Recent Advances in the Application of SelectfluorTMF-TEDA-BF4 as a Versatile Mediator or Catalyst in Organic Synthesis

Stavber, Stojan

doi:10.3390/molecules16086432

Cited by 82 publications

(44 citation statements)

References 81 publications

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“…This reaction can be considered as an alternative to the regioselective oxidation of the exocyclic sulfur atom of ketene dithioacetal 1 with m‐ CPBA, even if Selectfluor is a much more expensive reagent. Anyway, Selectfluor was previously reported as a powerful oxidizing agent able to easily oxidize sulfur atoms, such as in thioglycosides, into their sulfinyl derivatives in a few minutes …”

Section: Resultsmentioning

confidence: 99%

Synthesis of 2‐Substituted Thioglycals from Carbohydrate‐Derived Ketene Dithioacetals

et al. 2020

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A novel strategy for the synthesis of 2-substituted thioglycals has been developed from a carbohydrate-derived ketene dithioacetal in a two-step sequence. The introduction of various electrophilic groups at the double bond of the ketene dithioacetal was achieved before the elimination of the thioalkyl group to yield 2-substituted thioglycals. Removal of the [a] G. Merieux, M. Buchotte, M. Muzard, R. Plantier-Royon the corresponding exo-glycals in the furanose series. Recently, trifluoromethylated six-membered thioglycals were prepared via a multi-step synthetic sequence with a regioselective [4+2]cycloaddition between a fluorinated dithiocarboxylate and 1acetoxybutadiene in the first step. [18] As carbohydrate-derived sulfonium compounds are known to be an interesting class of glycosidase inhibitors, [19] we were also interested in the alkylation at the sulfur atom of the C-2 substituted thioglycals leading to 6-membered ring unsaturated sulfonium compounds. Scheme 7. Synthesis of 2-substituted thioglycals 15 and 16. Scheme 8. Preparation of sulfonium compound 18 and 18′ from thioglycal 16.

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Section: Resultsmentioning

confidence: 99%

Synthesis of 2‐Substituted Thioglycals from Carbohydrate‐Derived Ketene Dithioacetals

et al. 2020

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“…However, to the best of our knowledge, this active radical species has never been applied in oxygen incorporation reactions. We envisioned that a combination of phenol and Selectfluor6 in the presence of O 2 may produce the superoxide species I and the fluorine radical II ,5, 7 then I might serve as an active O‐transfer agent for organic substrates in the presence of the fluorine radical. Based on this hypothesis, we herein present our recent discovery in the activation of dioxygen by a combined phenol/Selectfluor system and its application in the oxidation‐dimerization of alkynes to access 2‐ene‐1,4‐diones under metal‐free conditions (Scheme ).…”

Section: Methodsmentioning

confidence: 99%

Activation of Dioxygen in Air by a Phenol/Selectfluor System: An Application in the Oxidation‐Dimerization of Alkynes to 2‐Ene‐1,4‐diones

Zhang

Wang

et al. 2014

Asian J Org Chem

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Activation of dioxygen in air by a combined phenol/Selectfluor system has been revealed. This technique has been exploited to develop an approach to 2-ene-1,4-diones via an oxidation-dimerization of alkynes under metal-free conditions.Dioxygen is no doubt the most "green" oxidant as well as the ideal oxygen source due to its natural, inexpensive, and environmentally benign characteristics. [1] However, with its triplet ground state, dioxygen is not kinetically favored for use in the oxidation of organic substrates. [2] Thus, the activation of dioxygen becomes the crucial process in the direct utilization of dioxygen as the terminal oxidant and/or the oxygen source in organic synthesis. [1, 2] Over the past few decades, transition-metal-mediated dioxygen activation has witnessed rapid progress. [1] A range of transition metals including Pd, [1a, b, d-f, i] Cu, [1h, 3a, b] Fe, [2b] Ni, [3c] Mn, [3d-f] and Ag [3g] have been investigated for achieving this purpose. In sharp contrast, relatively little attention has been focused toward the activation of dioxygen by organic molecules, though they serve as more "green" dioxygen activators than transition metals, [4] which is especially important in the pharmaceutical discipline. In this regard, Tan and Wille [4a] reported that dioxygen activation by S-radicals enables the oxidative conversion of C C bonds into a-diketones, Alexanian and co-workers [4b,c] developed an intramolecular and an intermolecular dioxygenation of alkenes involving activation of dioxygen by hydroxamic acid derivatives, and recently, Lei and co-workers [4d] have reported that dioxygen activation by sulfinic acids enables aerobic oxysulfonylation of alkenes leading to secondary and tertiary b-hydroxysulfones. Despite increasing advances, [4] the

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“…ing a number of photocatalysts (Table 2, entries 9-11), we observed that {Ir[dF(CF 3 )ppy] 2 (dtbpy)}PF 6 gave a much higher yield at 52% compared with Ru(bpy) 3 Cl 2 . Finally, variation of the base to potassium hydroxide ( Table 2, entries [12][13][14] provided an increase of yield to 68%. Interestingly, we noticed a trace amount of a disulfenylated side product 18c when the iridium photocatalyst is used, suggesting that at some point the thiophenol reagent (or product sulfide) is oxidized and reacts with a second equivalent of thiophenol.…”

Section: Cluster Syn Lettmentioning

confidence: 98%

Photocatalytic Oxidative C–H Thiolation: Synthesis of Benzothiazoles and Sulfenylated Indoles

Dinh¹,

Nguyen²,

Aceves³

et al. 2019

Synlett

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We report studies on the photocatalytic formation of C–S bonds to form benzothiazoles via an intramolecular cyclization and sulfenylated indoles via an intermolecular reaction. Cyclic voltammetry (CV) and density functional theory studies suggest that benzothiazole formation proceeds via a mechanism that involves an electrophilic sulfur radical, while the indole sulfenylation likely proceeds via a nucleophilic sulfur radical adding into a radical cationic indole. These conditions were successfully extended to several thiobenzamides and indole substrates.

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Recent Advances in the Application of SelectfluorTMF-TEDA-BF4 as a Versatile Mediator or Catalyst in Organic Synthesis

Cited by 82 publications

References 81 publications

Synthesis of 2‐Substituted Thioglycals from Carbohydrate‐Derived Ketene Dithioacetals

Synthesis of 2‐Substituted Thioglycals from Carbohydrate‐Derived Ketene Dithioacetals

Activation of Dioxygen in Air by a Phenol/Selectfluor System: An Application in the Oxidation‐Dimerization of Alkynes to 2‐Ene‐1,4‐diones

Photocatalytic Oxidative C–H Thiolation: Synthesis of Benzothiazoles and Sulfenylated Indoles

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