Novel synthesis of chiral 1,2-aminophosphine ligands and their applications in asymmetric catalysis [Elektronische Ressource] / von Tanasri Bunlaksananusorn

Bunlaksananusorn, Tanasri

Description

Tanasri Bunlaksananusorn Novel Synthesis of Chiral 1,2-Aminophosphine Ligands and Their Applications in Asymmetric Catalysis M nchen, 2003 Dissertation zur Erlangung des Doktorgrades der Fakult t f r Chemie und Pharmazie der Ludwig-Maximilians-Universit t M nchen Novel Synthesis of Chiral 1,2-Aminophosphine Ligands and Their Applications in Asymmetric Catalysis Von Tanasri Bunlaksananusorn aus Yala, Thailand M nchen, 2003 Erkl rung : Diese Dissertation wurde im Sinne von § 13 Abs. 3 bzw. 4 der Promotionsordnung vom 29. Januar 1998 von Professor Dr. Paul Knochel betreut. Ehrenwrtliche Versicherung : Diese Dissertation wurde selbst ndig, ohne unerlaubte Hilfe erarbeit. M nchen, am 14.08.2003 Tanasri Bunlaksananusorn Dissertation eingereicht am 14.08.2003 1. Gutachter: Prof. Dr. Paul Knochel 2 Gutachter: Prof. Dr. em. Wolfgang Steglich M ndliche Pr fung am 25.09.2003 öThis work was carried out from March 2000 to October 2003 under the supervision of Professor Paul Knochel at the Fakult t f r Chemie und Pharmazie, Ludwig-Maximilians-University, Munich. I would like to thank Prof. Paul Knochel for giving me the opportunity to do my PhD in his group and his encouragement during my PhD work. I also would like to thank Prof. Steglich for agreeing to be my Zweigutacter , as well as Prof.

Informations

• Publié par: ludwig-maximilians-universitat_munchen
• Publié le: 01 janvier 2003
• Nombre de lectures: 14
• Langue: English

Extrait

Tanasri Bunlaksananusorn










Novel Synthesis of Chiral 1,2-Aminophosphine Ligands
and Their Applications in Asymmetric Catalysis












M nchen, 2003



Dissertation zur Erlangung des Doktorgrades
der Fakult t f r Chemie und Pharmazie
der Ludwig-Maximilians-Universit t M nchen










Novel Synthesis of Chiral 1,2-Aminophosphine Ligands and Their
Applications in Asymmetric Catalysis






Von

Tanasri Bunlaksananusorn

aus Yala, Thailand

M nchen, 2003

Erkl rung :

Diese Dissertation wurde im Sinne von § 13 Abs. 3 bzw. 4 der Promotionsordnung vom 29.
Januar 1998 von Professor Dr. Paul Knochel betreut.

Ehrenwrtliche Versicherung :

Diese Dissertation wurde selbst ndig, ohne unerlaubte Hilfe erarbeit.

M nchen, am 14.08.2003
Tanasri Bunlaksananusorn








Dissertation eingereicht am 14.08.2003
1. Gutachter: Prof. Dr. Paul Knochel
2 Gutachter: Prof. Dr. em. Wolfgang Steglich


M ndliche Pr fung am 25.09.2003




?This work was carried out from March 2000 to October 2003 under the supervision of
Professor Paul Knochel at the Fakult t f r Chemie und Pharmazie, Ludwig-Maximilians-
University, Munich.



I would like to thank Prof. Paul Knochel for giving me the opportunity to do my PhD in his
group and his encouragement during my PhD work.

I also would like to thank Prof. Steglich for agreeing to be my Zweigutacter , as well as
Prof. Karaghiosoff, Prof. Pf ndler, Prof. Zipse, Prof. Langhals for the interest shown in this
manuscipt by accepting to be referees.

I would like to thank Ludwig-Maximilians-University of Munich for financial support.

I thank Dr. Lutz Ackerman and FrØdØric Liron for the correction of this manuscript.

Vladimir Malakhov und Krystyna danke ich f r die tatkr ftige Unterst tzung im Labor. Fr
die administrative Unterst tzung bedanke ich mich bei Gabi Fried und Beatrix Cammelade.

Special thank go to my great lab mates Katja Tappe, Lionel Aufauvre, Andrei Gavriouchine,
Viet Anh Vu and Yevgeniy Snitkovskyy for listening my songs and their invaluable help in
the lab. I am indebted to Dr. Alain Louis Rodriguez for his precious help and his patience.

Furthermore, my appreciation is extended to all the members of AK Knochel who came and
went throughout my PhD that have helped me with suggestion and support with their
sympathy, which have made my time here in Germany great experience.

Finally, I would like to thank my mother, elder brothers and younger sister in Thailand for
their great support through my time abroad.

?Parts of this PhD have been published

[1] P. Knochel, A. Boudier, L. O. Bromm, E. Hupe, J. A. Varela, A. L. Rodriguez, C.
Koradin, T. Bunlaksananusorn, H. Laaziri, F. Lhermitte, Selective transformations
mediated by main-group organometallics , Pure Appl. Chem. 2000, 72, 1699.

[2] A. L. Rodriguez, T. Bunlaksananusorn, P. Knochel, Potassium tert-Butoxide Catalyzed
Addition of Carbonyl Derivatives to Styrenes , Org. Lett. 2000, 21, 3285.

[3] T. Bunlaksananusorn, A. L. Rodriguez, P. Knochel, t-BuOK-catalyzed addition of
ketones and nitriles to vinylic silanes, phosphines and thio derivatives , J. Chem. Soc.,
Chem. Commun. 2001, 745.

[4] P. Knochel, E. Hupe, W. Dohle, D. M. Lindsay, Q. Veronique, V. Bonnet, A. Boudier, F.
Kopp, S. Demay, N. Seidel, M. I. Calaza, V. A. Vu, I. Sapountzis, T. Bunlaksananusorn,
Functionalized main-group organometallics for organic synthesis , Pure Appl. Chem.
2002, 74, 11.

[5] T. Bunlaksananusorn, P. Knochel, t-BuOK-catalyzed addition phosphines to functional-
ized alkenes: a convenient synthesis of polyfunctional phosphine derivatives ,
Tetrahedron Lett. 2002, 43, 5817.

[6] T. Bunlaksananusorn, K. Polborn, P. Knochel, New P,N-Ligands for the Performance of
Asymmetric Ir-Catalyzed Reactions , Angew. Chem. Int. Ed. 2003, 42, 3941.

[7] T. Bunlaksananusorn, A. P. Luna, M. Bonin, L. Micouin, P. Knochel, New Applications
of Camphor-Derived P,N-Ligands for Asymmetric Pd- and Ir-Catalyzed Reactions ,
Synlett 2003, in press.





















Table of Contents


Introduction


1 Overview............................................................................................................................1

1.1 Chiral P,P-ligands..............................................................................................................2

1.1.1 Synthesis via S 2 reactions ...................................................................................4 N
1.1.2 Syvia oxidative couplings..........................................................................5
1.1.3 Synthesis via Diels-Alder reactions.......................................................................6
1.1.4 Syvia Michael additions ............................................................................7

1.2 Chiral P,N-Ligands...8

1.2.1 Phosphinooxazoline ligands..................................................................................8
1.2.2 Axially chiral aminophosphine ligands ...............................................................10
1.2.3 Iminophosphine ligands.......................................................................................11
1.2.4 Phosphinoarylpyridine ligands............................................................................13

2 Objectives ........................................................................................................................15


Results and Discussion


1 Addition of nucleophiles to alkenes...............................................................................16

1.1 Addition of carbonyl derivatives to styrenes...................................................................17

1.1.1 Nitriles as nucleophiles........................................................................................18
1.1.2 Ketones as nucleophiles.......................................................................................20
1.1.3 Imines as nucleophiles.........................................................................................21
1.1.4 Other ...............................................................................................22
1.1.5 Mechanism...........................................................................................................22
1.1.6 Addition-elimination reactions............................................................................23
1.1.7 Summary..............................................................................................................24

1.2 Addition of carbonyl derivatives to functionalized alkenes ............................................25

1.2.1 Addition of nitriles to functionalized alkenes......................................................25
1.2.2 Addition of ketones to vinyl phosphines .............................................................28
1.2.3 Summary..............................................................................................................29

1.3 Hydrophosphination of alkenes.......................................................................................29

1.3.1 Hydrophosphination of functionalized alkenes ...................................................29
1.3.2 Addition of phosphine oxides to trisubstituted alkenes.......................................32
1.3.3 Addition-elimination reactions............................................................................33
1.3.4 Summary34


2 Synthesis of chiral P,N-ligands and their applications in asymmetric catalysis.......34

2.1 Preparation of chiral alkenyl triflates 61 .........................................................................36

2.2 Negishi cross-coupling of pyridylzinc reagents 70-71....................................................37

2.3 Hydrophosphination of alkenylpyridines 63a-f...............................................................39

2.4 Reduction of phosphine oxides 65a-g. ............................................................................42

2.5 Applications in asymmetric catalysis ..............................................................................45

2.5.1 Pd-catalyzed enantioselective allylic substitution ...............................................45
2.5.2 Pd-catalyzed enantioselective allylic amination..................................................46
2.5.3 Ir-catalyzed asymmetric hydroboration of meso-bicyclic hydrazine .................47
2.5.4 Ir-catalyzed asymmetric hydrogenation of trisubstituted alkenes .......................49

2.6 Summary....................................