The Grieco elimination is an

organic reaction Organic reactions are chemical reactions involving organic compounds. The basic organic chemistry reaction types are addition reactions, elimination reactions, substitution reactions, pericyclic reactions, rearrangement reactions, Mechanistic Organ ...

describing the

elimination reaction An elimination reaction is a type of organic reaction in which two substituents are removed from a molecule in either a one- or two-step mechanism. The one-step mechanism is known as the E2 reaction, and the two-step mechanism is known as the E1 ...

of an aliphatic

primary alcohol A primary alcohol is an alcohol in which the hydroxy group is bonded to a primary carbon atom. It can also be defined as a molecule containing a “–CH2OH” group. In contrast, a secondary alcohol has a formula “–CHROH” and a tertiary ...

through a

selenide A selenide is a chemical compound containing a selenium anion with oxidation number of −2 (Se2−), much as sulfur does in a sulfide. The chemistry of the selenides and sulfides is similar. Similar to sulfide, in aqueous solution, the selenide ion ...

to a terminal

alkene In organic chemistry, an alkene is a hydrocarbon containing a carbon–carbon double bond. Alkene is often used as synonym of olefin, that is, any hydrocarbon containing one or more double bonds.H. Stephen Stoker (2015): General, Organic, an ...

. It is named for

Paul Grieco Paul Grieco is an organic chemist at Montana State University. His research focuses on the total synthesis of natural products and the study of solvent effects in various organic reactions. He has received several awards for his work, including t ...

. The alcohol first reacts with ''o''-nitrophenylselenocyanate and

tributylphosphine Tributylphosphine is the organophosphorus compound with the formula P(CH). Abbreviated or PBu, it is a tertiary phosphine. It is an oily liquid at room temperature, with a nauseating odor. It reacts slowly with atmospheric oxygen, and rapidly with ...

to form a

via a

nucleophilic substitution In chemistry, a nucleophilic substitution is a class of chemical reactions in which an electron-rich chemical species (known as a nucleophile) replaces a functional group within another electron-deficient molecule (known as the electrophile). The ...

on the electron-deficient

selenium Selenium is a chemical element with the symbol Se and atomic number 34. It is a nonmetal (more rarely considered a metalloid) with properties that are intermediate between the elements above and below in the periodic table, sulfur and tellurium, ...

. In the second step, the selenide is oxidized with

hydrogen peroxide Hydrogen peroxide is a chemical compound with the formula . In its pure form, it is a very pale blue liquid that is slightly more viscous than water. It is used as an oxidizer, bleaching agent, and antiseptic, usually as a dilute solution (3%� ...

to give a

selenoxide Organoselenium compounds (or seleno-organic) are chemical compounds containing carbon-to-selenium chemical bonds. Organoselenium chemistry is the corresponding science exploring their properties and reactivity. Selenium belongs with oxygen and sulf ...

. This structure decomposes to form an alkene by an E_i elimination mechanism with expulsion of a

selenol Selenols are organic compounds that contain the functional group with the connectivity C–Selenium, Se–H. Selenols are sometimes also called selenomercaptans and selenothiols. Selenols are one of the principal classes of organoselenium compound ...

in a fashion similar to that of the

Cope elimination The Cope reaction or Cope elimination, developed by Arthur C. Cope, is an elimination reaction of the N-oxide to form an alkene and a hydroxylamine. Mechanism and applications The reaction mechanism involves an intramolecular 5-membered cyclic tr ...

. This reaction takes part in the synthesis of ring C of the Danishefsky Taxol synthesis.

References

* ''Organoselenium chemistry. A facile one-step synthesis of alkyl aryl selenides from alcohols'' Paul A. Grieco, Sydney Gilman, Mugio Nishizawa;

J. Org. Chem. ''The Journal of Organic Chemistry'', colloquially known as ''JOC'', is a peer-reviewed scientific journal for original contributions of fundamental research in all branches of theory and practice in organic and bioorganic chemistry. It is publ ...

; 1976; 41(8); 1485-1486. * ''Olefin synthesis. Rate enhancement of the elimination of alkyl aryl selenoxides by electron-withdrawing substituents'' K. Barry Sharpless and Michael W. Young

; 1975; ; 947 - 949. {{DEFAULTSORT:Grieco Elimination Elimination reactions Olefination reactions Name reactions