Oxidation of Diphenyl Diselenide with 2,3-Dichloro-5,6-dicyanobenzoquinone (DDQ). A New Method for the Electrophilic Phenylselenenylation of Alkenes under Mild Conditions

Tiecco, Marcello; Testaferri, Lorenzo; Temperini, Andrea; Bagnoli, Luana; Marini, Francesca; Santi, Claudio

doi:10.1055/s-2001-18091

Cited by 41 publications

(12 citation statements)

References 4 publications

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“…In recent decades, great attention has been devoted to seeking suitable selenium sources, which can serve as reactive electrophilic intermediates to induce the generation of seleniranium ion I . From a conceptual point of view, two different strategies have been chosen: directly using electrophilic selenenylating agents, such as phenylselenenyl halides, phenyl selenocyanate, or N -phenylselenophthalimide, or preparing electrophilic selenium species in situ by the oxidation of diselenides through electrochemical processes or by the use of oxidants, such as Oxone, 2,3-dichloro-5,6-dicyanobenzoquinone (DDQ), hypervalent iodine reagent, ammonium persulfate, or m -chloroperbenzoic acid . Although they represent useful platforms for β-hydroxy selenides, the preparation and handling of toxic and moisture-sensitive selenylating agents, the necessity to perform the reactions in the presence of transition metals , and nonoptimal chemical yields narrow the practical applicability of these methods.…”

Section: Introductionmentioning

confidence: 99%

Iodosobenzene-Mediated Three-Component Selenofunctionalization of Olefins

Zhang

Wang

et al. 2021

J. Org. Chem.

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A three-component reaction of olefin, diselenide and water, alcohols, phenol, carboxylic acid, or amine by a commercially available hypervalent iodine(III) reagent, PhIO, was developed. This method provides access to a wide range of vicinally functionalized selenoderivatives under ambient conditions with mostly excellent yields and high diastereoselectivity. The developed reaction displays high levels of functional group compatibility and is suitable for the late-stage functionalization of styrenefunctionalized biomolecules. Preliminary investigations on the mechanism of the reaction are also presented.

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Section: Introductionmentioning

confidence: 99%

Iodosobenzene-Mediated Three-Component Selenofunctionalization of Olefins

Zhang

Wang

et al. 2021

J. Org. Chem.

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“…In these reactions, the electrophiles RSeCl and RSeBr can be obtained from the reaction of diselenides with SO 2 Cl 2 (or Cl 2 ) and Br 2 respectively, or are commercially available [63–65] . Alternatively, the electrophile can be prepared in situ by the oxidative cleavage of the Se–Se bond of diorganyl diselenides using stoichiometric or over‐stoichiometric amounts of several reagents, such as KBr/ m ‐CPBA, [66] [PhI(OAc) 2 ], [67,68] I 2 /DMSO, [69–70] (NH 4 ) 2 S 2 O 8 , [71,72] Oxone®, [73–76] 2,3‐dichloro‐5,6‐dicyanobenzoquinone (DDQ), [77] ceric ammonium nitrate (CAN), [78] SelectFluor®, [79,80] and transition metal (TM)‐based reagents [81–84] …”

Section: Introductionmentioning

confidence: 99%

Oxyselenocyclization of 2‐Allylphenols for the Synthesis of 2,3‐Dihydrobenzofuran Selenides

et al. 2021

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The reaction between Oxone® and various di(hetero)aryl or alkyl diselenides enables the formation of an electrophilic selenium species in situ capable to induce the oxyselenocyclization of 2‐allylphenols. This versatile and safe protocol was explored to combine two privileged scaffolds into the structure of products: the 2,3‐dihydrobenzofuran core and an organoselenium moiety. Fifteen 2‐[(organoselanyl)methyl]‐2,3‐dihydrobenzofurans were produced, broadening considerably the number of known examples of this hybrid compound. Moreover, preparation of sulfur and tellurium 2,3‐dihydrobenzofurans derivatives was also successfully demonstrated.

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“…Upon treatment with PhSeBr and AgSbF 6 under conditions similar to the cyclization (2 h at −90 °C, then 8 h at −80 °C), followed by addition of methanol, 14 yields the expected methoxyselenated compounds 15 and 16 in 41% and 27% yields, respectively. Similar products from allylbenzene have been observed under more standard selenoetherification conditions …”

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confidence: 99%

Seleniranium Ion-Triggered Reactions: New Aspects of Friedel−Crafts and N-Detosylative Cyclizations

Lim

RajanBabu

2009

Org. Lett.

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Seleniranium ions at low temperatures (-90 to -78 °C) will initiate effective Friedel-Carfts cyclization if a suitably placed arene is allowed to react even when the arene is unactivated. These intermediates generated from N-aryl-N-tosylamides, undergo a novel, surprisingly efficient, detosylative cyclization to form 5-or 6-membered nitrogen heterocycles. A debenzylation route is preferred if both benzyl and tosyl groups are present in the substrate.rajanbabu.1@osu.edu. Supporting InformationAvailable: Full experimental details of synthesis of substrates, cyclzation reactions, spectroscopic and chromatographic data for characterization of compounds. This material is available free of charge via the Internet at http://pubs.acs.org NIH Public Access Author ManuscriptOrg Lett. Author manuscript; available in PMC 2010 July 2. Published in final edited form as:Org Lett. Electrophilic cyclizations of alkenyl carboxylic acids, alcohols, amines, amides and functionalized dienes initiated by seleniranium ions have been broadly applied for the syntheses of diverse heterocyclic and carbocyclic compounds. 1 Intermolecular additions of carbon nucleophiles including electron-rich aromatic derivatives to seleniranium ions are also known and these reactions have been developed to a level that it is now possible to carry out highly diastereoselective additions, using enantiopure selenium reagents. 2 Even though mechanistically related intramolecular additions of carbon nucleophiles to putative seleniranium ion intermediates were among the earliest examples of selenium-induced cyclizations, 3 subsequent developments in this area have been sporadic. In one such rare example, Déziel in 1998 4 reported that 4-arylbutenes (1) with electron-rich aryl groups undergo competitive carbocyclization when the reaction is conducted in a mixture of CH 2 Cl 2 and methanol (Scheme 1). The major side product, the β-methoxyselenide, 4, is readily converted into the cyclic product 3 by protic or Lewis acids. Formation of the methoxylated product 4 cannot be avoided since in the absence of methanol the reaction gave poor yields. Yet another limitation of this potentially powerful Friedel-Crafts cyclization is that non-activated arenes (e. g., phenyl) do not participate in this reaction. 3j,4,5a While searching for a general route to 1-methylenetetralin and analogous heterocyclic compounds in connection with our asymmetric hydrovinylation approach to 2,3-pyrrolidinoindoles (Figure 1), we decided to revisit this area. We expected the alkene-forming elimination reaction to be more facile via a selenide as compared to an iodide 5 or sulfide 6 arising from alternate cyclizations, especially for the synthesis of the more sensitive N and O containing heterocycles. Several novel observations that were made during the course of these investigations form the basis of this paper.Our studies (Eq 1, 2; Table 1) started with cyclizations of two prototypical substrates, but-3-enyl 4-methoxyphenyl ether (5a) and N-phenyl-N-(but-3-enyl)-4-toluenesulfonam...

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Oxidation of Diphenyl Diselenide with 2,3-Dichloro-5,6-dicyanobenzoquinone (DDQ). A New Method for the Electrophilic Phenylselenenylation of Alkenes under Mild Conditions

Cited by 41 publications

References 4 publications

Iodosobenzene-Mediated Three-Component Selenofunctionalization of Olefins

Iodosobenzene-Mediated Three-Component Selenofunctionalization of Olefins

Oxyselenocyclization of 2‐Allylphenols for the Synthesis of 2,3‐Dihydrobenzofuran Selenides

Seleniranium Ion-Triggered Reactions: New Aspects of Friedel−Crafts and N-Detosylative Cyclizations

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