ࡱ> ~q`LbjbjqPqP 4::````t `   $N h 9III   I I   A,~/`K : 0 0` P P P ," Y ` IIII FUNCTIONALIZATION OF THE BICYCLO[3.2.1]-OCTADIENE SKELETON VIA PHOTOCATALYTIC OXYGENATION OF A (BENZO)FURAN DERIVATIVE FUNKCIONALIZACIJA BICIKLO[3.2.1]OKTADIENA FOTOKATALITI KOM OKSIGENACIJOM (BENZO)FURANSKOG DERIVATA Dragana Vuk1, Ilijana Kikaa1, Ott Horvth2, Irena `kori1 1Department of Organic Chemistry, Faculty of Chemical Engineering and Technology, University of Zagreb, Maruliev trg 19, 10000 Zagreb, Croatia, iskoric@fkit.hr 2Department of General and Inorganic Chemistry, Institute of Chemistry, Faculty of Engineering, University of Pannonia, PO Box 158, Veszprm H-8201, Hungary, otto@vegic.uni-pannon.hu A simple and efficient protocol is utilized for the synthesis of novel functionalized benzobicyclo[3.2.1]octadiene derivatives by photocatalytic oxygenation of a furan derivative using an kationic and anionic free-base porphyrins as well as cationic and anionic manganese(III) porphyrins under different reaction conditions [1]. The course and yields of these reactions were compared to those of the thermal reaction using m-chloroperbenzoic acid as the oxidizing agent. The deviating reaction pathways with anionic and cationic metalloporphyrins may be attributed to simultaneous electronic and steric effects. Application of free-base and metalated watersoluble porphyrins for photocatalytic oxygenation of the furan ring fused to the rigid methano-bridged skeleton proved to be regioselective and flexible compared to the thermal reactions with mCPBA, giving at the same time novel potentially biologically active bicyclo[3.2.1]octenes with the basic skeleton of which is incorporated in many natural compounds. EMBED ChemDraw.Document.6.0 Annulation of a benzene to the outer side of the furan ring, however, led to the formation of only one type of product, independently of the photocatalyst used [2]. Different oxygenation mechanisms leading to the same end-product, the10-membered keto-lactone derivative, have been suggested for the metalloporphyrins and the corresponding free bases. Z   & ( * , . 0 p r hiʾtlt]]G+jhomCJOJQJU^JaJmH sH hom6CJ]aJmH sH homCJaJhomCJH*aJmH sH homCJaJmH sH  homH*homB*H*phhomB*phhomCJaJmH sH homB*H*mH phsH homB*mH phsH %hom5B*CJ\aJmH phsH hom5B*CJ\aJph%hom5B*CJ\aJmH phsH  , . p o p ghLgdom $7$8$H$a$gdom$'7$8$H$`'a$gdom$'7$8$H$`'a$gdom $7$8$H$a$gdomLisD>@JLռuf[WhVhom5CJ\aJhom5CJ\aJmH sH  *homB*CJaJphhomCJaJU *homCJaJmH sH homCJaJmH sH +jhomCJOJQJU^JaJmH sH 1jhmAhomCJOJQJU^JaJmH sH 1j4U homCJOJQJUV^JaJmH sH "homCJOJQJ^JaJmH sH [1] I. Kikaa, O. Horvth, I. `kori, Journal of Molecular Structure1034 (2013) 62-68. [2] I. Kikaa, O. Horvth, I. `kori, Tetrahedron Letters52(2011) 6255-6259. 21h:pD. A!"#$% Dd F0  # Abn&1|^4&zJDnB&1|^4&zPNG  IHDRH)sRGBPLTE                                       pHYsV IDATx^\ w7^7>`SJ! 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[!\! q!s!s! \!]! #! ]!^! s!t!t! ^!X! )!Yž *!k} &ChemDraw can't interpret this label.7&Yž #R)B%@&`' (`*cationic/anionic Mn(III)porphyrin or 1O2 (non-metalated porphyrin)"Ȫ;9twt"bJ 7u" 7v" [e%'c# `O"DoJi "R[` 7"Em 7"w 7"mt 7"}{S +7}[2P}2PぶeW# `O" t"u" """ u"v" " v"w" """" w"x" " x"y" """" t"y" " w"z" " {"|" " x"|" "" z"}" " }"~" " |"" " z"{" "" ~""" "" " ~"" " "" " "" """"" "" " "" """ "" " "" """ "" " ""$*F$! ^&ChemDraw can't interpret this label.L8hn, l > 380 nm" ? w     O#P# K! 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