Palladium-catalyzed formation of oxazolidinones from biscarbamates: a mechanistic study

Download

10.3762:bjoc.7.33.pdf

Date

2011-2-24

Author

Kilbas, Benan
Balci, Metin

Metadata

Show full item record

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

Item Usage Stats

112
views

68
downloads

Oxazolidinones can be synthesized starting from cyclic biscarbamates via a palladium-catalyzed reaction. To test the proposed mechanism of this reaction, first, bicyclonorcarene endoperoxides derived from cyano and carbomethoxy cycloheptatrienes were synthesized and converted into the corresponding diols. The reaction of diols with toluenesulfonyl isocyanate followed by a palladium catalyzed reaction furnished oxazolidinone derivatives in similar yields. It was shown that, if one face of the double bond is blocked by substituents such as H or CN, the reaction also takes place. On the basis of these results, it was assumed that an antiperiplanar orientation of the metal and nucleophile is not necessary to form oxazolidinones. The metal is probably bonded to the allylic system from the same face as the nucleophile.

Subject Keywords

Organic Chemistry, Bicyclic endoperoxides, Biscarbamates, Oxazolidinone, Pd-catalyzed allylic reaction, Singlet oxygen

URI

https://hdl.handle.net/11511/50975

Journal

Beilstein Journal of Organic Chemistry

DOI

https://doi.org/10.3762/bjoc.7.33

Collections

Department of Chemistry, Article

Suggestions

OpenMETU
Core

Naphthazarin-Polycyclic Conjugated Hydrocarbons and Iptycenes Dengiz, Çağatay; GUTIERREZ, Gregory D.; SWAGER, Timothy M. (American Chemical Society (ACS), 2017-07-21) The synthesis of a set of naphthazarin-containing polycyclic conjugated hydrocarbons is described herein. Sequential Diels-Alder reactions on a tautomerized naphthazarin core were employed to access the final conjugated systems. Complete conjugation across the backbone can be achieved through complexation with BF2, as observed by (HNMR)-H-1 analysis and UV/vis spectroscopy. Precise synthetic control over the degree of oxidation of naphthazarin quinone Diels-Alder adduct 10 is additionally demonstrated and e...
Fam-zinc catalyzed asymmetric 1,3-dipolar cycloaddition reactions of azomethine ylides and Koyuncu, Hasan; Doğan, Özdemir; Department of Chemistry (2007) In the first part of this study, four new chiral ligands (FAM) were synthesized and used in catalytic amounts in asymmetric 1,3-dipolar cycloaddition reactions of azomethine ylides. This method leads to the synthesis of chiral pyrrolidines, which are found in the structure of many biologically active natural compounds and drugs. It was found that using 10 mol% of one of these chiral ligands with different dipolarophiles (dimethyl maleate, dimethyl fumarate, methyl acrylate, tert-butyl acrylate, and Nmethylm...
Transition structures, energetics, and nucleus-independent chemical shifts for divinylcyclobutene-to-cyclooctatriene rearrangement: A DFT study Zora, Metin (American Chemical Society (ACS), 2004-02-06) The minimum energy reaction paths and nucleus-independent chemical shifts (NICS) for the Cope rearrangement of cis-3,4-divinylcyclobutene, obtained by (U)B3LYP/6-31G* calculations, are reported. Three transition structures (endo-boatlike, chairlike, and exo-boatlike) have been located, giving rise to formation of cis,cis,cis-, cis,cis,trans-, and trans,cis, trans- 1, 3,5-cyclooctatrienes, respectively. The minimum energy path proceeds through an endo-boatlike, aromatic transition structure. The reaction pat...
Enantioselective Michael Addition of Nitroalkanes to Nitroalkenes Catalyzed by Chiral Bifunctional Quinine-Based Squaramides Kanberoğlu, Esra; Tanyeli, Cihangir (Wiley, 2015-10-26) A family of chiral bifunctional acid-/base-type quinine/squaramide organocatalysts is shown to be highly active promoters of the conjugate addition of 1-nitropropane to various trans-β-nitroalkenes. The cooperation of the quinine and the sterically encumbered squaramide moieties catalyzed the Michael addition reactions at 0 °C by using a catalyst loading of only 2 mol % to afford the 1,3-dinitro Michael adducts with excellent enantioselectivity and diastereoselectivity (up to 95 % ee and syn/anti isomers
Manganese(iii)acetate-based free-radical additions of -dicarbonyl compounds to bicyclic systems Fedalla, Mohammad Ali; Balcı, Metin; Department of Chemistry (2007) Additions of carbon-centered radicals to alkenes are useful method for cyclic compounds formation. Manganese(III)-based oxidative free-radical cyclizations, where the radicals are generated and terminated oxidatively, are established as efficient methods for the construction of cyclic molecule. Treatment of a mixture of dimedone, Mn(OAc)3, and Cu(OAc)2 in glacial acetic acid with homobenzonorbornadiene (80) (4h at 50 C) gave furan derivative (107), dihydrofuran adduct (108), in addition to rearranged produc...

Citation Formats

B. Kilbas and M. Balci, “Palladium-catalyzed formation of oxazolidinones from biscarbamates: a mechanistic study,” Beilstein Journal of Organic Chemistry, pp. 246–253, 2011, Accessed: 00, 2020. [Online]. Available: https://hdl.handle.net/11511/50975.