Iron-Catalyzed Synthesis of Fused Aromatic Compounds via C–H Bond Activation

84 Pages·2014·6.79 MB·English

by  Arimasa Matsumoto (auth.)

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
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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
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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
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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.
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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
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