Grieco elimination

The Grieco elimination is an organic reaction describing the elimination reaction of an aliphatic primary alcohol through a selenide to a terminal alkene.^[1]^[2] It is named for Paul Grieco.

The alcohol first reacts with o-nitrophenylselenocyanate and tributylphosphine to form a selenide via a nucleophilic substitution on the electron-deficient selenium. In the second step, the selenide is oxidized with hydrogen peroxide to give a selenoxide. This structure decomposes to form an alkene by an E_i elimination mechanism with expulsion of a selenol in a fashion similar to that of the Cope elimination. This reaction takes part in the synthesis of ring C of the Danishefsky Taxol synthesis.

The elimination step is common with the Clive-Reich-Sharpless olefination that uses PhSeX as the selenium source.^[3]

References

^ Grieco, Paul A.; Gilman, Sydney; Nishizawa, Mugio (1976). "Organoselenium chemistry. A facile one-step synthesis of alkyl aryl selenides from alcohols". J. Org. Chem. 41 (8): 1485–1486. doi:10.1021/jo00870a052.
^ Sharpless, K. Barry; Young, Michael W. (1975). "Olefin synthesis. Rate enhancement of the elimination of alkyl aryl selenoxides by electron-withdrawing substituents". J. Org. Chem. 40 (7): 947–949. doi:10.1021/jo00895a030.
^ Hassner, A.; Namboothiri, I. (2011). Organic Syntheses Based on Name Reactions: A Practical Guide to Over 800 Transformations (3rd ed.). p. 91. ISBN 9780080966311.

Zdroj:https://en.wikipedia.org?pojem=Grieco_elimination
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[1] Grieco, Paul A.; Gilman, Sydney; Nishizawa, Mugio (1976). "Organoselenium chemistry. A facile one-step synthesis of alkyl aryl selenides from alcohols". J. Org. Chem. 41 (8): 1485–1486. doi:10.1021/jo00870a052.

[2] Sharpless, K. Barry; Young, Michael W. (1975). "Olefin synthesis. Rate enhancement of the elimination of alkyl aryl selenoxides by electron-withdrawing substituents". J. Org. Chem. 40 (7): 947–949. doi:10.1021/jo00895a030.

[3] Hassner, A.; Namboothiri, I. (2011). Organic Syntheses Based on Name Reactions: A Practical Guide to Over 800 Transformations (3rd ed.). p. 91. ISBN 9780080966311.

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v t e Alkenes
Alkenes	Ethene (C₂H₄) Propene (C₃H₆) Butene (C₄H₈) Pentene (C₅H₁₀) Hexene (C₆H₁₂) Heptene (C₇H₁₄) Octene (C₈H₁₆) Nonene (C₉H₁₈) Decene (C₁₀H₂₀)
Preparations	Dehydrohalogenation from haloalkane Dehydration reaction from alcohol Semihydrogenation from alkyne Bamford–Stevens reaction Barton–Kellogg reaction Boord olefin synthesis Chugaev elimination Cope reaction Corey–Winter olefin synthesis Grieco elimination Hofmann elimination Horner–Wadsworth–Emmons reaction Hydrazone iodination Julia olefination Kauffmann olefination McMurry reaction Peterson olefination Ramberg–Bäcklund reaction Shapiro reaction Takai olefination Wittig reaction Olefin metathesis Ene reaction Cope rearrangement
Reactions	Hydrogenation Halogenation Hydration Electrophilic addition Oxymercuration reaction Hydroboration Cyclopropanation Epoxidation Dihydroxylation Ozonolysis Hydrohalogenation Polymerization Diels–Alder reaction Wacker process Dehydrogenation Ene reaction Friedel-Crafts Alkylation