2,3-dioxabicyclo[2.2.2]oct-7-en-5-one: Synthesis and reactions of the keto endoperoxide of phenol

Adam, W
Balcı, Metin
Kilic, H
The photooxygenation of 1,4-cyclohexadiene (3) affords the diastereomeric hydroperoxy endoperoxides exo-4 and endo-4 and the diastereomeric hydroperoxides trans-5 and cis-5 in a ratio of 87: 9:3.5:0.5. Selective reduction of hydroperoxide group in the endoperoxides exo-4 and endo-4 in the presence of titanium tetraisopropoxide-diethyl sulfide gave the corresponding hydroxy endoperoxides exo-7 and endo-7, which on PCC oxidation leads to the phenol-derived keto endoperoxide 2. The triphenylphosphine deoxygenation of the keto endoperoxide 2 produces a 9:1 mixture of 1,2- and 1,4-dihydroxybenzenes 10 and 11, while the CoTPP-catalyzed rearrangement affords the bisepoxide 12, malealdehyde (13), and beta-lactone 14. The mechanisms of these transformations are presented.


A new method for the synthesis of stipitatic acid isomers: Photooxygenation of ethyl 6H-cyclohepta[d][1,3]dioxole-6-carboxylate
Dastan, A; Saracoglu, N; Balcı, Metin (2001-09-01)
Photooxygenation of the cycloheptatriene derivative 9 gave the bicyclic endoperoxide 14. Cleavage of the peroxide linkage in 14 with thiourea resulted in the formation of 16. Treatment of the endoperoxide 14 with a catalytic amount of triethylamine provided a new isomer of stipitatic acid 11, and 16. Pyrolysis or the CoTPP (TPP = tetraphenylporphyrin) catalyzed reaction of 14 resulted in the formation of iso-stipitatic acid 10, and 18,
A novel and short synthesis of (1,4/2)-cyclohex-5-ene-triol and its conversion to (+/-)-proto-quercitol
Gultekin, MS; Salamci, E; Balcı, Metin (2003-07-29)
(1,4/2)-Cyclohex-5-ene-triol was synthesized starting from cyclohexa-1,4-diene with two different approaches. Photooxygenation of cyclohexa-1,4-diene and epoxy-cyclohexene afforded anti-2,3-dioxabicyclo[2.2.2]oct-7-en-5-yl hydroperoxide and anti-7-oxabicclo[4.1.0]hept-4-en-3-yl hydroperoxide, respectively. Hydroperoxy endoperoxide was reduced with aqueous sodium bisulfite; hydroperoxy-epoxide with dimethylsulfide-titanium tetraisopropoxide to give 7-oxabicyclo[4.1.0]hept-4-en-3-ol. Acidic hydrolysis of the ...
Özkar, Saim (Elsevier BV, 1985-01-01)
The photochemical reaction of tricarbonyl-η6-1,3,5-cycloheptatriene-chromium(0) (I) with tricyclo[,7]undeca-3,5-diene (II) in n-pentane at 248 K yields the [4 + 6]-cycloadduct tricarbonyl-η6-pentacyclo[,15.02,8.03,7]octadeca-11,13,16-triene-chromium(0) (III). Detachment of the pentacyclic triene ligand from chromium can be achieved with trimethylphosphite. The constitutions of complex III and of the pentacyclic hydrocarbon IV were determined by spectroscopic means.
Addition of dibromocarbene to cyclobutene: characterisation and mechanism of formation of the products
Algi, Fatih; Hokelek, Tuncer; Balcı, Metin (2004-10-01)
Cyclobutene reacted with dibromocarbene in solution to give 1,5-dibromocyclopent-1-ene (9), 1,2,6, 6-tetrabromobicyclo[3.1.0]hexane (10), and 1,2,3,6-tetrabromocyclohex-1-ene (11), in a ratio of 1:4:8, respectively. Compounds 10 and 11 were found to be formed from a second carbene addition and rearrangement under the given reaction conditions.
2,1,3-Benzooxadiazole, thiophene and benzodithiophene based random copolymers for organic photovoltaics: Thiophene versus thieno[3,2-b]thiophene as pi-conjugated linkers
Göker, Seza; Hizalan, Gonul; Aktas, Ece; Kutkan, Seda; Çırpan, Ali; Toppare, Levent Kamil (2017-04-02)
Three conjugated random copolymers comprising benzodithiophene and thiophene as the donor units and benzooxadiazole as the acceptor unit, spaced with thiophene and thieno[3,2-b]thiophene π-bridges, were designed and synthesized. The effects of different linkers on the optical and electrochemical properties were investigated. The polymer containing a thieno[3,2-b]thiophene π-bridge revealed a red shifted absorption compared to its thiophene analogue. Morphological and photovoltaic properties of a polymer:ful...
Citation Formats
W. Adam, M. Balcı, and H. Kilic, “2,3-dioxabicyclo[2.2.2]oct-7-en-5-one: Synthesis and reactions of the keto endoperoxide of phenol,” JOURNAL OF ORGANIC CHEMISTRY, pp. 5926–5931, 2000, Accessed: 00, 2020. [Online]. Available: https://hdl.handle.net/11511/57841.