HFIP‐Mediated Decarboxylative [4+3]‐Annulation of Azaoxyallyl Cations with Isatoic Anhydride

Kim, Eun Jin; Lee, Chang Yoon; Kim, Sung‐Gon

doi:10.1002/adsc.202000439

Cited by 24 publications

(19 citation statements)

References 66 publications

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“…Isatoic anhydride undergo a decarboxylative [4 + 3] annulation with aza-oxyallyl anions to provide 1,4-benzodiazepines (Scheme ). This reaction required elevated temperatures and HFIP as an additive to attain the desired 1,4-benzodiazepine products. No product was observed in the absence of HFIP, whereas conducting the reaction at ambient temperature provided α-substituted amino ester.…”

Section: Pericyclic Reactionsmentioning

confidence: 99%

HFIP in Organic Synthesis

et al. 2022

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1,1,1,3,3,3-Hexafluoroisopropanol (HFIP) is a polar, strongly hydrogen bond-donating solvent that has found numerous uses in organic synthesis due to its ability to stabilize ionic species, transfer protons, and engage in a range of other intermolecular interactions. The use of this solvent has exponentially increased in the past decade and has become a solvent of choice in some areas, such as C–H functionalization chemistry. In this review, following a brief history of HFIP in organic synthesis and an overview of its physical properties, literature examples of organic reactions using HFIP as a solvent or an additive are presented, emphasizing the effect of solvent of each reaction.

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Section: Pericyclic Reactionsmentioning

confidence: 99%

HFIP in Organic Synthesis

et al. 2022

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“…Recently, Feng and co‐workers developed the [4+3]‐cycloaddition of azaoxyallyl cations with anthranils for the construction of benzodiazepine derivatives [15f] . Several research groups, including ours, have developed synthetic routes for 1,4‐benzodiazepine‐3,5‐diones using the [4+3]‐cycloaddition of azaoxyallyl cations with isatoic anhydrides and anthranils [15a–c] . Saha's group, as well as our own, reported the [4+3]‐cycloaddition of azaoxyallyl cations with δ‐hydroxyl‐α,β‐unsaturated carbonyls, resulting in seven‐membered 1,4‐oxazepanes [15d,e] …”

Section: Figurementioning

confidence: 95%

Organocatalytic Enantioselective [4+3]‐Cycloadditions of Azaoxyallyl Cations with 2‐Aminophenyl Enones

et al. 2021

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The first organocatalytic asymmetric [4 + 3]-cycloaddition of 2-aminophenyl α,β-unsaturated carbonyls with in situ generated azaoxyallyl cations was developed, and enantioenriched functionalized seven-membered 1,4-benzodiazepine-3ones were obtained in good yields and with excellent enantioselectivities. This approach was also extended to the first asymmetric [4 + 3]-cycloaddition of δ-hydroxy α,β-unsaturated carbonyls, affording 1,4-oxazepanes in one step under mild conditions. Several of the novel adducts demonstrated promising bioactivity in the prevention of peripheral nerve degeneration.

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“…and CF 3 C 6 H 5 as a solvent (Scheme 31). [51a] The reaction involved the cascade reaction of decarboxylative addition of HFIP to isatoic anhydride then addition to aza‐oxyallyl cation at room temperature followed by intramolecular substitution at 80 °C to yield 1,4‐benzodiazepinediones. Notably, various substituents on benzene ring of 105 could be well tolerated; however, EDG substituted substrates afforded better yield than EWG substituted ones.…”

Section: Cycloaddition Reactions Involving Aza‐oxyallyl Cations As Th...mentioning

confidence: 99%

Aza‐oxyallyl Cations and Their Applications in (3+m) Cycloaddition Reactions

Deeksha

Singh

2022

Eur J Org Chem

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Aza‐oxyallyl cations, as proposed by Sheehan in the 1960s have garnered significant attention among the synthetic organic community, owing to their diverse reactivity profile for constructing N‐scaffolds of biological interest. During its initial growth, aza‐oxyallyl cations were used effectively as a 3‐unit synthon as 1,3 dipoles to create N‐heterocycles via cycloaddition reactions, wherein aza‐oxyallyl cation served as electrophilic counterpart. Recently, new variations of aza‐oxyallyl cations reactivity have been reported, including its usage as a 1,4 dipole in cycloaddition reactions, domino reactions, and the unique alkylating ability of heteroatoms. This review article provides an update of the recent developments in this area and the prevailing mechanistic insight.

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HFIP‐Mediated Decarboxylative [4+3]‐Annulation of Azaoxyallyl Cations with Isatoic Anhydride

Cited by 24 publications

References 66 publications

HFIP in Organic Synthesis

HFIP in Organic Synthesis

Organocatalytic Enantioselective [4+3]‐Cycloadditions of Azaoxyallyl Cations with 2‐Aminophenyl Enones

Aza‐oxyallyl Cations and Their Applications in (3+m) Cycloaddition Reactions

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