In 1836 the first organoselenium compound, diethyl selenide, was prepared by Löwig,1 and it was isolated in the pure form in 1869.2 Early selenium chemistry involved the synthesis of simple aliphatic compounds such as selenols (RSeH), selenides (RSeR), and diselenides (RSeSeR); however, because of their malodorous nature, these compounds were difficult to handle. This, combined with the instability of certain derivatives and difficulties in purification, meant that selenium chemistry was slow to develop. By the 1950s, the number of known selenium compounds had increased significantly, but it was not until the 1970s, when several new reactions leading to novel compounds with unusual properties were discovered, that selenium chemistry began to attract more general interest.3-9 Aryl-substituted compounds were synthesized that were found to be less volatile and more pleasant to handle than the earlier aliphatic compounds. Compounds containing selenium in high oxidation states are relatively easy to manipulate using modern techniques.4c Organoselenium chemistry has now become a well-established field of research, and recent advances have been brought about by the potential technical applications of selenium compounds. Today selenium compounds find application in many areas including organic synthesis,4 biochemistry,5 xerography,6 the synthesis of conducting materials7 and semiconductors,8 and ligand chemistry.4c,9 Many of these aspects of selenium chemistry are wellcovered elsewhere in the literature; however, the subject of hypervalency has not attracted much attention and is the focus of this review.10

Organoselenium chemistry: role of intramolecular interactions.

Chiral selenium compounds in organic synthesis

Reductive transformation of α,β-epoxy ketones and other compounds promoted through photoinduced electron transfer processes with 1,3-dimethyl-2-phenylbenzimidazoline (DMPBI)

The organoselenium-mediated reduction of α,β-epoxy ketones, α,β-epoxy esters, and their congeners to β-hydroxy carbonyl compounds: Novel methodologies for the synthesis of aldols and their analogues

A suitable oxidative system is crucial to electrophilic selenium catalysis (ESC) This short review offers the overview of recent development in ESC with electrophilic N-F reagents as the oxidants Several highly selective transformations of alkenes such as allylic or vinylic imidation, pyridination, syn-dichlorination, oxidative cyclization and asymmetric cyclization have been described

https://www.mdpi.com/1420-3049/22/5/835/pdf

Electrophilic Selenium Catalysis with Electrophilic N-F Reagents as the Oxidants.

A novel access to β-hydroxy carbonyl compounds from the corresponding α,β-epoxy carbonyl compounds has been attained through the recyclable use of diphenyl diselenide or diphenyl ditelluride as an electroreduction mediator in a MeOH-NaClO 4 -(Pt) system α,β-Epoxy ketones are converted to the corresponding aldols in the presence of malonic esters Similarly, α,β-epoxy esters and nitriles can be reduced to the corresponding β-hydroxy compounds in the presence of acetic acid

Electroreductive ring-opening of .alpha.,.beta.-epoxy carbonyl compounds and their homologs through recyclable use of diphenyl diselenide or diphenyl ditelluride as a mediator

1,5-Dicarbonyl compounds and their enol silyl ethers were prepared by the reaction of α,β-unsaturated ketones and enol silyl ethers or ketene silyl acetals by using an electrogenerated acid (EG acid) as a catalyst. Similar reaction of 1-trimethylsiloxy-1,3-butadiene with enones produced six-membered adducts as the result of a double-Michael process.

Electrogenerated acid-catalyzed Michael reaction of enol silyl ethers and ketene silyl acetals to α,β-unsaturated carbonyl compounds

The methanesulfonates of α-hydroxy esters were converted to the corresponding deoxygenated esters in 70–88% yields by the indirect electrolysis with diphenyl diselenide as a recyclable reagent in a divided cell. This deoxygenation method may involve the formation of α-phenylselenoester by replacement of α-methylsulfonyloxyl group with phenylselenide anion followed by capture of the α-phenylseleno group with phenylselenide anion.

Electroreductive Deoxygenation of Methanesulfonates of α-Hydroxy Esters via a Catalytic Selenation–Deselenation Sequence

Selective dehalogenation of 6,6-dibromopenicillanates by indirect electroreduction with diphenyl diselenide as a recyclable mediator

Indirect electroreductive transformations of α,β-epoxy carbonyl compounds 1 mediated by diphenyl diselenide ((PhSe)2) as a recyclable reagent to their β-hydroxy derivatives 2 in 80–90% yields were ...

Masahiko Kusumoto

Papers

Electroreductive ring-opening of .alpha.,.beta.-epoxy carbonyl compounds and their homologs through recyclable use of diphenyl diselenide or diphenyl ditelluride as a mediator

Electrogenerated acid-catalyzed Michael reaction of enol silyl ethers and ketene silyl acetals to α,β-unsaturated carbonyl compounds

Electroreductive Deoxygenation of Methanesulfonates of α-Hydroxy Esters via a Catalytic Selenation–Deselenation Sequence

Selective dehalogenation of 6,6-dibromopenicillanates by indirect electroreduction with diphenyl diselenide as a recyclable mediator

Indirect electroreduction of α,β-epoxy carbonyl compounds and their analogues by use of a (PhSe)2/sacrificial anode system