Sulfonated N-heterocyclic carbenes and their importance in Palladium catalyzed cross coupling reactions in water [Elektronische Ressource] / eingereicht von Sutapa Roy

Sutapa

Informations

• Publié par: technischen_universitat_darmstadt
• Publié le: 01 janvier 2009
• Nombre de lectures: 59
• Langue: English
• Poids de l'ouvrage: 1 Mo

Extrait

SulfonatedN -Heterocyclic carbenes and
their importance in Palladium catalyzed
Cross-Coupling Reactions in Wa ter





Vom Fachbereich Chemie der Technischen UniverDsairtmästt adt
zur Erlangung des akademischen Grades eines
Doctor rerum naturalium (Dr. rer. nat.)
genehmigte
Dissertation
eingereicht von
M.Sc. Sutapa Roy
aus Bethua dahari, India

Referent: f . D rP.r oH. Plenio
Korreferent: D rP.ro Bf. Schmidt
Tag der Einreichung: 21. Sepr t20e0m9b
Tag der mündlichen Prüfung: 02. November 2009
Darmstadt 2009
D 17

















































F or my Parents…….
&a nRdit iskiast.e rs Dipika


























Acknowledgement
The entire work embodied in this thesis is tlhte orfe siunvestigation carried out by me from
October 2005 to March 2009 under the supervision oPfrof. Dr. Herbert Plenio from
Anorganische Chemie im Eduard Zintl-Instituti, sTcehceh Unniverstät Darmstadt. It is my great
pleasure to thank Prof H Plenio who has given me otphportunity to carry out my doctoral
study in his research group and to work in a rceoamlpleytitive and attractive research area of
homogeneous organometallic catalysis and also dpironvgi financial support from DFG.
I am grateful to all my lab-mates Dr. Axel Kölrl,h Dofr.e-Ing. Markus an der Heiden, Dr.-Ing.
Steffen Leuthäußer, Dr.-Ing. Holger Weychard, Dhrr.i sCtoph Fleckenstein, Dr.-Ing. Dirk Schöps,
Dr. Volodymyr Sashuk, Dipl.-Ing. Tim Vorfalt,- IDnig.p lSt.efanie Wolf, Dipl.-Ing. Marc Schilz,
Dipl.-Ing. Jan Pschierer, Dipl.-Ing. Lar st hPeiecr kh feolrp, support and cooperation in the
laboratory. I would like to give thanks to TiMma racn dsp ending time for reading my thesis
with appropriate suggestion and also to Stef,f iVo,l oJdaynmyr for their valuable suggestions. I
would like to give special thanks to Frau Eilfleern a Pnfde Frau Annette Przewosnik for their all
kinds of help to solve my problems. I would ltihkaen kt oDr. Klaus Wannowius for his help and
assistance instead of his busy schedule of w oorukl.d I l ike to thank Frau Jana Wendlig and
Frau A. Przewosnik and the Organic Chemistry NMRp adretment for recording NMR spectra.
I am really indebted to Frau Hella Wambold, my nhebiorg for her all types of support, caring,
nourishment to survive an easy, comfortable ando yeanbjle life in a foreign country.
It is my great privilege to thank my fatherg-ulriek ePr offi. Biswanath Chakravarty for his all
kinds of support, cooperation, affection andc eg.u iId raenally owe to Prof. Asit Ranjan Sarkar
and Prof. Ashoke Prasun Chattopadhyay, Prof Dinadbhaun Pramanik for their valuable advice,
guidance, suggestion and inspiration in rIe aalm lhiafpep. y to convey thanks to my English
teacher Mr. Prabodh Kumar Naskar (like grandfath efro)r his caring, blessing, encouragement
and affection.
I would like to convey thanks to my friends l.i kAen aDnrya Debnath, Dr. Pallavi Debnath, Dr.
Sagarika Dev, Dr. Angshuman Raychowdhury, Dr. Suypar iDas, Dr. Monalisa Panda, Ms. Kuheli
Brahma, Mrs. Supriya Barman, Dr. Diksha Dani,o Durs.u mMi Upadhyay, Dr. Barnali Roy and Mr.
Sanat Kumar Nag (who induced the interest of chetmryi sin my school class) and many well-
wishers and friends whose blessings, supportrse aentid nggs always with me.
No word is sufficient to convey gratitude to mry fdrei aend Dr. Subhas Chandra Pan for his
constant support and well wishes and love whiuncph airas llel in real life. The biggest support
and strength I am acquiring from my family, my aunndt sisters and brothers (including small
Aabir) and grandparents (who are only in my mem.o r y )

























Table of Contents
1 Introduction…………………………………………………………………………………………………………….…1
1. 1 N-Heterocyclic Carbenes (NHCs)…………………………………………………………………..…….…....1
1.2 Comparison between NHCs and Phosphine…s………………………….........................2
1.3 Pincer type N-heterocyclic ligands……………………………………………………….………...2
1.4 Palladium Catalyzed Cross-coupling Rnesa…c…ti…o………………………………………………....7
1.4.5 Palladium-NHC Catalyzed Suzuaki -CMroiysas-uCroupling Reaction……………….…10
1.5 Cross-Coupling with Terminal AlkynSeo n:o gtahseh ira Reaction…….........................24
1.6 Olefin Metathesis………………………………………………….……………………………………..30
1.6.1 Historical Background………………………………………………………………..……………...……..31
1.6.2 Ruthenium Complexes…………………………………………………………………….……34
1.6.3 Applications of Ruthenium-baysetds… C…a…ta…l…………………..…………………….....36
1.6.4 Mechanistic Considerations ouf mR-ubthaesnedi Catalysts………………………….……42
1.6.5 Structural Diversity and RutheCn icuom-pNleHxes……………….………………………..43
2 Strategic Plans……………………………………………………………………..……………………………..... 47
2.1 Strategy for Designing New NHC LigCa nbdos:nd Cf-orming methodology…..……..….47
2.2 Design of Ligands and catalytic pro…to…co…l………………….…………………………..…..48
2.3 Strategy for designing pincer-type npeh-otsapghgied NHCs: C=C methodology……...50
3 Results and Discussion………………………………………………………………………..………………..…..52
3.1 Synthesis of imidazolium/imidazoliniutms… …sa…l………………………….…………….…...…52
3.1.7 Synthesis of meta-sulfonatedi nIiumi dsaazlotsl………………………………….……..….59
3.1.8 Synthesis of para-sulfonatedi nIiumid asazoltls………………………………………..……60
3.1.9 Synthesis of meta-sulfonatediu mIm siadlatzso…l…………………….………………….…...61
3.1.10 Synthesis of para-sulfonatedliu mIm sidaaltzso……………………….……………..…......62


3.2 Direct method of Sulfonation of imnidi)auzmol es(alts ………...………………………….…...62
3.3 Palladium-π-allyl(NHC) complexes…………………………………………………………….65
3.4 Catalytic Study: Palladium catalyze-dc oCurpolsisng Reactions…………………………….…65
3.5 Suzuki-Miyaura Coupling reaction………………………………………………………….…….66
3.5.10 Catalytic Studies in Watgere n(eriant esdit uc atalysis)………….…….……………..….69
3.5.11 Catalytic StudOie/sn -inBu OHH (1:1):Pd-π-allyl complex ……..………………. .…….752
3.5.12 Conclusion and Outlook………………………………………….……………….….…..81
3.6 Sonogashira Coupling Reaction…………………………………….………………………….….…..82
3.6.7 Catalytic studOie/sis oin- PHrOH mixture (1:1) (In situ catalysis) …….….…85… .2
3.6.8 Conclusion and Outlook……………………………………………………………………………....…….89
4 Ru Catalyzed C=C double bond forming methodol oOgyle:fin metathesis……………….…….9 0
4.1 Design and Synthesis of Ligands…………………………………………………………..…..…..90
4.5 Synthesis of iodo-alkyl-mesitylimidnaiuzomli diiodides……………………………………………92
4.6 Synthesis of (phosphonium-alkyl)-mideasziotylildiminium diiodides………………………..94
4.7 Formation of Ruthenium(P-C pincera llkigyalidnedn)e() complexes………………………….98
4.7.1 Direct Method……………………………………………………………………………………………….…..99
4.7.2 Indirect Method…………………………………………………………………………..….103
4.7.3 Synthesis of Ru[1-decyl-(dsiphiennoy)l-p3h-o(mesityl)imidazolinidine]dichloro
(alkylidene)] complex………………………………………………………………..105
4.7.4 Conclusion and Outlook…………………………………………………………………..105
5 Summary and Outlo…o…k…………………………………………………………………………………………..106
6 Experimental Part…………………………………………………………………………………………………..111
6.1 General Considerations………………………………………………………………………………………….111
6.2 Synthesis of Aniline derivatives…………………………………………………………….……..113