Nickel-catalyzed coupling reaction of alkyl halides with aryl Grignard reagents in the presence of 1,3-butadiene: mechanistic studies of four-component coupling and competing cross-coupling reactions

Iwasaki, Takanori; Fukuoka, Asuka; Yokoyama, Wataru; Min, Xin; Hisaki, Ichiro; Yang, Tao; Ehara, Masahiro; Kuniyasu, Hitoshi; Kambe, Nobuaki

doi:10.1039/c7sc04675h

Cited by 47 publications

(28 citation statements)

References 110 publications

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“…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

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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.

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Section: Intermolecular Dicarbofunctionalization Of Alkenesmentioning

confidence: 99%

Nickel‐CatalyzedDicarbofunctionalization of Alkenes^†

2020

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“…In the course of these investigations,K ambea nd coworkers isolated the anionic nickelate complex [PhNi(h 1 ,h 3 -C 8 H 12 )] À from as olution of [Ni(cod) 2 ]( cod = cycloocta-1,5diene), PhLi, buta-1,3-diene, and 12-crown-4 in high yields. [31] This complex contains two dimerized diene units and has a structure analogoust ot hat of the palladate anion shown in Scheme1.T he apparently high tendency of nickel to mediate the dimerization of the diene contrasts the behavior of the palladates, which moreover showed only al owered binding affinity to the diene. This lowered binding affinity gives rise to coordinately unsaturated complexes,w hich are prone to aggregation reactions and, ultimately,t he formation of palladium black.…”

Section: Comparison With Nickel/diene and Cobalt/diene Catalystsmentioning

confidence: 95%

“…Herein, we report the observation of transient anionic nanoclusters formed in palladium/diene-catalyzed cross-coupling reactions.A sK ambea nd co-workers have shown, this catalyst system works well for the coupling of alkyl halides with Grignardr eagents. [27][28][29][30][31] The postulated reactionm echanism starts with the in situ formation of am ononuclear bis(h 3 -allyl) palladium complex (Scheme 1). [27][28][29][30][31] Thet ransfer of an organyl group from the Grignard reagent to the palladium center then affords an anionic intermediate, which undergoes oxidative addition of an alkyl halide in an S N 2-type process.T he resulting heteroleptic neutral speciesr eleases the cross-coupling product in ar eductive elimination and regenerates the bis(h 3 -allyl) palladium complex.…”

Section: Introductionmentioning

confidence: 99%

Formation of Transient Anionic Metal Clusters in Palladium/Diene‐Catalyzed Cross‐Coupling Reactions

Kolter

Koszinowski

2019

Chemistry A European J

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Despite their considerable practical value, palladium/1,3‐diene‐catalyzed cross‐coupling reactions between Grignard reagents RMgCl and alkyl halides AlkylX remain mechanistically poorly understood. Herein, we probe the intermediates formed in these reactions by a combination of electrospray‐ionization mass spectrometry, UV/Vis spectroscopy, and NMR spectroscopy. According to our results and in line with previous hypotheses, the first step of the catalytic cycle brings about transmetalation to afford organopalladate anions. These organopalladate anions apparently undergo SN2‐type reactions with the AlkylX coupling partner. The resulting neutral complexes then release the cross‐coupling products by reductive elimination. In gas‐phase fragmentation experiments, the occurrence of reductive eliminations was observed for anionic analogues of the neutral complexes. Although the actual catalytic cycle is supposed to involve chiefly mononuclear palladium species, anionic palladium nanoclusters [PdnR(DE)n]−, (n=2, 4, 6; DE=diene) were also observed. At short reaction times, the dinuclear complexes usually predominated, whereas at longer times the tetra‐ and hexanuclear clusters became relatively more abundant. In parallel, the formation of palladium black pointed to continued aggregation processes. Thus, the present study directly shows dynamic behavior of the palladium/diene catalyst system and degradation of the active catalyst with increasing reaction time.

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“…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%

“…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. In 2017, Engle et al demonstrated an ickel-catalyzed b,g-dicarbofunctionalization of alkenyl carbonyl compounds with aryl iodides and alkylzincs.…”

Section: Nickel Catalysismentioning

confidence: 99%

Transition‐Metal‐Catalyzed Three‐Component Difunctionalizations of Alkenes

Zhang

Liu

Chen

et al. 2018

Chemistry An Asian Journal

244

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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.

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Nickel-catalyzed coupling reaction of alkyl halides with aryl Grignard reagents in the presence of 1,3-butadiene: mechanistic studies of four-component coupling and competing cross-coupling reactions

Abstract: The detailed reaction mechanism of anionic Ni complex-promoted C–C bond forming reactions was clarified by experimental and theoretical methods.

Cited by 47 publications

References 110 publications

Nickel‐CatalyzedDicarbofunctionalization of Alkenes^†

Nickel‐CatalyzedDicarbofunctionalization of Alkenes^†

Formation of Transient Anionic Metal Clusters in Palladium/Diene‐Catalyzed Cross‐Coupling Reactions

Transition‐Metal‐Catalyzed Three‐Component Difunctionalizations of Alkenes

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Nickel-catalyzed coupling reaction of alkyl halides with aryl Grignard reagents in the presence of 1,3-butadiene: mechanistic studies of four-component coupling and competing cross-coupling reactions

Abstract: The detailed reaction mechanism of anionic Ni complex-promoted C–C bond forming reactions was clarified by experimental and theoretical methods.

Cited by 47 publications

References 110 publications

Nickel‐CatalyzedDicarbofunctionalization of Alkenes†

Nickel‐CatalyzedDicarbofunctionalization of Alkenes†

Formation of Transient Anionic Metal Clusters in Palladium/Diene‐Catalyzed Cross‐Coupling Reactions

Transition‐Metal‐Catalyzed Three‐Component Difunctionalizations of Alkenes

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Nickel‐CatalyzedDicarbofunctionalization of Alkenes^†

Nickel‐CatalyzedDicarbofunctionalization of Alkenes^†