Mn(III)-based C-C bond formation: regioselective alpha '-allylation of various alpha,beta-unsaturated, alpha and beta-alkoxy alpha,beta-unsaturated ketones

Date

2005-08-22

Author

Tanyeli, Cihangir

Metadata

Show full item record

This work is licensed under a Creative Commons Attribution-NonCommercial-NoDerivatives 4.0 International License.

Item Usage Stats

106
views

0
downloads

The Manganese(III) -based regioselective alpha'-keto radical generation of unsaturated ketones is a versatile synthetic procedure with broad applicability. The generated alpha'-keto radical slowly creates a metal enolate in a solvent at reflux. The resultant metal enolate affords the corresponding alpha'-allylated alpha,beta-unsaturated ketones in good yields. This method is the first example of the metal mediated regioselective alpha'-allylation of alpha,beta-unsaturated ketones. The ketones that have alpha or beta-alkoxy groups also work efficiently.

Subject Keywords

Organic Chemistry, Biochemistry, Drug Discovery

URI

https://hdl.handle.net/11511/42893

Journal

TETRAHEDRON

DOI

https://doi.org/10.1016/j.tet.2005.06.031

Collections

Department of Chemistry, Article

Suggestions

OpenMETU
Core

Asymmetric aldol addition of alpha-azido ketones to ethyl pyruvate mediated by a cinchona-based bifunctional urea catalyst Okumus, Seda; Tanyeli, Cihangir; Demir, Ayhan Sıtkı (Elsevier BV, 2014-07-30) The first asymmetric synthesis of ethyl 4-aryl-3-azido-2-hydroxy-2-methyl-4-oxobutanoates via a cinchona organocatalyst induced aldol addition of alpha-azido ketones to ethyl pyruvate has been developed. The coupling reaction under optimized conditions was carried out to furnish tetrafunctionalized synthons with enantioselectivities of up to 91:9 and enriched diastereoselectivities of up to 95:5 (syn:anti).
Reinvestigation of the synthetic and mechanistic aspects of Mn(III) acetate mediated oxidation of enones Demir, Ayhan Sıtkı; Reis, O; Igdir, AC (Elsevier BV, 2004-04-05) Mn(OAc)(3) mediated alpha'-acetoxylation of alpha,beta-unsaturated enones is reinvestigated from a synthetic and mechanistic point of view and an improved procedure based on the use of acetic acid as a co-solvent is presented. Excellent results were obtained for a variety of structurally diverse and synthetically important enones under the optimized conditions.
Mn(III) acetate-mediated regioselective benzylation of various alpha,beta-unsaturated and beta-alkoxy-alpha,beta-unsaturated ketones Tanyeli, Cihangir (Elsevier BV, 2003-09-22) We describe herein the results of manganese(III) acetate mediated alpha'-benzylation of various a,p-unsaturated and beta-alkoxy-alpha,beta-unsaturated ketones in moderate yields.
Intermolecular heterocyclization of alkynones with 2-mercaptoacetaldehyde under metal-free conditions: synthesis of 2,3-disubstituted thiophenes Vatansever, Erol Can; Kilic, Kubra; Ozer, Merve Sinem; KOZA, GANİ; Menges, Nurettin; Balcı, Metin (Elsevier BV, 2015-09-30) A concise and regioselective approach for the synthesis of 2,3-disubstituted thiophene derivatives has been developed. The synthetic strategy relies on the reaction of an in situ generated 2-mercaptoacetaldehyde with various alkynones. Furthermore, we calculated the energy gap between the HOMO and the LUMO orbitals of all compounds and observed that the introduction of a strong electron-withdrawing group decreased the HOMO-LUMO energy gap.
Manganese(III) acetate based tandem oxidation of various α and β-alkoxy α,β-unsaturated ketones Tanyeli, Cihangir; Sezen, Bengü (Elsevier BV, 2002-12-09) We described the unusual results of manganese(III) acetate based tandem oxidation of various alpha and beta-alkoxy alpha,beta-unsaturated ketones to afford the corresponding alpha'-acetoxy-alpha'-phenyl substituted oxidation products in good yields. The tandem oxidation to monoacetoxylation ratio can be tuned by the amount of manganese(III) acetate.

Citation Formats

C. Tanyeli, “Mn(III)-based C-C bond formation: regioselective alpha ’-allylation of various alpha,beta-unsaturated, alpha and beta-alkoxy alpha,beta-unsaturated ketones,” TETRAHEDRON, pp. 8212–8217, 2005, Accessed: 00, 2020. [Online]. Available: https://hdl.handle.net/11511/42893.