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Synthesis Directed Towards 8-Hydroxyphenanthridines Functionalized in the C-Ring

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Synthesis Directed Towards 8-Hydroxyphenanthridines Functionalized in the C-Ring Synthesis directed towards 8-hydroxyphenanthridines functionalized in the C-ring Aleksander Granum Dalevold Chemistry 60 study points DEPARTMENT OF CHEMISTRY Faculty of mathematics and natural sciences UNIVERSITETET I OSLO April / 2021 1 ACKNOWLEDGMENT To my supervisor, Professor Lise-Lotte Gundersen; thank you for making it possible to work in your research group and for all the guidance and help in this thesis. To Mathias Ryslett Lepsøe; thanks for the discussions, help and all the funny moment in the lab and office. Thanks to Frode Rise and Dirk Petersen for practical and theoretical knowledge and providing valuable NMR instrument time. Thanks to Osamu Sekiguchi for running the MS service for MS values on all my products. Finally, I will thank my family for always being there for me and giving me endless of support. Aleksander Granum Dalevold Oslo, April 2021 i ABSTRACT Microwave-mediated intramolecular Diels-Alder of furan (IMDAF) reactions were utilized to synthesize two 8-hydroxyphenanthridines (VII). Three more 8-hydroxyphenanthridines were given (VII, XV), synthesized by members of our group. All five were used for further functionalization. By O-alkylation, ten phenanthridines (X, XIII, XV) were synthesized, none previously reported in literature. Compound XVI oxidized when stored to compound XVII which were used for later synthesis. Acylation of VII (R1 = Cl, R2 = H) produced two new phenanthridinyl esters (XIV) while triflation of the same 8-hydroxyphenanthridine formed compound VIII. This compound was further used in a Suzuki coupling reaction with phenylboronic acid to produce compound IX. The O-allylated phenanthridines (X, XVII) were used in Claisen rearrangements. Five ortho substituted 8-hydroxyphenanthridines (XII) were produced and isolated, while four had complications. By analyzing the five isolated ortho substituted 8-hydroxyphenanthridines (XII), it turned out that they were selective towards ortho substitution in 7-position to the hydroxy group. ii Scheme i: Synthesis of 8-hydroxyphenanthridine derivatives presented in this thesis. iii TABLE OF CONTENT ACKNOWLEDGMENT ........................................................................................................................ i ABSTRACT ............................................................................................................................................ii TABLE OF CONTENT ........................................................................................................................ iv ABBREVIATIONS AND SYMBOLES ............................................................................................... vi 1. Introduction ....................................................................................................................................... 1 1.1 Phenanthridine alkaloids in nature, their biological activities, and their importance .......... 2 1.1.1 Naturally occurring phenanthridine alkaloids .................................................................. 2 1.1.2 Phenanthridine containing compounds currently used in medicine ................................ 3 1.1.3 Problem of drug resistance and phenanthridine-based drugs in the future ................... 4 1.2 Phenanthridine synthesis in other groups ................................................................................. 6 1.2.1 Biphenyl ring-closure reactions ........................................................................................... 7 1.2.2 C10a-C10b bond-forming reaction ..................................................................................... 9 1.2.3 Palladium-catalyzed cascade reactions ............................................................................... 9 1.2.4 Ring expansion and contraction reactions ....................................................................... 10 1.3 Chemistry of named reactions relevant for this work............................................................ 11 1.3.1 The Suzuki-Miyaura reaction ........................................................................................... 11 1.3.2 The Diels-Alder reaction .................................................................................................... 14 1.3.3 Intermolecular Diels-Alder reaction of furan (IMDAF) ................................................. 15 1.3.4 The Claisen rearrangement reaction ................................................................................ 16 1.4 Microwave synthesis .................................................................................................................. 17 1.5 Current and previous phenanthridine synthesis strategies in our group ............................. 18 1.5.1 IMDAF-based synthesis development .............................................................................. 18 1.5.2 Dihydrophenanthridine oxidation .................................................................................... 21 1.5.3 Phenanthridine-8-ol functionalization .............................................................................. 22 2. Results and discussion ..................................................................................................................... 23 2.1 Synthesis of 8-hydroxyphenanthridines .................................................................................. 23 2.1.1 Synthesis of Synthesis of 2,4-dichloro-6-(furan-2-yl)aniline (46) ................................... 23 2.1.2 Synthesis of 2,4-dichloro-6-(furan-2-yl)-N-(prop-2-yn-1-yl)aniline (46a) and 2,4- dichloro-6-(furan-2-yl)-N,N-di(prop-2-yn-1-yl)aniline (47b) ................................................... 24 2.1.3 Microwave mediated synthesis of 2,4-dichlorophenanthridin-8-ol (48a) and 4-chloro-2- nitrophenanthridin-8-ol (48b) .................................................................................................... 25 2.1.4 Other 8-hydroxyphenanthridines ..................................................................................... 25 2.2 Functionalization on the 8-position of 8-hydroxyphenanthridine......................................... 26 iv 2.2.1 O-Alkylation ........................................................................................................................ 26 2.2.1.1 O-alkylation of different 8-hydroxyphenanthridines with various reagents ............. 26 2.2.1.2 Synthesis of 8-(allyloxy)-2,4-dichloro-5-methyl-5,6-dihydrophenanthridine (64) and 8-(allyloxy)-2,4-dichloro-5-methylphenanthridin-6(5H)-one (65) ........................................... 28 2.2.2 Synthesis of phenanthridine esters .................................................................................... 30 2.2.2.1 Synthesis of 2,4-dichlorophenanthridin-8-yl benzoate (69) ......................................... 30 2.2.2.2 Synthesis of 2,4-dichlorophenanthridin-8-yl acetate (70) ............................................ 31 2.2.3 Triflation and Suzuki coupling reaction ........................................................................... 32 2.2.3.1 Synthesis of 2,4-dichlorophenanthridin-8-yl trifluoromethanesulfonate (71 ............. 32 2.2.3.2 Synthesis of 2,4-dichloro-8-phenylphenanthridine (73) ............................................... 33 2.2.4 Conclusion ........................................................................................................................... 33 2.3 Claisen rearrangement .............................................................................................................. 34 2.3.1 Screening of conditions for the microwave-mediated Claisen rearrangement of 8- (allyloxy)-2,4-dichlorophenanthridine (56) ............................................................................... 34 2.3.2 Four ortho substituted 8-hydroxyphenanthridines synthesized by Claisen rearrangement ............................................................................................................................. 37 2.3.3 Synthesis of 2,4-dichloro-7-(2-methylallyl)phenanthridin-8-ol (79a), 2,4-dichloro-7-(2- methylprop-1-en-1-yl)phenanthridin-8-ol (79b) and 6,8-dichloro-2,2-dimethyl-2,3- dihydrofuro[3,2-i]phenanthridine (79c) .................................................................................... 38 2.3.4 Attempts to synthesize 2,4-dichloro-7-(2-methylbut-3-en-2-yl)phenanthridin-8-ol (80) ....................................................................................................................................................... 41 2.3.5 Synthesis of 9-allyl-2,4-dichloro-7-methylphenanthridin-8-ol (81) ................................ 43 2.4.8 Synthesis of 7-allyl-4-chloro-8-hydroxy-5-methylphenanthridin-6(5H)-one (82a) and 6- chloro-2,5-dimethyl-2,3-dihydrofuro[3,2-i]phenanthridin-4(5H)-one (82b) .......................... 46 2.4.9 Conclusion ........................................................................................................................... 48 3. Future research ................................................................................................................................ 49 4. Conclusion ........................................................................................................................................ 51 5. Experimental .................................................................................................................................... 52 6. Appendix .......................................................................................................................................
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