Absolute configuration by circular dichroism [Elektronische Ressource] : quantum chemical CD calculations / vorgelegt von Katja Maksimenka

Amelie Fried

Informations

• Publié par: julius-maximilians-universitat_wurzburg
• Publié le: 01 janvier 2010
• Nombre de lectures: 42
• Langue: Deutsch
• Poids de l'ouvrage: 21 Mo

Extrait

Absolute Configuration by Circular Dichroism:
Quantum Chemical CD Calculations



D ISSERTATION ZUR ERLANGUNG DES
NATURWISSENSCHAFTLICHEN D OKTORGRADES
DER JULIUS -M AXIMILIANS -U NIVERSITÄTW ÜRZBURG





vorgelegt von

Katja Maksimenka

aus
Minsk, Weiβrussland



Würzburg 2010





Eingereicht am:
bei der Fakultät für Chemie und Pharmazie.


1. Gutachter:
2. Gutachter:
der Dissertation.


1. Prüfer:
2. Prüfer:
3. Prüfer:
des öffentlichen Promotionskolloquiums.


Datum des öffentlichen Promotionskolloquiums:


Doktorurkunde ausgehändigt am:
Die vorliegende Arbeit wurde in der Zeit von Juli2 200bis April 2007
am Institut für Organische Chemie
der Bayerischen Julius-Maximilians-Universität Würzburg angefertigt.






Ich danke herzlich Herrn Prof. Dr. Dr. h.c. G.an Bnr infgmür
die Möglichkeit an diesem faszinierenden Thema zu tarebne,i
die umfassende Unterstützung und
die Geduld und Verständnis















Teile der im Rahmen dieser Arbeit erzielten Esrgee bwnarisen bereits Gegenstand
[18, 30–41, 44]von Publikationen sowie von Postern und Vorträgen.
















To my boys,
Roma, Matvei and Stepane




Contents i








Contents

1. Introduction 1
2. Elucidation of the absolute configuration 9
2.1. Non-chiroptical methods..........................................10 ...................
2.2. Chiroptical approaches...........................................11 ....................
2.2.1 .Optical rotation and optical rotatory dispersion (OR..D.).....................12
2.2.2 .Circular dichroism........................................15 ..........................
2.2.2.1 .Methods for the interpretation of CD spectra.........................17
2.2.2.2 .Circular dichroism in the solid state................................................23
2.2.3 .Other chiroptical techniques: VCD and ROA................................25
3. Theoretical background 27
3.1 .CD and UV spectra via quantum chemical calculations..............................28
3.1.1 .Rotatory strength..........................................28 .........................
3.1.2 .Oscillator strength........................................30 .........................
3.2 .Theoretical approaches used for computation
of the electronic excitations.....................................30 ...................
3.2.1 .Configurational Interaction (CI) methods........................................31
3.2.2 .Time-Dependent Density Functional Theory (TDDFT)
and DFT/MRCI................................................35 .......................
ii Contents
3.3 .General proceedings of simulating CD and UV spec.t.ra..............................40
3.3. 1.Investigation of the conformational behavior.................................40
3.3. 2.Steps towards CD and UV spectra...............................................43
4. Configurational assignment by CD calculations 48
4.1 A.pplication of semiempirical methods........................... .......................48
4.1. 1.Ancistrotanzanine A (5)...................................... ...................48
4.1. 2.Isoplagiochin D6 )(.......................................... ...................54
4.1. 3T.he biaryl amide7 ........................................... ...................58
4.1. 4T.he bi[10]paracycloph8an.e. .................................. ...........62.......
4.1. 5.Sorbicillactone 9B ).(........................................ ....................67
4.1. 6.The benz[e]indole derivat10ive.. ...................................... ..........71..............
4.2 S.emiempirical and TDDFT methods resulting in almost eth same
accuracy ...................................................... .........79..........
4.2. 1B.isisonigerone 11( ).......................................... ...................79
4.2. 2N.igerone (12).............................................. .....................84
4.2. 3T.he ‘leuco’ phenylanthracene deriv13at ivoef knipholone.......... ..........88
4.2. 4Hy.droxyoxosorbicillinol14 ().................................. ............97.......
4.2. 5.Resistoflav15in )(............................................................... .......................101
4.3 C.ases where TDDFT and DFT/MRCI methods are superior
to semiempirical approaches...................................5 ........................10
4.3. 1T.aClo 16( )..................................................................................................105
4.3. 2G.ephyromycin (17 )...........................................................109
4.3. 3N.eoechinulin A 18( )..........................................................117
4.3. 4K.nipholone 19( )..............................................................124
4.3. 5.Knipholone anthrone 20( ).................................................132 ....
4.4 Ch.allenging cases for the prediction of molec.u.l.ar.. C.D............................138
4.4 .1Jo.ziknipholones A 21() and B (22).................................138 .................
4.4 .2P.etrosifungin A (23 ).................................................................................145
Contents iii

5. Circular dichroism in the solid state 150
5.1. Dioncophyline A 24() – a rewarding model compound......................151 .
5.2. CD computations of the monomer........................................................154
5.3. Consideration of dyads – neighboring effect...................................................157
6. Summary 164
7. Zusammenfassung 172
List of Abbreviations 180
Literature and Notices 183