A study of [2 + 2] cycloaddition–retroelectrocyclization in water: observation of substrate-driven transient-nanoreactor-induced new reactivity

Neethu, K M; Nag, Kritika; Dar, Arif Hassan; Bajaj, Ashima; Gopal, Arya; Gowri, Vijayendran; Nagpure, Mithilesh; Sartaliya, Shaifali; Sharma, Raina; Solanki, Arun Kumar; Ali, Md. Ehesan; Muthukrishnan, Azhagumuthu; Jayamurugan, Govindasamy

doi:10.1039/d3ob00053b

Cited by 5 publications

(2 citation statements)

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“…The reaction of 1 with TCNE in an aqueous medium containing a surfactant results in the formation of a 6,6-dicyano-heteropentafulvene derivative 37 as an additional byproduct along with the typical TCBD adduct 4 ( Scheme 14 ) [ 117 ]. The yields and formation ratios of 4 and 37 depend on the type and concentration of the surfactant employed.…”

Section: Reviewmentioning

confidence: 99%

Perspectives on push–pull chromophores derived from click-type [2 + 2] cycloaddition–retroelectrocyclization reactions of electron-rich alkynes and electron-deficient alkenes

Yamada

2024

Beilstein J. Org. Chem.

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Various push–pull chromophores can be synthesized in a single and atom-economical step through [2 + 2] cycloaddition–retroelectrocyclization (CA–RE) reactions involving diverse electron-rich alkynes and electron-deficient alkenes. In this review, a comprehensive investigation of the recent and noteworthy advancements in the research on push–pull chromophores prepared via the [2 + 2] CA–RE reaction is conducted. In particular, an overview of the physicochemical properties of the family of these compounds that have been investigated is provided to clarify their potential for future applications.

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Section: Reviewmentioning

confidence: 99%

Perspectives on push–pull chromophores derived from click-type [2 + 2] cycloaddition–retroelectrocyclization reactions of electron-rich alkynes and electron-deficient alkenes

Yamada

2024

Beilstein J. Org. Chem.

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“…Moreover, organic solvents have until very recently been used as reaction media rather than a benign solvent. Nevertheless, Jayamurugan and co‐workers [3] have recently reported how the reaction can actually be performed in water in the presence of surfactants, and under some conditions the TCBD product can be further transformed into a 4,6,6‐tricyanoamidopentafulvene upon subsequent reaction with water.…”

Section: Introductionmentioning

confidence: 99%

Clicking together Alkynes and Tetracyanoethylene

Nielsen

2023

ChemPhysChem

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The [2+2] cycloaddition – retro‐electrocyclization (CA‐RE) reaction allows ready synthesis of redox‐active donor‐acceptor chromophores from an electron‐rich alkyne and electron‐poor olefins like tetracyanoethylene (TCNE). The detailed mechanism of the reaction has been subject of both computational and experimental studies. While several studies point towards a stepwise mechanism via a zwitterionic intermediate for the first step, the cycloaddition, the reaction follows neither simple second‐order nor first‐order kinetics. Recent studies have shown that the kinetics can be understood if an autocatalytic step is introduced in the mechanism, in which complex formation with the donor‐substituted tetracyanobutadiene (TCBD) product possibly facilitates nucleophilic attack of the alkyne onto TCNE, generating the zwitterionic intermediate of the CA step. This Concept highlights the convenient use of the “click‐like” CA‐RE reaction to obtain elaborate donor‐acceptor chromophores and the recent mechanistic results.

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Yb(OTf)₃‐Catalyzed C=C Bond Cleavage‐Reassembly Enabling Bicyclization: Regioselective Synthesis of Heteroarylated Pentacyclic Indoles

Liu,

Zhu,

Liu

et al. 2024

Adv Synth Catal

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An Yb(OTf)3‐catalyzed [2+2] cycloaddition /retro‐electrocyclization (CA‐RE)/bicyclization of 1‐(2‐aminoarylaklynyl)‐naphthalen‐2‐ols and 3‐alkylideneoxindoles is reported, enabling a direct C=C bond cleavage‐reassembly process to regioselectively synthesize a variety of quinoline‐tethered benzo[5,6]chromeno[2,3‐b]indoles in 31–84% yields. Exchanging the amino group for a hydroxyl group in the arylalkynyl unit of the naphthalen‐2‐ol substrate resulted in chromenyl chromeno[2,3‐b]indoles via a similar cascade process.

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A study of [2 + 2] cycloaddition–retroelectrocyclization in water: observation of substrate-driven transient-nanoreactor-induced new reactivity

Abstract: Organic solvents limit [2+2] cycloaddition-retroelectrocyclization (CA–RE) in biological fields. We examined the formation of 1,1,4,4-tetracyanobuta-1,3-dienes (TCBDs) through CA–RE reactions and their unusual reactivity to produce N-heterocyclic compounds when surfactant nature...

Cited by 5 publications

References 39 publications

Perspectives on push–pull chromophores derived from click-type [2 + 2] cycloaddition–retroelectrocyclization reactions of electron-rich alkynes and electron-deficient alkenes

Perspectives on push–pull chromophores derived from click-type [2 + 2] cycloaddition–retroelectrocyclization reactions of electron-rich alkynes and electron-deficient alkenes

Clicking together Alkynes and Tetracyanoethylene

Yb(OTf)₃‐Catalyzed C=C Bond Cleavage‐Reassembly Enabling Bicyclization: Regioselective Synthesis of Heteroarylated Pentacyclic Indoles

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A study of [2 + 2] cycloaddition–retroelectrocyclization in water: observation of substrate-driven transient-nanoreactor-induced new reactivity

Abstract: Organic solvents limit [2+2] cycloaddition-retroelectrocyclization (CA–RE) in biological fields. We examined the formation of 1,1,4,4-tetracyanobuta-1,3-dienes (TCBDs) through CA–RE reactions and their unusual reactivity to produce N-heterocyclic compounds when surfactant nature...

Cited by 5 publications

References 39 publications

Perspectives on push–pull chromophores derived from click-type [2 + 2] cycloaddition–retroelectrocyclization reactions of electron-rich alkynes and electron-deficient alkenes

Perspectives on push–pull chromophores derived from click-type [2 + 2] cycloaddition–retroelectrocyclization reactions of electron-rich alkynes and electron-deficient alkenes

Clicking together Alkynes and Tetracyanoethylene

Yb(OTf)3‐Catalyzed C=C Bond Cleavage‐Reassembly Enabling Bicyclization: Regioselective Synthesis of Heteroarylated Pentacyclic Indoles

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Yb(OTf)₃‐Catalyzed C=C Bond Cleavage‐Reassembly Enabling Bicyclization: Regioselective Synthesis of Heteroarylated Pentacyclic Indoles