Aerobic α-hydroxylation of β-keto esters and amides by co-catalysis of SmI3 and I2 under mild base-free conditions

Yu, Shun‐Ming; Cui, Kai; Lv, Fei; Yang, Zhen‐Yu; Yao, Zhu‐Jun

doi:10.1016/j.tetlet.2016.05.052

Cited by 15 publications

(6 citation statements)

References 45 publications

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“…For example, dicyclopropyl substituted diketene 8 derived from 7 reacted with amines to afford 9 in 81–98 % yields (Scheme 4b) [21] . For some aryl amines, external bases or catalysts like imidazole [22] and DMAP [23] or strong refluxing conditions are required [24] . The spiroepoxy‐ β ‐lactones 10 derived from 5 reacted with secondary amines to give 11 under mild conditions (Scheme 4c) [25] .…”

Section: Synthesis Of β‐Keto Amidesmentioning

confidence: 99%

“…Using air as the clean and green oxidant, Yao and co‐workers [23] reported a SmI 3 /I 2 co‐catalyzed hydroxylation of α ‐substituted β ‐keto amides 360 to yield 361 in >90 % yields under very mild conditions by (Scheme 72a). Nishiwaki and co‐workers [165] developed an α ‐oxidation of unsubstituted amides (R 4 = H) to α ‐hydroxy derivatives 362 by m ‐CPBA.…”

Section: Reactivities Of β‐Keto Amidesmentioning

confidence: 99%

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β‐Keto Amides: A Jack‐of‐All‐Trades Building Block in Organic Chemistry

Zheng

et al. 2021

Eur J Org Chem

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β‐Keto amides are a versatile class of compounds that find wide applications in organic chemistry owing to the juxtaposition of multiple reaction sites within their molecular structures. Due to the importance of β‐keto amides in modern organic chemistry, numerous novel preparation methods, synthetic applications and unprecedented reactivities have been recorded over the past decade. Taking advantage of transition‐metal‐catalysis and organocatalysis, β‐keto amides have emerged into a jack‐of‐all‐trades building block for many stereoselective or tandemized multicomponent reactions. But so far, no reviews have been documented on these recent achievements with β‐keto amides. Our Review aims to provide a thorough summary regarding: (a) the synthesis of β‐keto amides, (b) the reactivities of β‐keto amides, (c) the synthetic applications of β‐keto amides in various important heterocyclic compounds, and (d) the coordination of β‐keto amides with main group elements and transition metals and the relevant applications.

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Section: Synthesis Of β‐Keto Amidesmentioning

confidence: 99%

Section: Reactivities Of β‐Keto Amidesmentioning

confidence: 99%

β‐Keto Amides: A Jack‐of‐All‐Trades Building Block in Organic Chemistry

Zheng

et al. 2021

Eur J Org Chem

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“…It has been proved that the peroxide intermediate was formed during the aerobic hydroxylation of carbonyl compounds. [8,14] Generally,this intermediate is reduced efficiently by phosphine reductants such as P(OEt) 3 and PPh 3 . [7,9] Considering no phosphine reductant used but comparable yield obtained in this work, next, we focus on determining whether there is another species playing the role to reduce peroxide intermediates.…”

Section: Identifying the Reductant For Peroxide Intermediatesmentioning

confidence: 99%

1,5,7‐Triazabicyclo[4.4.0]dec‐5‐ene Enhances Activity of Peroxide Intermediates in Phosphine‐Free α‐Hydroxylation of Ketones

et al. 2021

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The critical role of double hydrogen bonds was addressed for the aerobic α‐hydroxylation of ketones catalyzed by 1,5,7‐triazabicyclo[4.4.0]dec‐5‐ene (TBD), in the absence of either a metal catalyst or phosphine reductant. Experimental and theoretical investigations were performed to study the mechanism. In addition to initiating the reaction by proton abstraction, a more important role of TBD was revealed, that is, to enhance the oxidizing ability of peroxide intermediates, allowing DMSO to be used rather than commonly used phosphine reductants. Further characterizations with nuclear Overhauser effect spectroscopy (NOESY) confirmed the presence of double hydrogen bonds between TBD and the ketone, and kinetic studies suggested the attack of dioxygen on the TBD‐enol adduct to be the rate‐determining step. This work should encourage the application of TBD as a catalyst for oxidations.

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“…described a transition‐metal free Cs 2 CO 3 ‐initiated α‐hydroxylation of carbonyl compounds with oxygen [3b] . Subsequently, Gnanaprakasam and co‐workers reported a transition‐metal free α‐hydroxylation of ketones and amides using KO‐ t ‐Bu and atmospheric air as oxidant [4c] . And Maulide et al.…”

Section: Introductionmentioning

confidence: 99%

Highly Efficient DMSO‐Promoted α‐Hydrolysis of α‐Halohydroxamates under Mild Conditions

Lee

Kim

2021

Eur J Org Chem

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A novel and efficient method for the nucleophilic α‐hydrolysis of α‐halohydroxamates with water under metal‐free conditions is described. In this reaction, the simple and readily available dimethyl sulfoxide (DMSO) was used as a catalyst, while water served as the nucleophile and oxygen source. This method was successfully employed in the synthesis of secondary α‐hydroxy‐α‐alkyl and α‐hydroxy‐α‐arylhydroxamates as well as tertiary α‐hydroxy‐α‐dialkylhydroxamates. Furthermore, the α‐hydrolysis of α‐halo‐α‐dialkylhydroxamates was achieved in the absence of the DMSO catalyst. This is a novel, mild, less toxic, and facile strategy for α‐hydroxylation of amides.

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Aerobic α-hydroxylation of β-keto esters and amides by co-catalysis of SmI3 and I2 under mild base-free conditions

Cited by 15 publications

References 45 publications

β‐Keto Amides: A Jack‐of‐All‐Trades Building Block in Organic Chemistry

β‐Keto Amides: A Jack‐of‐All‐Trades Building Block in Organic Chemistry

1,5,7‐Triazabicyclo[4.4.0]dec‐5‐ene Enhances Activity of Peroxide Intermediates in Phosphine‐Free α‐Hydroxylation of Ketones

Highly Efficient DMSO‐Promoted α‐Hydrolysis of α‐Halohydroxamates under Mild Conditions

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