Zinc-Catalyzed Alkyne–Carbonyl Metathesis of Ynamides with Isatins: Stereoselective Access to Fully Substituted Alkenes

Ao, Chaoqun; Yang, Xiaohan; Jia, Shi-Kun; Xu, Xinfang; Yuan, Yanqiu; Zhang, Dan

doi:10.1021/acs.joc.9b02350

Cited by 27 publications

(7 citation statements)

References 83 publications

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“…The metathesis reaction between carbonyls and alkynes is a powerful method for the synthesis of α,ß-unsaturated ketones and has received much attention in the construction of heterocycles and in natural product synthesis. − This well-understood reaction involves an oxete intermediate, which is unstable toward ring opening and the formation of the enone product (Scheme a) . Since carbonyl–alkyne [2 + 2] cycloadditions are orbital-symmetry forbidden in the ground state, either photo-irradiation or the use of a catalyst , has been established as an avenue to overcome the kinetic barriers.…”

Section: Introductionmentioning

confidence: 99%

Oxophosphonium-alkyne cycloaddition reactions: reversible formation of 1,2-oxaphosphetes and six-membered phosphorus heterocycles

et al. 2020

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While the metathesis reaction between alkynes and carbonyl compounds is an important tool in organic synthesis, the reactivity of alkynes with isoelectronic main-group R 2 EO compounds is unexplored. Herein, we show that oxophosphonium ions, which are the isoelectronic phosphorus congeners to carbonyl compounds, undergo [2 + 2] cycloaddition reactions with different alkynes to generate 1,2-oxaphosphete ions, which were isolated and structurally characterized. The strained phosphorus−oxygen heterocycles open to the corresponding heterodiene structure at elevated temperature, which was used to generate six-membered phosphorus heterocycles via hetero Diels−Alder reactions. Insights into the influence of the substituents at the phosphorus center on the energy profile of the oxygen atom transfer reaction were obtained by quantum-chemical calculations.

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Section: Introductionmentioning

confidence: 99%

Oxophosphonium-alkyne cycloaddition reactions: reversible formation of 1,2-oxaphosphetes and six-membered phosphorus heterocycles

et al. 2020

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“…2016 年, 马晨课题组 [9] 发展了一例铜催化的炔与磺酰叠氮环加成启动的多组分反应策略来合成一系列图式 2 靛红与异腈酸酯 1,3-偶极环加成/反 1,3-偶极开环的可能机理 Scheme 2 Proposed mechanism for the 1,3-dipolar cycloaddition/inverse 1,3-dipolar ring opening of isatins with isocyanoacetate 2019 年, 胡文浩和张丹等 [11]…”

Section: 靛红衍生物的合成unclassified

Recent Advances in the Synthesis of Benzoheterocyclic Compounds Involving Isatins

Jia¹,

Luo²,

Chen³

et al. 2021

Chinese Journal of Organic Chemistry

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Isatin is a natural small molecule compound of the indole class. Due to its unique structure, low cost and easy availability, the use of isatin as a starting material to construct complex and diverse heterocyclic compounds has been a research hotspot in the field of organic synthesis. Since isatin possess rich reaction sites, it has a significant step advantage in converting it into similar heterocycles. In recent years, the great progress has been made in the construction of heterocyclic compounds based on domino reactions involving isatins. According to the different types of heterocycles, the research progress in the synthesis of benzoheterocyclic compounds by the domino reactions related to isatins is briefly discussed.

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“…Vieregge and co-workers were the first group to report catalytic CAM reactions in 1959, employing BF 3 as reaction promoter . From developments in the field in the past few decades, it has been established that the CAM reaction can be promoted through either the activation of the carbonyl moiety, which can be achieved by oxophilic Lewis acid (such as FeCl 3 , GaCl 3 , SbF 5 and triflate salts of Zn, Yb, In, and Sc) or Brønsted acid (pTSA, TfOH, TFA, and HBF 4 ) catalysis, or the activation of the alkyne moiety by employing π-electrophilic Lewis acid (such as AgSbF 6 , , AuCl 3 , or Pd-complexes) catalysis. , However, many of these reactions required harsh conditions or used high loadings of transition metal catalysts. Several catalytic systems are applicable to only one type of either intermolecular or intramolecular CAM reactions.…”

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confidence: 99%

Carbocation-Catalyzed Intramolecular and Intermolecular Carbonyl-Alkyne Metathesis Reactions

2023

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The carbonyl-alkyne metathesis (CAM) reaction is a versatile, stereoselective, and atom-economical method to access a diverse range of α,βunsaturated carbonyl compounds, which are useful synthetic precursors and constitute an important structural motif in biologically active substances. In this work, we developed an efficient organic Lewis acid catalytic system to promote both the intramolecular and intermolecular CAM reactions. This type of versatile catalytic activity has been rarely demonstrated for other established CAM catalysts. Our metal-free protocol was applied to a broad range of substrates to produce a diverse family of useful organic structures.

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Zinc-Catalyzed Alkyne–Carbonyl Metathesis of Ynamides with Isatins: Stereoselective Access to Fully Substituted Alkenes

Cited by 27 publications

References 83 publications

Oxophosphonium-alkyne cycloaddition reactions: reversible formation of 1,2-oxaphosphetes and six-membered phosphorus heterocycles

Oxophosphonium-alkyne cycloaddition reactions: reversible formation of 1,2-oxaphosphetes and six-membered phosphorus heterocycles

Recent Advances in the Synthesis of Benzoheterocyclic Compounds Involving Isatins

Carbocation-Catalyzed Intramolecular and Intermolecular Carbonyl-Alkyne Metathesis Reactions

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