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Synthesis of Novel Extremely Sterically Hindered Tertiary Alkylamines

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Synthesis of Novel Extremely Sterically Hindered Tertiary Alkylamines Synthesis of Novel Extremely Sterically Hindered Tertiary Alkylamines von der Fakultät für Naturwissenschaften der Technischen Universität Chemnitz genehmigte Dissertation zur Erlangung des akademischen Grades doktor rerum naturalium (Dr. rer. nat.) vorgelegt von M.Sc. Tharallah A. Shoker geboren am 18. April 1985 in Nabi Chit, Lebanon eingereicht am 17. January 2018 Gutachter: Prof. Dr. Klaus Banert JP Dr. Evgeny Kataev Tag der Verteidigung: 16. April 2018 Die vorliegende Arbeit wurde in der Zeit von Oktober 2015 bis Oktober 2017 am Institut für Chemie an der Fakultät für Naturwissenschaften der Technischen Universität Chemnitz unter der Leitung von Prof. Dr. Klaus Banert angefertigt. 2 Bibliographic Description Synthesis of Novel Extremely Sterically Hindered Tertiary Alkylamines SHOKER, THARALLAH Technische Universität Chemnitz, Fakultät für Naturwissenschaften Dissertation, 2017, 208 pages. Abstract Three advanced methodologies for the preparation of extremely sterically hindered tertiary alkyl amines have been developed. The syntheses of 28 novel tertiary alkylamines that accommodate unusual steric hindrance are detailed. The electrophilic amination of alkyl Grignard reagents with N-chlorodialkylamines, in the presence of N,N,N′,N′-tetramethylethylenediamine (TMEDA) as a key additive, gives a variety of unprecedentedly sterically hindered tertiary alkylamines in good yields. Alternative strategy to 1-adamantyl-substituted (1-Ad) sterically hindered tertiary amines, which involved instead an SN1 reaction between 1-Ad cation with various secondary amines, is described. A complementary strategy to 1-Ad-based sterically hindered tertiary amines, which involves an iminium salt intermediate, is also reported. Salient features of the three protocols that are detailed here include unusual tolerance of steric hindrance, mild reaction conditions employed, ease of product isolation-purification, and absence of catalysts/transition metals. The molecular structures of two faithful examples of extremely sterically hindered tertiary alkylamines were determined by single crystal X-ray diffraction, and the height “h” of nitrogen pyramid of these compounds were measured. The NMR spectra show a restriction in rotation at room temperature among many hindered tertiary amines, and some of them exhibit two complete sets of peaks for two non-equivalent rotamers at room temperature. 15N NMR has been applied to study the structural changes in highly sterically hindered tertiary amines. Most of these compounds have been shown to undergo Hofmann type elimination reaction upon thermolysis at 100 C in inert solvents, like toluene. Keywords: Steric hindrance, tertiary amines, 1-adamantyl compounds, N-chloroamines, nucleophilic substitution, N,N,N′,N′-tetramethylethylenediamine, temperature-dependent NMR spectroscopy, pyramidal configuration of nitrogen, nitrogen NMR. 3 Bibliografische Beschreibung Synthese neuer extrem sterisch gehinderter tertiärer Alkylamine Abstract In der vorliegenden Arbeit wurden drei Methoden zur Synthese von tertitären Aminen mit extremer sterischer Hinderung entwickelt und zur Synthese von 28 neuen tertiären Alkylaminen mit entsprechender sterischer Hinderung angewendet. Die elektrophile Aminierung von Grignard-Reagenzien mit N-Chlordialkylaminen, unter Zusatz von N,N,N′,N′-Tetramethylethylendiamin (TMEDA) als Schlüsselkomponente, ermöglicht einen einfachen Zugang zu einer Vielzahl von tertiären Aminen mit extremer sterischer Hinderung mit guten Ausbeuten. Eine alternative Synthesestrategie unter SN1-Bedingungen führt zu sterisch-gehinderten 1-Adamantyl-substituierten (1-Ad) tertiären Aminen durch die Reaktion eines 1-Ad-Kations mit unterschiedlichen sterisch-gehinderten sekundären Aminen. Angelehnt an die zuvor beschriebene Reaktion können auch sterisch gehinderte Imine über eine Iminium-Salz-Zwischenstufe zu sterisch-gehinderten 1-Ad-substituierten tertiären Aminen umgesetzt werden. Auch in diesen Fall zeichnet sich die Reaktion durch eine bemerkenswerte Toleranz gegenüber sterischer Hinderung, milden Reaktionsbedingungen, leichte Produktisolierbarkeit und die Abwesenheit von Übergangsmetallkatalysatoren aus. Die molekulare Struktur zweier repräsentativer tertiärer Alkylamine mit extremer sterischer Hinderung wurde mittels Röntgeneinkristallstrukturanalyse untersucht und die Höhe “h” ihrer Stickstoff-Pyramide bestimmt. Die NMR-Spektren zeigen bei RT eine Einschränkung der freien Rotation um die N-C-Bindungsachse, teilweise führt dies zu vollständig getrennten Signalsätzen für die einzelnen Rotamere. 15N-NMR-Spektroskopie wurde ebenfalls zur Untersuchung von Strukturveränderungen genutzt. In inerten Lösungsmitteln, wie Toluol, zeigen die Verbindungen bei 100 °C in den meisten Fällen eine Hofmann-Eliminierung. Stichworte: Sterische Hinderung, tertiäre Amine, 1-Adamantylverbindungen, N-Chloramine, N,N,N′,N′-Tetramethylethylendiamin, Nucleophile Substitution, temperaturabhängige NMR- Spektroskopie, Pyramidale Konfiguration des Stickstoffs, Stickstoff-NMR. 4 Acknowledgments Acknowledgment is due to those individuals without whom completion of this body of work would not have been possible: Professor Klaus Banert (advisor), Dr. M. Hagedorn, Dr. A. Ihle, Dr. M. Müller, M. Heck, T. Pester, E. Gutzeit, M. Hofmann, J. Buschmann, K. Weigand, S. Bochmann, J. Seifert, Ms. Christiane Dienel, Ms. B. Kempe (for performing elemental analyses), Dr. R. Buschbeck (for measuring HRMS), Dr. M. Wӧrle (for performing single crystal X-ray diffraction), and Prof. A. D. Boese (for performing the theoretical calculations). 5 For my parents, my sisters, and my brothers. 6 Table of Contents List of Tables ............................................................................................................................................... 9 List of Figures ............................................................................................................................................. 9 List of Schemes ........................................................................................................................................ 10 List of Abbreviations and Symbols ........................................................................................................ 12 List of New Compounds .......................................................................................................................... 14 I. Introduction ........................................................................................................................................ 16 II. Purpose of the Work ........................................................................................................................ 22 III. Results and Discussions ............................................................................................................. 23 1. Electrophilic Amination of Alkyl Grignard Reagents with N-Chloroamines...................... 23 1.1 Initial Studies ......................................................................................................................... 23 1.2 Preparation of Various (tert-Alkyl)-Based Tertiary Amines. ............................................ 29 1.3 Preparation of the Novel 2-(tert-Butyl)-1,1,3,3-tetramethylisoindoline (12b), 2-(tert- Butyl)-1,1,3,3-tetraethylisoindoline (12d), and Related Compounds. .......................................... 32 1.4 Preparation of Novel Extremely Sterically Hindered Bridgehead-Bonded Tertiary Alkylamines. ...................................................................................................................................... 35 1.5 Preparation of N-(tert-Butyl)-N-isopropyladamantan-1-amine (18). ............................... 45 2. Electrophilic Amination of Alkyl Grignard Reagents with N,N-Dichloroamines. .............. 50 3. SN1–Type Reaction between Various Secondary Amines and 1-Adamantyl Cation. ......... 53 3.1 Initial Studies. ........................................................................................................................ 54 3.2 Preparation of Various Novel (1-Ad)-Based N,N,N-Tri(tert-alkyl) Cyclic Amines. ........ 58 3.3 Attempts for the Preparation of Sterically Hindered Six-Membered Cyclic Amines. ... 60 3.4 Attempts for the Preparation of N,N-Di-tert-Butyladamantan-1-amine (19) and Related Compounds. ....................................................................................................................................... 63 4. SN1–Type Reaction between Various Imines and 1-Adamantyl Triflate. ............................ 67 4.1 Initial Studies. ........................................................................................................................ 67 4.2 Preparation of Various Highly Sterically Hindered Enamines. ....................................... 68 5. Applications ............................................................................................................................... 70 5.1 Non-Planar Structures of Extremely Sterically Hindered Tertiary Alkylamines. .......... 70 5.2 Preparation of Sequent Series of Sterically Hindered Amines for 15N NMR Studies. .... 72 5.3 Elimination Rate of Some Sterically Hindered Tertiary Amines ..................................... 74 7 5.4 Dynamic NMR Studies ......................................................................................................... 75 IV. Conclusion ....................................................................................................................................
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