78872-19-2

Upstream product

• 71098-88-9 N-phenylselanylphthalimide 
• 97014-39-6 5-hexenyltributyltin 
• 33631-66-2 cyclopentylmethylmercury chloride 
• 1666-13-3 diphenyl diselenide 
• 78872-18-1 5-hexenyl phenyl selenide 
• 26841-80-5 bis(6-heptenoyl) peroxide 

Relevant academic research and scientific papers

Photosensitized electron transfer promoted reductive activation of carbon-selenium bonds to generate carbon-centered radicals: Application for unimolecular group transfer radical reactions

The investigation presented in this paper explores the mechanistic aspects and synthetic potentials of photosensitized electron transfer (PET) promoted reductive activation of organoselenium substrates. PET activation of substrates 1-5 is achieved through a photosystem comprised of light-absorbing 1,5-dimethoxynaphthalene (DMN) as electron donor and ascorbic acid as co-oxidant. The fluorescence quenching of 1DMN* by organoselenium compounds 1-5, correlation of fluorescence quenching rate constant with the reduction potentials of 1-5, and the dependence of photodissociation quantum yields of 1-5 on their concentration suggests the occurrence of electron-transfer (ET) processes between 1DMN* and 1-5. Steady state photolysis of organoselenium substrates (R2CHSePh) in the presence of 1DMN* and ascorbic acid leads to the cleavage of the -C-Se-bond to produce a carbon-centered radical and PhSe- species via the intermediacy of R2CH-SePh-.. The mechanistic interpretation for the reductive activation of -C-Se- bonds and the synthetic utility of observed cleavage pattern is extended for the unimolecular group transfer radical sequences.

Photosensitized One-electron Reductive Cleavage of a Carbon-Selenium Bond: a Novel Chemoselective Deselenenylation and Phenylselenenyl Group Transfer Radical Chain Reaction

A novel photosensitized one-electron reduction of organoselenium compounds leading to chemoselective deselenenylation and phenylselenyl group transfer radical chain processes is reported.

Cyclization of alkene-containing tetraalkylstannes

We have discovered a novel cyclization reaction, achieved through selective electrophilic cleavage of an organotin compound containing remote alkene functionality. The reaction has proven to be quite general with respect to a variety of substitution patte

Reaction of 5-hexenyltributyltin with pseudohalogens: cyclization vs. double bond addition

Reaction of 5-hexenyltributyltin with pseudohalogen electrophiles leads to either double bond addition products or cyclization products.When electrophiles containing non-nucleophilic counterions are used, predominately cyclization products are formed.

Reactions of Alkylmercurials with Heteroatom-Centered Acceptor Radicals

The relative reactivities of alkylmercury halides toward PhS., PhSe., or I. decrease drastically from R = tert-butyl to R = sec-alkyl to R = n-butyl, indicative that R. is formed in the rate-determining step in the attack of these radicals upon RHgCl.The alkyl radicals thus formed will enter into chain reactions in which a heteroatom-centered radical (A.) is regenerated from substrates such as RS-SR, ArSe-SeAr, ArTe-TeAr, PhSe-SO2Ar, Cl-SO2Ph; ZCH=CHA (A = Cl, I, SPh, SO2Ph); or PhCCHA (A = I, SPh, SO2Ph). β-Styrenyl (PhCH=CHA, Ph2C=CHA) and β-phenethynyl (PhCCA) systems with A = I, Br, SO2Ph also enter into chain reactions with mercury(II) salts with the ligands PhS, PhSe, PhSO2, or (EtO)2PO.The relative reactivities of a series of reagents toward t-Bu. and of PhCH=CHA, Ph2C=CHA, and PhCCA toward c-C6H11. are reported as well as the regioselectivity of t-Bu. attack observed for 1,2-disubstituted ethylenes (ZCH=CHA) with Z and A from the group Ph, Cl, Br, I, SO2Ph, SPh, Bu3Sn.Reactions of (E)- and (Z)-PhCH=CHI or MeO2CCH=CHI with t-Bu. or c-C6H11. occurred in a regioselective and stereospecific (retention) manner.Reactions of (E)- and (Z)-ClCH=CHCl occurred in a nonstereospecific manner in which the E/Z product ratio increased with the bulk of the attacking radical.A similar effect on the E/Z product ratios was observed for (Z)-MeO2CCH=CHCl.

SH2 Reactions of Diphenyl Diselenide; Preparation and Reactions of Bridgehead Selenides

For the SH2 process R* + PhSeSePh -> PhSeR + PhSe*, k = ca. 5 * 107 l mol-1 s-1 at 80 deg C in benzene when R is primary alkyl; with 1-adamantyl radicals this SH2 displacement affords a route to 1-adamantyl phenyl selenide which, on oxidation and pyrolysis of the resultant selenoxide, gives adamantan-1-ol; in contrast the selenoxide from bicyclononan-1-yl phenyl selenide decomposes via bicyclonon-1-ene.