Benzyne‐Induced Ring Opening Reactions of DABCO: Synthesis of 1,4‐Disubstituted Piperazines and Piperidines

Seo, Jeongseob; Kim, Daegeun; Ko, Haye Min

doi:10.1002/adsc.202000375

Cited by 14 publications

(8 citation statements)

References 28 publications

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“…Other than thiols, methyl acrylate, allyl acetate, methyl acetate, fluoride, and 2,4-pentanedione were all employed as nucleophiles in this transformation. Recently, they reported the same type of MCR by using nitrogen nucleophile as the third component . In 2017, Tian et al.…”

Section: Multicomponent Reactions (Mcrs)mentioning

confidence: 99%

“…Recently, they reported the same type of MCR by using nitrogen nucleophile as the third component. 596 In 2017, Tian et al achieved an aryne MCR with enantioenriched tertiary benzylic amines 8-88 and various nucleophiles, such as benzenethiol, thiolate, thiocarboxylic acid, sulfinic acid, sodium sulfinate, selenol, malononitrile, and azidosilane, furnishing structurally diverse benzylic compounds 8-89 in moderate to excellent yields (Scheme 137b). 597 An overall stereospecific nucleophilic substitution with inversion of the configuration and excellent retention of enantiopurity occurred via an S N 2 reaction pathway on the in situ generated ammonium salt.…”

Section: Isocyanide-triggered Mcrsmentioning

confidence: 99%

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o-Silylaryl Triflates: A Journey of Kobayashi Aryne Precursors

2021

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Arynes are among the most active organic intermediates and have found numerous applications in expeditious preparation of substituted arenes. In the past 20 years, chemists have witnessed a resurgence in aryne chemistry, which is mainly attributed by the extensive utilization of Kobayashi's method, a fluoride-induced removal of the TMS group with concomitant departure of its ortho OTf group on o-silylaryl triflates. Nowadays, o-silylaryl triflates are the most frequently employed aryne precursors. This review provides an overview of the history of Kobayashi's method, its methodological achievements, and its applications in the synthesis of natural products, bioactive molecules, and polycyclic aromatic hydrocarbons.

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Section: Multicomponent Reactions (Mcrs)mentioning

confidence: 99%

Section: Isocyanide-triggered Mcrsmentioning

confidence: 99%

o-Silylaryl Triflates: A Journey of Kobayashi Aryne Precursors

2021

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“…在该反应中, 1,4-二氮杂双环[2,2,2]辛烷可作为亲核试剂进攻芳炔生成 1,3-两性离子中间体, 随后与亲核试剂反应生成各种结构复杂的苯联哌嗪类衍生物, 其中硫醇、丙烯酸甲酯、乙酸烯丙酯、乙酸甲酯、氟化物和 2,4-戊二酮均可作为亲核试剂. 2020 年, 该课题组 [84] 接着报道了同类型的三组分反应. 两者反应历程类似, 唯一不同的是后者使用氮亲核试剂作为第三组分.…”

Section: Tmsunclassified

Recent Progress on Arylation with Aryne through Three-Component Reaction

Chen¹,

Yang²,

Li³

et al. 2023

Chinese Journal of Organic Chemistry

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The three component reaction has the advantages of simple operation and efficient reaction, in line with the principles of atomic economy and green environmental protection. At present, the arylation without transition metal catalyst is mainly divided into three types of as following: (1) the direct arylation, (2) the insertion of aryne into σ-bond or π-bond, and (3) the three-component reactions involving aryne. Compared with the direct arylation and the insertion of aryne into σ-bond or π-bond, the mechanism of three component reactions involving aryne is still unclear, and the published reviews are still lacking. In order to facilitate the scientific researchers to consult and understand the three-component reaction involved in aryne, the progresses in the three-component reaction involving aryne in recent years are reviewed. Keywords aryne; three component reaction; carbon and heteroatom; arylation 芳炔作为一类重要的反应活性中间体一直备受人们的关注, 其参与的反应为构建碳-碳键和碳-杂键提供了新的反应模式 [1][2][3][4][5][6] , 并且在天然产物、生物碱和药物中间体的合成中具有广泛的应用 [7] . 自 1983 年 Kobayashi 课题组 [8] 首次报道 2-(三甲基甲硅烷基)苯基三氟甲磺酸酯为苯炔前体, 在氟负离子作用下高效生成苯炔的方法以来(Scheme 1), 芳炔参与的芳基化反应推动了芳炔化学的快速发展.

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“…Considered in the beginning as lab curiosities and mechanistic probes, these fleeting species have been enjoying a renaissance in synthetic chemistry over the past two decades. , The breakthrough was the use of 2-(trimethylsilyl)aryl triflates to generate the strained triple bond systems by a fluoride-induced 1,2-elimination under mild and almost neutral reaction conditions . This invention by Kobayashi paved the way to a wide variety of different reactions, such as various types of cycloadditions, nucleophilic additions, σ-bond insertions, multicomponent reactions, and rearrangements . Common to all of them is that 1,2-bisfunctionalized arenes are obtained as products (Scheme ).…”

Section: Introductionmentioning

confidence: 99%

Phosphine-Catalyzed Aryne Oligomerization: Direct Access to α,ω-Bisfunctionalized Oligo(ortho-arylenes)

Bürger¹,

Ehrhardt²,

Barber

et al. 2021

J. Am. Chem. Soc.

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A phosphine-catalyzed oligomerization of arynes using selenocyanates was developed. The use of JohnPhos as a bulky phosphine is the key to accessing α,ω-bisfunctionalized oligo(ortho-arylenes) with RSe as the substituent at one terminus and CN as the substituent at the other. The in situ formation of R3PSeR′ cations, serving as sterically encumbered electrophiles, hinders the immediate reaction that affords the 1,2-bisfunctionalization product and instead opens a competitive pathway leading to oligomerization. Various optimized conditions for the predominant formation of dimers, but also for higher oligomers such as trimers and tetramers, were developed. Depending on the electronic properties of the electrophilic reaction partner, even compounds up to octamers were isolated. Optimization experiments revealed that a properly tuned phosphine as catalyst is of crucial importance. Mechanistic studies demonstrated that the cascade starts with the attack of cyanide; aryne insertion into n-mers leading to (n+1)-mers was ruled out.

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Benzyne‐Induced Ring Opening Reactions of DABCO: Synthesis of 1,4‐Disubstituted Piperazines and Piperidines

Cited by 14 publications

References 28 publications

o-Silylaryl Triflates: A Journey of Kobayashi Aryne Precursors

o-Silylaryl Triflates: A Journey of Kobayashi Aryne Precursors

Recent Progress on Arylation with Aryne through Three-Component Reaction

Phosphine-Catalyzed Aryne Oligomerization: Direct Access to α,ω-Bisfunctionalized Oligo(ortho-arylenes)

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