The Synthesis of N-substituted ferrocenes and C-H activation towards the synthesis of organosilanols [Elektronische Ressource] / vorgelegt von Salih Özçubukçu

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• Publié par: rheinisch-westfalischen_technischen_hochschule_-rwth-_aachen
• Publié le: 01 janvier 2007
• Nombre de lectures: 14
• Langue: English

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The Synthesis of N-Substituted Ferrocenes
and
C–H Activation Towards the Synthesis of
Organosilanols
¨Salih Oz¸cubukc¸u
DissertationThe Synthesis of N-Substituted Ferrocenes
and
C–H Activation Towards the Synthesis of
Organosilanols
Von der Fakulta¨t fu¨r Mathematik, Informatik und Naturwissenschaften der
Rheinisch-Westfa¨lischen Technischen Hochschule Aachen zur Erlangung des akademischen
Grades eines Doktors der Naturwissenschaften genehmigte Dissertation
vorgelegt von
Master of Science
¨Salih Ozc¸ubukc¸u
aus Gaziantep (Tu¨rkei)
Berichter: Universit¨atsprofessor Dr. Carsten Bolm
Universit¨atsprofessor Dr. Dieter Enders
Tag der mu¨ndlichen Pru¨fung: 22 Januar 2007
Diese Dissertation ist auf den Internetseiten der Hochschulbibliothek online verfu¨gbar.For everybodyThe work presented in this thesis was carried out at the Institute of Organic Chemistry of the
RWTH-Aachen University, under the supervision of Prof. Dr. Carsten Bolm between January
2003 and July 2006.
I would like to thank Prof. Dr. Carsten Bolm for giving me the opportunity to work on this
exciting research topic, excellent conditions and support in his research group. I would like to
thank Prof. Dr. Dieter Enders for his kind assumption of the co-reference.
Parts of this work have already been published or submitted:
¨’Organosilanols as Catalysts in Asymmetric Aryl Transfer Reactions’ Ozc¸ubukc¸u, S.; Schmidt,
F.;Bolm,C.Org. Lett. 2005,7,1407. (ThisarticlehasbeenhighlightedinSynfact2005,0,41.)
¨’A General and Efficient Synthesis of Nitrogen-Substituted Ferrocenes’ Ozc¸ubukc¸u, S.; Scmitt,
E.; Leifert, A.; Bolm, C.; Synthesis 2007, 389.
¨’DiastereoselectiveCatalyticC–HActivationofFerrocenes’Ozc¸ubukc¸u,S.;Bolm,C.;Manuscript
in Prep.viiiContents
1 Introduction 1
1.1 C–H Activation Reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
1.1.1 Stoichiometric C–H Activation Reactions . . . . . . . . . . . . . . . . . . 3
1.1.2 Pioneer Studies on Catalytic C–H Activation Reactions . . . . . . . . . . 4
1.1.3 Murai’s Catalytic C–H Activation . . . . . . . . . . . . . . . . . . . . . . 5
1.1.4 Catalytic Olefin Insertion into the C–H Bond . . . . . . . . . . . . . . . . 12
1.1.5 Catalytic Dehydrogenation of Alkanes . . . . . . . . . . . . . . . . . . . . 14
1.1.6 Catalytic Borylation of C–H Bonds . . . . . . . . . . . . . . . . . . . . . . 15
1.1.7 Catalytic Insertion of Nitrogen into the C–H Bond . . . . . . . . . . . . . 17
1.1.8 Catalytic Insertion of Oxygen into the C–H Bond . . . . . . . . . . . . . . 20
1.2 Objectives of the Research . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22
1.3 Results and Discussions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22
1.3.1 Diastereoselective C–H Activation of Ferrocenyl Oxazolines . . . . . . . . 23
1.3.2 Application of Different Type of Substrates . . . . . . . . . . . . . . . . . 27
1.4 Summary and Outlook . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 30
2 Organosilanols 31
2.1 Properties of Organosilanols . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 32
2.1.1 Acidity and Basicity of Organosilanols . . . . . . . . . . . . . . . . . . . . 32
2.1.2 Biologically Active Silanols . . . . . . . . . . . . . . . . . . . . . . . . . . 32
2.2 General Synthesis of Organosilanols . . . . . . . . . . . . . . . . . . . . . . . . . 36
2.2.1 Synthesis of Silanols From Si–H Compounds . . . . . . . . . . . . . . . . 37
2.2.2 Synthesis of Silanols by the Hydrolysis of Halosilane . . . . . . . . . . . . 41
2.2.3 Synthesis of Silanols via the Cleavage of Si–O Bond . . . . . . . . . . . . 42
2.2.4 Synthesis of Silanols by the Hydrolysis of Si–N Bond . . . . . . . . . . . . 43
ixx
2.2.5 Synthesis of Silanols by the Cleavage of Si–Ph Bond . . . . . . . . . . . . 43
2.3 Application of Silanols . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 44
2.3.1 Cross-coupling Reactions of Silanols . . . . . . . . . . . . . . . . . . . . . 44
2.3.2 The Silanol Moiety as a Directing Group . . . . . . . . . . . . . . . . . . 46
2.3.3 Silandiol-Based Anion Receptors . . . . . . . . . . . . . . . . . . . . . . . 47
2.4 Objectives of the Research . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 48
2.5 Results and Discussion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 49
2.5.1 Synthesis of Ferrocene-based Organosilanols . . . . . . . . . . . . . . . . . 49
2.5.2 Application of Organosilanols in Asymmetric Reactions . . . . . . . . . . 51
2.5.3 Organosilanols as Directing Group on Ferrocenes . . . . . . . . . . . . . . 53
2.5.4 Synthesis of Ferrocene-Based Disilanols . . . . . . . . . . . . . . . . . . . 54
2.5.5 Hydrogen Bond Catalyzed Hetero-Diels-Alder Reaction . . . . . . . . . . 56
2.5.6 On the Way to a Silanol Analog of Prolinols . . . . . . . . . . . . . . . . . 58
2.6 Summary and Outlook . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 59
3 N-Substituted Ferrocene Derivatives 61
3.1 Syntheses of Ferrocenyl Amine . . . . . . . . . . . . . . . . . . . . . . . . . . . . 61
3.2 Synthesis of 1,1’-Diamino Ferrocene . . . . . . . . . . . . . . . . . . . . . . . . . 64
3.3 Objectives of the Research . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 65
3.4 Results and Discussions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 66
3.4.1 A General Synthesis of Ferrocenyl Amines . . . . . . . . . . . . . . . . . . 66
3.4.2 Pyrazole as a Directing Group on Ferrocenes . . . . . . . . . . . . . . . . 70
3.4.3 Bispyrazoles as Potential Ligands . . . . . . . . . . . . . . . . . . . . . . . 73
3.4.4 A Small Extension of Bispyrazoles . . . . . . . . . . . . . . . . . . . . . . 73
3.5 Summary and Outlook . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 75
4 Experimental Section 77
4.1 General Methods and Chemicals . . . . . . . . . . . . . . . . . . . . . . . . . . . 77
4.1.1 Solvents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 77
4.1.2 Determination of the Physical Data . . . . . . . . . . . . . . . . . . . . . 78
4.2 C–H Activation of Ferrocene Compounds . . . . . . . . . . . . . . . . . . . . . . 80
4.2.1 General Procedure A for C–H Activation Reactions. . . . . . . . . . . . . 80
4.2.2 Synthesisof(S,R )-2-(triethylsilane)ferrocenyl-5-tert-butyloxazoline(S,R )-p p
75 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 80