Synthesis of hydroxyl-containing oxindoles and 3,4-dihydroquinolin-2-ones through oxone-mediated cascade arylhydroxylation of activated alkenes

Zhang, Ming‐Zhong; Liu, Long; Gou, Quan; Wang, Qi; Li, Yang; Li, Wanting; Luo, Fengjian; Yuan, Min; Chen, Tieqiao; He, Wei‐Min

doi:10.1039/d0gc02205e

Cited by 25 publications

(14 citation statements)

References 59 publications

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“…[17d] Our group reported an intra-molecular trans-arylhydroxylation of tertiary α,β-unsaturated amides for the synthesis of hydroxyl-containing oxindoles and 3,4-dihydroquinolin-2-ones (Scheme 1C, a). [18] A two-step one-pot intermolecular hydroxyazidation of α,β-unsaturated amides was also reported by Ohshima, Shibasaki and co-workers in 2005 (Scheme 1C, b). [19] Inspired by these works, we envisaged that the direct trans-dihydroxylation of α,β-unsaturated amides might be realized through in situ generation of epoxides under suitable reaction conditions.…”

Section: Introductionsupporting

confidence: 56%

Metal‐Catalyst‐Free One‐Pot Aqueous Synthesis of trans‐1,2‐Diols from Electron‐Deficient α,β‐Unsaturated Amides via Epoxidation Using Oxone as a Dual Role Reagent

et al. 2023

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In organic synthesis, incorporating two functional groups into the carbon-carbon double bond of α,β-unsaturated amides is challenging due to the electron-deficient nature of the olefin moiety. Although a few examples of dihydroxylation of α,βunsaturated amides have been demonstrated, producing cis-1,2-diols using either highly toxic OsO 4 or other specialized metal reagents in organic solvents, they are limited to several specific amides. We describe herein a general and one-pot direct synthesis of trans-1,2-diols from electron-deficient α,βunsaturated amides through dihydroxylation using oxone as a dual-role reagent in water. This reaction does not require any metal catalyst and produces non-hazardous and nontoxic K 2 SO 4 as the sole byproduct. Moreover, epoxidation products could also be selectively formed by adjusting the reaction conditions. By the strategy, the intermediates of Mcl-1 inhibitor and antiallergic bioactive molecule can be synthesized in one pot. The gram-scale synthesis of trans-1,2-diol which is isolated and purified by recrystallization further shows the potential applications of this new reaction in organic synthesis.

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Section: Introductionsupporting

confidence: 56%

Metal‐Catalyst‐Free One‐Pot Aqueous Synthesis of trans‐1,2‐Diols from Electron‐Deficient α,β‐Unsaturated Amides via Epoxidation Using Oxone as a Dual Role Reagent

et al. 2023

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“…15 Also, some strategies include domino Heck/borylation (Scheme 1a) 16 and aminooxyarylation of N -arylacrylamides (Scheme 1a), 17 which give intermediates that require one more step and a longer reaction time to obtain the desired products. Recently, He et al reported oxone-mediated arylhydroxylation of N -arylacrylamides (Scheme 1a), 18 but it suffers from regioselectivity. In this context, we are developing commercially viable and transition metal-free protocols using a green reagent “rongalite” in the presence of a mild base.…”

Section: Introductionmentioning

confidence: 99%

Transition metal-free functionalization of 2-oxindolesviasequential aldol and reductive aldol reactions using rongalite as a C1 reagent

et al. 2022

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“…Among these reactions, the arylhydroxylation of alkenes that introduce vital aryl and hydroxyl groups across the double bonds has attracted considerable interest. In contrast with intramolecular arylhydroxylation, intermolecular arylhydroxylation of alkenes to afford β-arylethylalcohol-based acyclic molecules is still a particularly difficult challenge because of the issues with regiocontrol.…”

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confidence: 99%

Directed Nickel-Catalyzed Selective Arylhydroxylation of Unactivated Alkenes under Air

et al. 2023

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An expeditious and novel nickel-catalyzed selective arylhydroxylation of unactivated alkenes with arylboronic acids was developed. This protocol is compatible with β,γand γ,δ-alkene amides, including traditionally challenging internal alkenes, to provide important β-arylethylalcohol scaffolds. The free hydroxyl group in the final product could be smoothly further transformed into other functional groups. Control experiments indicated that the oxygen atom of the hydroxyl group in the product is derived from the oxygen in the air.A s two of the most basic and abundant chemical bonds, carbon−carbon and carbon−oxygen bonds exist widely in nature. The carbooxygenation of alkenes represents a powerful and attractive synthetic tool for simultaneous formation of C(sp 3 )−C(sp/sp 2 /sp 3 ) and C(sp 3 )−O bonds in one sequence. 1 Among these reactions, the arylhydroxylation of alkenes that introduce vital aryl and hydroxyl groups across the double bonds has attracted considerable interest. In contrast with intramolecular arylhydroxylation, 2 intermolecular arylhydroxylation of alkenes to afford β-arylethylalcohol-based acyclic molecules is still a particularly difficult challenge because of the issues with regiocontrol.The β-arylethylalcohol motifs are commonly found in drugs, natural products, and biomacromolecules (Figure 1). 3 However, only a few examples have been reported to synthesize this important structure via arylhydroxylation of alkenes. In 2010, the Studer group reported for the first time a Mn(III)-mediated arylhydroxylation of electron-poor alkenes by using the strategy of oxidative radical addition of arylboronic acid to alkenes. 4 Later, utilizing the arylhydrazine or aryldiazonium salt as the arylation reagent, several examples of intermolecular Meerwein-type arylhydroxylation of conjugated alkenes via a radical pathway were successfully achieved by Ishibashi, 5 Jiao, 6 Heinrich, 7 Buchwald, 8 and Niu 9 independently (Scheme 1, eq 1). Nevertheless, the arylhydroxylation of unactivated alkenes has been impeded by their inherently low reactivity, complex side reactions, and

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Synthesis of hydroxyl-containing oxindoles and 3,4-dihydroquinolin-2-ones through oxone-mediated cascade arylhydroxylation of activated alkenes

Abstract: Hydroxyl-containing compounds are highly value-added organic molecules, and the establishment of novel methodologies for their elaboration is a long-standing challenge in organic synthesis. Here the first oxone-mediated direct arylhydroxylation of...

Cited by 25 publications

References 59 publications

Metal‐Catalyst‐Free One‐Pot Aqueous Synthesis of trans‐1,2‐Diols from Electron‐Deficient α,β‐Unsaturated Amides via Epoxidation Using Oxone as a Dual Role Reagent

Metal‐Catalyst‐Free One‐Pot Aqueous Synthesis of trans‐1,2‐Diols from Electron‐Deficient α,β‐Unsaturated Amides via Epoxidation Using Oxone as a Dual Role Reagent

Transition metal-free functionalization of 2-oxindolesviasequential aldol and reductive aldol reactions using rongalite as a C1 reagent

Directed Nickel-Catalyzed Selective Arylhydroxylation of Unactivated Alkenes under Air

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