Selenium abstraction from diethyl diselenide by tertiary phosphines

Cross, Ronald J.; Millington, Douglas

doi:10.1039/c39750000455

Cited by 10 publications

(5 citation statements)

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“…Similarly, it was known that analogous ditelluride species can be photolyzed to yield a mixture of the monotelluride and elemental tellurium. , Both S–S and C–S scission have also been demonstrated to occur during the photolysis of disulfides . In each case, the radical species produced from the photolysis of the dichalcogenide can be intercepted by tertiary phosphines to yield the corresponding phosphine chalcogenide. ,− …”

Section: Introductionmentioning

confidence: 88%

Diorganyl Dichalcogenides as Useful Synthons for Colloidal Semiconductor Nanocrystals

Brutchey

2015

Acc. Chem. Res.

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The ability to synthesize colloidal semiconductor nanocrystals in a well-controlled manner (i.e., with fine control over size, shape, size dispersion, and composition) has been mastered over the past 15 years. Much of this success stems from careful studies of precursor conversion and nanocrystal growth with respect to phosphine chalcogenide precursors for the synthesis of metal chalcogenide nanocrystals. Despite the high level of success that has been achieved with phosphine chalcogenides, there has been a longstanding interest in exploring alternate chalcogenide precursors because of issues associated with phosphine chalcogenide cost, purity, toxicity, etc. This has resulted in a large body of literature on the use of sulfur and selenium dissolved in octadecene or amines, thio- and selenoureas, and silyl chalcogenides as alternate chalcogenide precursors for metal chalcogenide nanocrystal synthesis. In this Account, emerging work on the use of diorganyl dichalcogenides (R-E-E-R, where E = S, Se, or Te and R = alkyl, allyl, benzyl, or aryl) as alternate chalcogenide precursors for the synthesis of metal chalcogenide nanocrystals is summarized. Among the benefits of these dichalcogenide synthons are the following: (i) they represent the first and only common precursor type that can function as chalcogen transfer reagents for each of the group VI elements (i.e., to make metal oxide, metal sulfide, metal selenide, and metal telluride nanocrystals); (ii) they possess relatively weak E-E bonds that can be readily cleaved under mild thermolytic or photolytic conditions; and (iii) the organic substituents can be tuned to affect the reactivity. These combined attributes have allowed dichalcogenide precursors to be employed for a wide range of metal chalcogenide nanocrystal syntheses, including those for In2S3, SnxGe1-xSe, SnTe, Cu2-xSySe1-y, ZnSe, CdS, CdSe, MoSe2, WSe2, BiSe, and CuFeS2. Interestingly, a number of metastable phases of compositionally complex semiconductors can be kinetically accessed through syntheses utilizing dichalcogenide precursors, likely as a result of their ability to convert at relatively low temperatures. These include the hexagonal wurtzite phases of CuInS2, CuInSe2, Cu2ZnSn(S1-xSex)4, and Cu2SnSe3 nanocrystals. The discovery of crystal phases on the nanoscale that do not exist in their bulk analogues is a developing area of nanocrystal chemistry, and dichalcogenides are proving to be a useful synthetic tool in this regard. The most recent application of dichalcogenide synthons for semiconductor nanocrystals is their use as precursors for surface ligands. While there is a rich history of using thiol ligands for semiconductor nanocrystals, the analogous selenol and tellurol ligands have not been studied, likely because of their oxidative instability. Dichalcogenides have proven useful in this regard, as they can be reduced in situ with diphenylphosphine to give the corresponding selenol or tellurol ligand that binds to the nanocrystal surface. This chemistry has been applied to the in situ sy...

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Section: Introductionmentioning

confidence: 88%

Diorganyl Dichalcogenides as Useful Synthons for Colloidal Semiconductor Nanocrystals

Brutchey

2015

Acc. Chem. Res.

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“…Following the pioneering work of Hoffmann and Walling on the desulfurization of thiols by phosphites, the deselenization of diselenides by phosphines has also been studied in detail. , In 1975, Cross and Millington reported the abstraction of selenium from diethyldiselenide by UV irradiation in the presence of diphenylmethylphosphine (Scheme ). The proposed free radical chain mechanism involves the light-induced formation of selenyl radicals from diethyldiselenide followed by their combination with the phosphine to produce [Ph 2 MePSeEt] • .…”

Section: Ncl Beyond Cys and Sec Junctionsmentioning

confidence: 99%

“…623,624 In 1975, Cross and Millington reported the abstraction of selenium from diethyldiselenide by UV irradiation in the presence of diphenylmethylphosphine (Scheme 73). 623 The proposed free radical chain mechanism involves the light-induced formation of selenyl radicals from diethyldiselenide followed by their combination with the phosphine to produce [Ph 2 MePSeEt] • . Decomposition of this phosphorus-centered radical yields the selenophosphine Ph 2 MeP = Se and the ethyl radical Et • .…”

Section: Short Range Acyl Transfers: Auxiliary-mediated Nclmentioning

confidence: 99%

Native Chemical Ligation and Extended Methods: Mechanisms, Catalysis, Scope, and Limitations

et al. 2019

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The native chemical ligation reaction (NCL) involves reacting a C-terminal peptide thioester with an N-terminal cysteinyl peptide to produce a native peptide bond between the two fragments. This reaction has considerably extended the size of polypeptides and proteins that can be produced by total synthesis and has also numerous applications in bioconjugation, polymer synthesis, material science, and micro-and nanotechnology research. The aim of the present review is to provide a thorough mechanistic overview of NCL and extended methods. The most relevant properties of peptide thioesters, Cys peptides, and common solvents, reagents, additives, and catalysts used for these ligations are presented. Mechanisms, selectivity and reactivity are, whenever possible, discussed through the insights of computational and physical chemistry studies. The inherent limitations of NCL are discussed with insights from the mechanistic standpoint. This review also presents a palette of O,S-, N,S-, or N,Se-acyl shift systems as thioester or selenoester surrogates and discusses the special molecular features that govern reactivity in each case. Finally, the various thiol-based auxiliaries and thiol or selenol amino acid surrogates that have been developed so far are discussed with a special focus on the mechanism of long-range N,S-acyl migrations and selective dechalcogenation reactions.

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“…However, a limitation of using trialkylphosphines for the reduction of alkyl selenosulfides is their propensity to deselenize the alkyl selenol component. [11][12][13][14] Our interest in the chemistry of selenosulfides comes from the recent discovery that N-(2selenoethyl)cysteine, in the form of its cyclic selenosulfide called SetCys, can be converted into cysteine residue (Cys) in the presence of TCEP (Fig. 1c).…”

Section: Mainmentioning

confidence: 99%

Thiol catalysis of selenosulfide bond cleavage by a triarylphosphine

Firstova

Melnyk

Diemer

2022

Preprint

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The arylthiol 4-mercaptophenylacetic acid (MPAA) is a powerful catalyst of selenosulfide bond reduction by the triarylphosphine 3,3′,3′′-phosphanetriyltris(benzenesulfonic acid) trisodium salt (TPPTS). Both reagents are water-soluble at neutral pH and are particularly adapted for working with unprotected peptidic substrates. Contrary to trialkylphosphines such as tris(2-carboxyethyl)phosphine hydrochloride (TCEP), TPPTS has the advantage of not inducing deselenization reactions. We believe that the work reported here will be of value for those manipulating selenosulfide bonds in peptidic or protein molecules.

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Selenium abstraction from diethyl diselenide by tertiary phosphines

Abstract: The photochemical deselenation of Et,Se, by Ph,MeP proceeds by an EtSe. radical chain mechanism to form Et,Se and Ph,MePSe in high yield.

Cited by 10 publications

References 0 publications

Diorganyl Dichalcogenides as Useful Synthons for Colloidal Semiconductor Nanocrystals

Diorganyl Dichalcogenides as Useful Synthons for Colloidal Semiconductor Nanocrystals

Native Chemical Ligation and Extended Methods: Mechanisms, Catalysis, Scope, and Limitations

Thiol catalysis of selenosulfide bond cleavage by a triarylphosphine

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