Iron-Catalyzed Synthesis of Fused Aromatic Compounds via C–H Bond Activation PDF
Preview Iron-Catalyzed Synthesis of Fused Aromatic Compounds via C–H Bond Activation
Springer Theses Recognizing Outstanding Ph.D. Research Arimasa Matsumoto Iron-Catalyzed Synthesis of Fused Aromatic Compounds via C–H Bond Activation Springer Theses Recognizing Outstanding Ph.D. Research For furthervolumes: http://www.springer.com/series/8790 Aims and Scope The series ‘‘Springer Theses’’ brings together a selection of the very best Ph.D. theses from around the world and across the physical sciences. Nominated and endorsed by two recognized specialists, each published volume has been selected for its scientific excellence and the high impact of its contents for the pertinent fieldofresearch.Forgreateraccessibilitytonon-specialists,thepublishedversions includeanextendedintroduction,aswellasaforewordbythestudent’ssupervisor explaining the special relevance of the work for the field. 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Arimasa Matsumoto Iron-Catalyzed Synthesis of Fused Aromatic Compounds via C–H Bond Activation Doctoral Thesis accepted by The University of Tokyo, Japan 123 Author Supervisor Dr. ArimasaMatsumoto Prof.EiichiNakamura The Universityof Tokyo The Universityof Tokyo Tokyo Tokyo Japan Japan ISSN 2190-5053 ISSN 2190-5061 (electronic) ISBN 978-4-431-54927-7 ISBN 978-4-431-54928-4 (eBook) DOI 10.1007/978-4-431-54928-4 Springer TokyoHeidelberg New YorkDordrecht London LibraryofCongressControlNumber:2014942163 (cid:2)SpringerJapan2014 Thisworkissubjecttocopyright.AllrightsarereservedbythePublisher,whetherthewholeorpartof the material is concerned, specifically the rights of translation, reprinting, reuse of illustrations, recitation,broadcasting,reproductiononmicrofilmsorinanyotherphysicalway,andtransmissionor informationstorageandretrieval,electronicadaptation,computersoftware,orbysimilarordissimilar methodology now known or hereafter developed. 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While the advice and information in this book are believed to be true and accurate at the date of publication,neithertheauthorsnortheeditorsnorthepublishercanacceptanylegalresponsibilityfor anyerrorsoromissionsthatmaybemade.Thepublishermakesnowarranty,expressorimplied,with respecttothematerialcontainedherein. Printedonacid-freepaper SpringerispartofSpringerScience+BusinessMedia(www.springer.com) Parts of this thesis have been published in the following journal articles: ‘‘Synthesis of Polysubstituted Naphthalenes by Iron-Catalyzed [2 + 2 + 2] Annulation of Grignard Reagents with Alkynes’’ Ilies, L.; Matsumoto, A.; Kobayashi, M.; Yoshikai, N.; Nakamura, E. Synlett 2012, 23, 2381–2384. ‘‘Phenanthrene Synthesis by Iron-Catalyzed [4 + 2] Benzannulation between Alkyne and Biaryl or 2-Alkenylphenyl Grignard Reagent’’, Matsumoto, A.; Ilies, L.; Nakamura, E. J. Am. Chem. Soc. 2011, 133, 6557–6559. Supervisor’s Foreword I am very pleased to see the doctoral thesis of my former student Dr. Arimasa Matsumotobeing publishedas apart ofthe Springer Theses. Thethesisdescribes the development of catalytic uses of iron for organic synthesis, more specifically, catalytic cleavage of an aromatic C–H bond for the creation of a new C–C bond under mild conditions. Organicmaterialsplaysignificantrolesinourdailyliferangingfromdrugsfor medication to plastics in industrial products. Organic semiconductors—organic molecules containing a number of benzene rings—are used in organic electrolu- minescent diodes and organic solar cells and may someday even replace the current technology based on metallic silicon that requires so much energy to produce from silica. Today’s synthesis of such aromatic molecules relies heavily ontheuseoftransitionmetalcatalyststhatarerare,expensive,andoftentoxic,and therefore may not necessarily be cost-effective or environmentally friendly. Thesupplyofthesemetalsisdwindlingandtheyarenotsuitableforindustrialuse in a country which, like Japan, does not have any domestic sources of such elements. These are strong reasons to focus on iron. Iron-56 is the most abundant heavymetalintheuniverse,becauseitistheheavieststableelementinsupernova nucleosynthesis.Iron,withits26protonsand30neutrons,hasthehighestbinding energy per nucleon, possesses 26 electrons in its atomic orbitals, puts unpaired electrons into compact 3d orbitals, and thus creates highly reactive catalysts; however, they are rather difficult to control. Research on iron catalysis for organic synthesis was pioneered by the late Prof. Jay K. Kochi in the early 1970s. His first report on an iron-catalyzed cross- coupling reaction was followed by the Kumada–Tamao–Corriu nickel catalysis and then by palladium catalysis, e.g., the Negishi and Suzuki–Miyaura coupling reactions.Arevivalofinterestinorgano-ironcatalysis(hereweexcludetheuseof iron (III) as a Lewis acid) came after 2000, and we became involved in it first through asymmetric carbometalation and then through cross-coupling chemistry. Arimasa joined our laboratories in 2006 when we started a search for a mild oxidant for C–H bond activation, and after a year of struggle he discovered 1, 2- dichloroisobutaneasanoxidantthatselectivelypromotesreductiveeliminationof aputativeironintermediate.Ourrecentstudiesinthisfieldareheavilyindebtedto Arimasa’s ingenuity. This discovery and ensuing research activities brought him vii viii Supervisor’sForeword suchhonorsasaResearchFellowshipfromtheJapanSocietyforthePromotionof Science(2009);PACIFICHEM2010StudentPosterAward;WakoPureChemical Industries Award in Synthetic Organic Chemistry, Japan (2013); and the 25th InternationalSymposiumonMolecularChirality(Chirality2013:ISCD-25)Poster Award. He received an Encouragement Award from the Dean of Science of The University of Tokyo for the excellence of his doctoral thesis. He worked as a visitingstudentattheUniversityofMichiganwithProf.MelanieSanfordin2009, and is currently Assistant Professor in the Department of Applied Chemistry, TokyoUniversityofSciencewithProf.KensoSoai.Hehas13publishedpapersto his credit. OnbehalfoftheDepartmentofChemistryatTheUniversityofTokyo,Iwould liketocongratulatehimontheSpringerThesesAward,andIearnestlyhopehecan continue exploring new facets of chemistry and teaching the next generation of chemists the joy of science. Tokyo, Japan, December 2013 Prof. Eiichi Nakamura Acknowledgments This study was performed under the direction of Prof. Eiichi Nakamura at the Department of Chemistry, Graduate School of Science, The University of Tokyo, from April 2009 to March 2012. I express my sincerest gratitude to Prof. Nakamura for his thorough profes- sional guidance, valuable suggestions, and continual encouragement during this study. I am also grateful to Assistant Prof. Laurean Ilies, whose daily advice and support made this work possible. I will always be thankful to Assistant Prof. Naohiko Yoshikai, who introduced me to organometallic chemistry. I also thank Associate Prof. Hayato Tsuji and Assistant Prof. Koji Harano for inspiring discussions and advice. I am grateful to Prof. Hiroyuki Isobe, Prof. Yutaka Matsuo, and AssociateProfessor ToshihiroOkamoto,who were former facultyof the Nakamura laboratory. Iron-catalyzed C–H bond activation chemistry enjoyed fruitful development through the efforts of Dr. Jakob Norinder, Dr. Adam Mieczkowski, Takeshi Yamakawa, Jun Okabe, Sobi Asako, and Motoaki Kobayashi. I would like to thank all the members of the Nakamura group. I am grateful to Ms. Kimiyo Saeki and Dr. Aiko Sakamoto for performing the elemental analysis of the synthesized compounds. FinancialsupportfromtheMinistryofEducation,Culture,Sports,Scienceand Technology for the Global COE program ‘‘Chemistry Innovation’’ and the Japan Society for the Promotion of Science (JSPS) is greatly appreciated. Finally, I would like to thank my family, Yoshio Matsumoto, Kazuko Matsumoto, and Noriyuki Matsumoto, for their support. ix Contents 1 General Introduction. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1 1.1 Shortage of Metal Resources. . . . . . . . . . . . . . . . . . . . . . . . . . 1 1.2 Iron for Organic Synthesis . . . . . . . . . . . . . . . . . . . . . . . . . . . 2 1.3 Iron-Catalyzed C–H Bond Activation. . . . . . . . . . . . . . . . . . . . 2 1.4 Synthesis of Fused Aromatics via C–H Bond Activation . . . . . . 4 1.5 Thesis Outline. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6 2 Iron-Catalyzed Naphthalene Synthesis from Alkyne and Grignard Reagent. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11 2.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11 2.2 Initial Finding of Naphthalene Formation. . . . . . . . . . . . . . . . . 11 2.3 Investigation of the Reaction Conditions . . . . . . . . . . . . . . . . . 13 2.4 Scope and Limitations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17 2.5 Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18 2.6 Experimental Part . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21 3 Iron-Catalyzed Phenanthrene Synthesis from Alkyne and Grignard Reagent. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 23 3.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 23 3.2 Iron-Catalyzed Phenanthrene Synthesis . . . . . . . . . . . . . . . . . . 23 3.3 Investigation of the Reaction Conditions . . . . . . . . . . . . . . . . . 25 3.4 Scope and Limitations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 27 3.5 Mechanistic Considerations. . . . . . . . . . . . . . . . . . . . . . . . . . . 28 3.6 Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 32 3.7 Experimental Part . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 33 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 64 4 Iron-Catalyzed Phenanthrene Synthesis from Alkyne and Aryl Bromide Mediated by Metallic Magnesium. . . . . . . . . . . 65 4.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 65 4.2 Chelation Assisted C–H Bond Arylation with Aryl Bromide and Magnesium . . . . . . . . . . . . . . . . . . . . . . . . . . . . 65 xi
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