Acyl azides: application to the synthesis of various heterocycles

Dengiz, Çağatay
Pyrazoles, isoindolinones, benzodizepinones and dihydroquinolinones are very important heterocycles for their biological properties. Many pharmaceutical agents include these units as core structures. Reactive molecules such as acyl azides, free radicals and formyl groups are used as key step reactants in these studies. Regiospesific hydrolysis and esterifications are used to reach target starting materials. Two different methodology are used for critical ring closure steps. Benzodiazepinones, and isoindolinones are obtained by base mediated ring closure reactions whereas thionyl chloride mediated procedure is used for dihydroquinolinones. Moreover, chloroacetonylation of the double bonds is also examined. Addition of acetylacetone to various alkenes was performed with in the presence of Mn(OAc)3 and HCl. Removal of one of the acetyl groups with ammonia under very mild conditions provided compounds derived from chloroacetonylation of the double bonds.


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
Design and synthesis of functional molecular squares
Akpınar, Handan; Akkaya, Engin Umut; Department of Chemistry (2006)
Self-assembly has big importance in synthesizing supramolecular structures. Highly fluorescent molecular squares with boradiazaindacene (BODIPY) building blocks were obtained via usage of metal driven self-asembly. The boradiazaindacene units were connected with the Pd(II) complex unit enforcing a near-90 degree angle between the building blocks. Thus, we believe we have the first example of BODIPY carrying fluorescent squares. With collective experience in BODIPY chemistry in our group, we may have the fir...
Chemoenzymatic synthesis of chiral hydroxymethyl cycloalkenols
Şenocak, Deniz; Demir, Ayhan Sıtkı; Department of Chemistry (2004)
Chiral cyclic alkenols with hydroxymethyl functionality are important structural units in many biologically active natural compouds such as prostaglandins, sesquiterpene antiviral agents, pentenomycins, xanthocidin, sarkomycin, etc. 1,3-cycloalkanediones are converted into bicyclic polyoxo derivatives with formaldehyde and trioxane in the presence of Lewis acid. Selective oxidation of the bicyclic compounds by using manganese(III)acetate followed by enzyme-catalyzed kinetic resolution afforded chiral bicycl...
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...
Darzens Reaction of Acyl Phosphonates with alpha-Bromo Ketones: Selective Synthesis of cis- and trans-Epoxyphosphonates
Demir, Ayhan Sıtkı; Emrullahoglu, Mustafa; Pirkin, Eser; Akca, Nazmiye (American Chemical Society (ACS), 2008-11-21)
Acyl phosphonates with alpha-halo ketones in the presence of bases at room temperature afford cis- and trans-epoxyphosphonates in good chemical yields and high selectivities using different bases. The diastereoselectivity of this reaction is easily controlled by changing the base. Changing the base from CS(2)CO(3) to DBU changed the diastereomeric ratio (trans/cis) from 3/2 to 9/1. Moreover, the treatment of the trans isomer with DBU showed a complete conversion to the corresponding cis isomer.
Citation Formats
Ç. Dengiz, “Acyl azides: application to the synthesis of various heterocycles ,” M.S. - Master of Science, Middle East Technical University, 2011.