Regioselective [2+2+2] Cycloaddition Reaction Using Allene‐ynes with Simple Allenes under Nickel Catalysis

Arai, Shigeru; Izaki, Arisa; Amako, Yuka; Nakajima, Masaya; Uchiyama, Masanobu; Nishida, Atsushi

doi:10.1002/adsc.201900719

Cited by 10 publications

(6 citation statements)

References 64 publications

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“…Whereas the theoretical study of Yang and Ehara focused on the cycloaddition of 1,6-ene-allenes and alkenes, recently, Arai et al 350 performed an experimental and theoretical study based on the [2 + 2 + 2] cycloaddition of 1,6-yne-allenes 349 and 352 and allenes 350 and 353 (Scheme 131). In all cases, the cycloaddition was chemoselective, taking place between the terminal double bond of the yne-allene and with the more substituted double bond of the external allene.…”

Section: Nickel Complexesmentioning

confidence: 99%

Mechanistic Studies of Transition-Metal-Catalyzed [2 + 2 + 2] Cycloaddition Reactions

2020

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The development of catalytic methodologies involving the formation of C−C bonds to enable the generation of cyclic systems constitutes a field of great relevance in synthetic organic chemistry. One paradigmatic process to accomplish this goal efficiently is the transition-metal-catalyzed [2 + 2 + 2] cycloaddition reaction, since it permits the formation of a wide range of highly functionalized 6-membered carbo-and heterocyclic molecules in a single step with high efficiency and perfect atom economy. A key feature of these transformations is the mechanistic pathway that they follow, since a deep knowledge of this mechanism may enable us to understand and improve the efficiency of the reaction. This review covers the mechanistic aspects, studied both from theoretical and experimental points of view, of the transition-metal-catalyzed [2 + 2 + 2] cycloaddition reaction involving all kinds of unsaturated substrates with metals such as Co, Ni, Ru, Rh, Ir, Pd, Zr, Ti, Ta, and Nb. A thorough overview is undertaken, from the seminal studies until the present day, of the key mechanistic aspects that influence the reactivity and selectivity of the reaction, comparing the involvement of different unsaturated substrates as well as the different transition metals used.

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Section: Nickel Complexesmentioning

confidence: 99%

Mechanistic Studies of Transition-Metal-Catalyzed [2 + 2 + 2] Cycloaddition Reactions

2020

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“…Given that previous cycloisomerization studies of unsaturated organic substrates have been successfully carried out using air-stable Ni[P(OPh) 3 ] 4 , , it was conceived that modification of the phosphite aryl moiety could improve the catalytic ability of these complexes. An increase in the steric bulk of the phosphite was proposed to improve the efficiency of various steps in the catalytic cycle, such as reductive elimination. , First, the aryl phosphites were prepared directly by reacting phenols and PCl 3 under basic conditions . Under these conditions, the phosphites 14b , 14d , and 14e were prepared in yields ranging from 65–73% (see the Supporting Information).…”

Section: Resultsmentioning

confidence: 99%

“…The group of Arai has also used a more air-stable nickel catalyst, nickel phenylphosphite, in carbocyanative cyclization reaction of allene-ynes or bis-allenes . Additionally, a nickel phosphite/Xantphos system has been used in a “head-to-head” [2 + 2] cycloaddition of bis-allenes . A similar nickel catalytic system has also been shown to convert allene-allenamides, to tricyclic species through sequential [2 + 2] and [4 + 2] cycloaddition reactions, in a stereoselective manner …”

Section: Introductionmentioning

confidence: 99%

Nickel Phosphite-Catalyzed Tetradehydro-Diels–Alder Reactions of (E)-3-ene-1,8-diynes

et al. 2023

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A nickel-catalyzed tetradehydro-Diels–Alder reaction of (E)-3-ene-1,8-diynes for the preparation of isoindolines, dihydroisobenzofurans, and tetrahydroisoquinolines has been developed. A series of air-stable nickel catalysts were used in this study, including the novel nickel(0)–phosphite catalysts, Ni[P(O-3,5-Me-Ph)3]4, Ni[P(O-1-naphthyl)3]4, and Ni[P(O-2-naphthyl)3]4. To help understand the type of intermediate in the initial cycloisomerization process, the trapping of nickellacycle intermediates with pinacolborane to yield vinyl boronates is also discussed.

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“…and trisubstituted allenes to give highly functionalized carbocycles (Scheme 54). 116 The reaction was performed in the presence of Ni[P(OPh) 3 ] 4 (10 mol%) in toluene at 100 °C and delivered regioselectively the bicyclic structures in 10-94% yield for oxygen-, nitrogen-, and carbon-tethered alleneynes. The reaction with a cyclic allene allowed the construction of a tricyclic system.…”

Section: Review Synthesismentioning

confidence: 99%

Recent Progress in Metal-Catalyzed [2+2+2] Cycloaddition Reactions

Matton¹,

Huvelle²,

Haddad³

et al. 2021

Synthesis

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Metal-catalyzed [2+2+2] cycloaddition is a powerful tool that allows rapid construction of functionalized 6-membered carbo- and heterocycles in a single step through an atom-economical process with high functional group tolerance. The reaction is usually regio- and chemoselective although selectivity issues can still be challenging for intermolecular reactions involving the cross-[2+2+2] cycloaddition of two or three different alkynes and various strategies have been developed to attain high selectivities. Furthermore, enantioselective [2+2+2] cycloaddition is an efficient means to create central, axial, and planar chirality and a variety of chiral organometallic complexes can be used for asymmetric transition-metal-catalyzed inter- and intramolecular reactions. This review summarizes the recent advances in the field of [2+2+2] cycloaddition.1 Introduction2 Formation of Carbocycles2.1 Intermolecular Reactions2.1.1 Cyclotrimerization of Alkynes2.1.2 [2+2+2] Cycloaddition of Two Different Alkynes2.1.3 [2+2+2] Cycloaddition of Alkynes/Alkenes with Alkenes/Enamides2.2 Partially Intramolecular [2+2+2] Cycloaddition Reactions2.2.1 Rhodium-Catalyzed [2+2+2] Cycloaddition2.2.2 Molybdenum-Catalyzed [2+2+2] Cycloaddition2.2.3 Cobalt-Catalyzed [2+2+2] Cycloaddition2.2.4 Ruthenium-Catalyzed [2+2+2] Cycloaddition2.2.5 Other Metal-Catalyzed [2+2+2] Cycloaddition2.3 Totally Intramolecular [2+2+2] Cycloaddition Reactions3 Formation of Heterocycles3.1 Cycloaddition of Alkynes with Nitriles3.2 Cycloaddition of 1,6-Diynes with Cyanamides3.3 Cycloaddition of 1,6-Diynes with Selenocyanates3.4 Cycloaddition of Imines with Allenes or Alkenes3.5 Cycloaddition of (Thio)Cyanates and Isocyanates3.6 Cycloaddition of 1,3,5-Triazines with Allenes3.7 Cycloaddition of Aldehydes with Enynes or Allenes/Alkenes3.8 Totally Intramolecular [2+2+2] Cycloaddition Reactions4 Conclusion

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Regioselective [2+2+2] Cycloaddition Reaction Using Allene‐ynes with Simple Allenes under Nickel Catalysis

Cited by 10 publications

References 64 publications

Mechanistic Studies of Transition-Metal-Catalyzed [2 + 2 + 2] Cycloaddition Reactions

Mechanistic Studies of Transition-Metal-Catalyzed [2 + 2 + 2] Cycloaddition Reactions

Nickel Phosphite-Catalyzed Tetradehydro-Diels–Alder Reactions of (E)-3-ene-1,8-diynes

Recent Progress in Metal-Catalyzed [2+2+2] Cycloaddition Reactions

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