Eco‐Friendly Olefin Dihydroxylation Catalyzed by Diphenyl Diselenide

Santoro, Stefano; Santi, Claudio; Sabatini, Michela; Testaferri, Lorenzo; Tiecco, Marcello

doi:10.1002/adsc.200800571

Cited by 105 publications

(54 citation statements)

References 45 publications

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“…Previously, it was reported that similar reactions can be performed in a water/MeCN (3:1) mixture using 10% of diphenyl diselenide [55] or water using 2% of selenocysteine at room temperature ( Figure 14) [56]. The latter was slightly better in terms of stereoselectivity but considerably slower, probably as a consequence of the reduced loading of the catalyst.…”

Section: Water As An Alternative Medium For Organoselenium-catalyzed mentioning

confidence: 99%

“…Several aspects of this reaction can be highlighted as addressing the principles of Green Chemistry: (1) the aqueous medium allowed us to avoid organic solvents both as reaction medium and for purification procedures, (2) the use of a stoichiometric amount of hydrogen peroxide increases the atom economy and the safety of the process mainly for large-scale production, and (3) the possibility of recycling and reusing the catalyst and the medium at least five times without any further treatment allows a reduction of the waste produced from the synthesis and the workup. Previously, it was reported that similar reactions can be performed in a water/MeCN (3:1) mixture using 10% of diphenyl diselenide [55] or water using 2% of selenocysteine at room temperature ( Figure 14) [56]. The latter was slightly better in terms of stereoselectivity but considerably slower, probably as a consequence of the reduced loading of the catalyst.…”

Section: Water As An Alternative Medium For Organoselenium-catalyzed mentioning

confidence: 99%

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Water and Aqueous Mixtures as Convenient Alternative Media for Organoselenium Chemistry

et al. 2016

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Abstract:Even if water is the natural environment for bioorganic reactions, its use in organic chemistry is often severely limited by the high insolubility of the organic derivatives. In this review, we introduce some examples of the use of water to perform organoselenium chemistry. We mainly discuss the advantages of this medium when the recyclability is demonstrated and when the water can control the selectivity of a reaction or enhance the reaction rate.

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Section: Water As An Alternative Medium For Organoselenium-catalyzed mentioning

confidence: 99%

Section: Water As An Alternative Medium For Organoselenium-catalyzed mentioning

confidence: 99%

Water and Aqueous Mixtures as Convenient Alternative Media for Organoselenium Chemistry

et al. 2016

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“…Selenium-catalyzed epoxidations are already established, [22] but the combination with a subsequent ring-opening reaction leading to dihydroxylated products was developed recently. [23] The alkene is epoxidized by the perseleninic acid and the epoxide is opened by an S N 2-type reaction (Scheme 8). The stereocontrol in these reactions depends on the steric and electronic properties of the substrate.…”

Section: Cyclizations · Homogeneous Catalysis · Oxidation · Seleniummentioning

confidence: 99%

Green Chemistry with Selenium Reagents: Development of Efficient Catalytic Reactions

Freudendahl¹,

Santoro²,

Shahzad³

et al. 2009

Angew Chem Int Ed

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cyclizations · homogeneous catalysis · oxidation · seleniumApplications of selenium reagents in organic chemistry have developed rapidly over the past years, and comprehensive reviews on this area have appeared.[1] Rather new, however, is the use of selenium-based catalysts in organic synthesis. We highlight new developments in organoselenium catalysis and in particular the use of selenium electrophiles and organoselenium compounds in carbonylation reactions and the oxidation of alkenes and carbonyl compounds. The use of organoselenium ligands for metal-catalyzed processes is not covered here; the topic has been reviewed recently elsewhere.[1f] Also their potential as efficient mimetics for selenoenzymes will not be discussed. [2] In this Highlight we will focus on the catalytic use of selenium electrophiles for selenenylations and halogenations as well as the use of perseleninic acids as catalytic oxidants for various substrates.The use of electrophilic selenium reagents is a very versatile strategy for functionalizing alkenes 1. To avoid the use of stoichiometric amounts of selenium reagents, researchers have sought for analogous catalytic methods. Selenenylation-deselenenylation sequences involve two steps: the initial selenofunctionalization is followed by oxidation of the organoselenium moiety in 2, which allows the regeneration of the reagent through b elimination giving 3 or substitution to provide 4 (Scheme 1). Various reagents can be used to activate the selenide moiety in 2 to undergo elimination or substitution. The most explored approach involves oxidation with an excess of persulfate.[3] The oxidant is initially responsible for the generation of the electrophilic selenenylating agent from the corresponding diselenide and then for the oxidation of the selenium moiety in 2 allowing the regeneration of the catalyst. This approach proved to be useful for functionalizations such as hydroxylations, alkoxylations, and cyclizations, and when chiral nonracemic diselenides were used, interesting levels of stereoselectivity were reached. [3] Depending on the substrate 5, either an addition-elimination sequence to yield 6 or a cyclization-elimination sequence to give 7 is possible by using an electrochemical procedure (Scheme 2).[4] The reaction is initiated by anodic oxidation of bromide to bromine. The latter reacts with the diselenide to afford the arylselenenyl bromide, which promotes the selenofunctionalization. Subsequent elimination of the selenium moiety via a tetravalent selenium compound gives the products 6 or 7 and regenerates the arylselenenyl bromide. Alternatively, hypervalent iodine reagents such as [bis(trifluoroacetoxy)iodo]benzene can be used as oxidants, in combination with catalytic amounts (5 mol %) of diselenides, to effect the conversion of butenoic acids 5 (R = H) to the corresponding butenolides 7 in yields of up to 95 %.[5] In a diselenide-catalyzed dihydroxylation of alkenes with ammonium persulfate as the oxidant both nucleophiles are hydroxy groups and diols of type 4 (Nu = Nu' =...

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“…Another important synthetic transformation is the stereoselective dihydroxylation of olefins, which is well known for its cis stereoselectivity when performed with osmium tetraoxide409 and ruthenium tetraoxide 410. Recently, a complementary system for the trans ‐dihydroxylation with diphenyl diselenide as a catalyst was developed (Scheme ) 401. Hydrogen peroxide was employed as the oxidizing agent and gave water as the only side product.…”

Section: Catalysis By Means Of Biorelevant Metalsmentioning

confidence: 99%

Biorelevant Metals in Sustainable Metal Catalysis—A Survey

2013

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A growing world population and increasing energy demands are without a doubt the most important challenges for mankind within this century. Catalysis is a key technology in various fields of chemistry and offers the potential to increase the material output of chemical synthesis without an unreasonable increase in the energy necessary for the production of new materials. Hence, the various disciplines of catalysis are “sustainable” by definition. However, for a wide range of catalytic transformations to take the necessary next step from academic research to industrial application, the catalytic processes do not only have to be sustainable with regard to the substrate‐to‐product conversions, but they also have to be sustainable with regard to parameters such as solvent, energy source, and the nature of the catalyst. Currently, the vast majority of transition‐metal‐catalyzed homogenous reactions are based upon late and expensive transition‐metal complexes. In the present review we summarize the current state of the art in sustainable metal catalysis, that is, catalysis based upon inexpensive biorelevant metals such as Ca, Mg, V, Mo, Mn, Fe, Co, Ni, Cu, Zn, B, Si, and Se. These metals are part of nature’s catalytic toolbox and have experienced a tremendous comeback in metal catalysis within the past 10 years.

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Eco‐Friendly Olefin Dihydroxylation Catalyzed by Diphenyl Diselenide

Abstract: The first general and efficient diphenyl diselenide-catalyzed dihydroxylation of double bonds is presented. Hydrogen peroxide can be used as the oxidizing agent, affording generally good yields and high diasteroselectivity.

Cited by 105 publications

References 45 publications

Water and Aqueous Mixtures as Convenient Alternative Media for Organoselenium Chemistry

Water and Aqueous Mixtures as Convenient Alternative Media for Organoselenium Chemistry

Green Chemistry with Selenium Reagents: Development of Efficient Catalytic Reactions

Biorelevant Metals in Sustainable Metal Catalysis—A Survey

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