chlorosilanes to alkyl halides and perfluoroarenes …”

Section: Nickel Catalysismentioning

confidence: 99%

“…[41] The corresponding allylsilanes were generated in good yields under the reactionc onditions. Recently,t he same group extended the electrophiles from chlorosilanes to alkyl halides [42,43] and perfluoroarenes. [44] The directing strategy was also applied in the nickel-mediated three-component difunctionalizationo ft erminala lkenes.…”

Section: Nickel Catalysismentioning

confidence: 99%

Transition‐Metal‐Catalyzed Three‐Component Difunctionalizations of Alkenes

Zhang

Liu

Chen

et al. 2018

Chemistry An Asian Journal

244

View full text Add to dashboard Cite

Three-component reactions can directly convert three reactants into the desired products in one pot and thus greatly shorten the synthetic path. Recently, transition-metal catalysis has been applied in the difunctionalization of alkenes and remarkable progress has been achieved to facilitate the construction of a wide range of functional molecules with high atom- and step-economic efficiency. This Focus Review highlights recent advances in this field.

show abstract

Multicomponent Coupling Reaction of Perfluoroarenes with 1,3-Butadiene and Aryl Grignard Reagents Promoted by an Anionic Ni(II) Complex

Cited by 43 publications

References 52 publications

Supramolecular Aggregation of Perfluoroorganyl Iodane Reagents in the Solid State and in Solution

Supramolecular Aggregation of Perfluoroorganyl Iodane Reagents in the Solid State and in Solution

Nickel‐CatalyzedDicarbofunctionalization of Alkenes^†

Transition‐Metal‐Catalyzed Three‐Component Difunctionalizations of Alkenes

Contact Info

Product

Resources

About

Multicomponent Coupling Reaction of Perfluoroarenes with 1,3-Butadiene and Aryl Grignard Reagents Promoted by an Anionic Ni(II) Complex

Cited by 43 publications

References 52 publications

Supramolecular Aggregation of Perfluoroorganyl Iodane Reagents in the Solid State and in Solution

Supramolecular Aggregation of Perfluoroorganyl Iodane Reagents in the Solid State and in Solution

Nickel‐CatalyzedDicarbofunctionalization of Alkenes†

Transition‐Metal‐Catalyzed Three‐Component Difunctionalizations of Alkenes

Contact Info

Product

Resources

About

Nickel‐CatalyzedDicarbofunctionalization of Alkenes^†