Recent applications of alkene metathesis for fine chemicals and supramolecular system synthesis

503 Pages·2007·10.114 MB·English

by  Franc Požgan, Pierre H Dixneuf

Metathesis Chemistry
From Nanostructure Design to
Synthesis of Advanced Materials
edited by

Yavuz İmamoğlu
Hacettepe University,
Beytepe, Ankara, Turkey
and
Valerian Dragutan
Romanian Academy
Bucharest, Romania
Technical Editor:
Solmaz Karabulut
Hacettepe University,
Beytepe, Ankara, Turkey
Published in cooperation with NATO Public Diplomacy Division
Proceedings of the NATO Advanced Study Institute on New Frontiers in
Metathesis Chemistry: From Nanostructure Design to Sustainable
Technologies for Synthesis of Advanced Materials
Antalya, Turkey
4 –16 September2006
AC.I.P. Catalogue record for this book is available from the Library of Congress.
ISBN 978-1-4020-6090-8 (PB)
ISBN 978-1-4020-6089-2 (HB)
ISBN 978-1-4020-6091 -5 (e-book)
Published by Springer,
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TABLE OF CONTENTS
Preface...........................................................................................................ix
List of participants .......................................................................................xv
PART I. DESIGN OF NEW GENERATIONS OF METATHESIS
CATALYSTS
New Ruthenium Catalysts for Alkene Metathesis..........................................3
Cédric Fischmeister, Pierre H. Dixneuf
Synthesis and Activity in Ring-Closing Metathesis of Phosphine
and NHC-Containing Ruthenium–Indenylidene (Bis)Pyridine
Complexes....................................................................................................29
Herve Clavier, Steven P. Nolan
Towards New Generations of Metathesis Metal–Carbene Pre-catalysts......39
Bart Allaert, Nicolai Dieltiens, Chris Stevens, Renata Drozdzak,
Ileana Dragutan, Valerian Dragutan and Francis Verpoort
Ruthenium–Aryloxide Catalysts for Olefin Metathesis................................79
Sebastien Monfette, Johanna M. Blacquiere, Jay C. Conrad,
Nicholas J. Beach, Deryn E. Fogg
Homobimetallic Ruthenium–N-Heterocyclic Carbene Complexes
for Olefin Metathesis....................................................................................91
Xavier Sauvage, Albert Demonceau, Lionel Delaude
Phosphine-Free EWG-Activated Ruthenium Olefin
Metathesis Catalysts: Design, Preparation, and Applications .................... 111
Karol Grela, Anna Michrowska, Michał Bieniek, Volodymyr Sashuk,
Anna Szadkowska
Metathesis Catalysts Stability and Decomposition Pathway......................125
Alexey V. Nizovtsev, Vladimir V. Afanasiev, Egor V. Shutko,
Natalia B. Bespalova
Ruthenium–Vinylidene Complexes: An Efficient Class of Homogeneous
Metathesis Catalysts...................................................................................137
Ileana Dragutan, Valerian Dragutan, Renata Drozdzak,
Francis Verpoort

v
vi Tableofcontents
Mesoporous Molecular Sieves as Supports for Metathesis Catalysts.........151
Hynek Balcar, Jiří Čejka
“Greener Shade of Ruthenium”: New Concepts of Activation,
Immobilization, and Recovery of Ruthenium Catalysts
for Green Olefin Metathesis.......................................................................167
Anna Michrowska, Łukasz Gułajski, Karol Grela
Ring-Opening Metathesis Activity of Ruthenium-Based
Olefin Metathesis Catalyst Coordinated
with 1,3-Bis(2,6-Diisopropylphenyl)-4,5-Dihydroimidazoline..................185
Solmaz Karabulut, Francis Verpoort
PART II. INTRICATE ORGANIC SYNTHESIS VIA METATHESIS
CHEMISTRY
Recent Applications of Alkene Metathesis for Fine Chemical
and Supramolecular System Synthesis.......................................................195
Franc Požgan, Pierre H. Dixneuf
The Olefin Metathesis Reactions Combined with Organo-Iron
Arene Activation Towards Dendrimers, and Polymers..............................223
Didier Astruc, Victor Martinez
Olefin Metathesis With Ruthenium-Arene Catalysts Bearing
N-Heterocyclic Carbene Ligands................................................................237
Lionel Delaude, Albert Demonceau
Olefin Metathesis Mediated By: - Schiff Base Ru-Alkylidenes -
Ru-Alkylidenes Bearing Unsymmetrical NHC Ligands............................251
Stijn Monsaert, Nele Ledoux, Bart Allaert, Renata Drozdzak,
Pascal Van Der Voort, Francis Verpoort
Cross-Metathesis of Vinyl-Substituted Organosilicon Derivatives
With Olefins and Dienes in the Presence of Grubbs Catalysts...................265
Cezary Pietraszuk, Helmut Fischer, Bogdan Marciniec
PART III. TAILORED POLYMERS BY METATHESIS
POLYMERIZATION
From Drug Cocktails to Tissue Engineering: Synthesis
of ROMP Polymers for Biomedical Applications......................................285
Kenneth D. Camm, Deryn E. Fogg
Table of contents vii
Precision Polyolefin Structure: Modeling Polyethylene Containing
Methyl and Ethyl Branches.........................................................................305
Giovanni Rojas, Kenneth B. Wagener

Modeling Low Density Polyethylene with Precisely Placed
Butyl Branches............................................................................................325
Giovanni Rojas, Kenneth B. Wagener
Correlating Precisely Defined Primary Structure with Crystalline
Properties in Halogen Containing Polyolefins............................................333
Emine Boz, Rufina G. Alamo, Kenneth B. Wagener
Synthesis of New Elastomers with Controlled Structures Based
on Alkylene Oxides, Grafted by ROMP.....................................................347
Bogdan Spurcaciu, Emil Buzdugan, Cristian-Andi Nicolae,
Ileana Dragutan, Valerian Dragutan
Investigation of the Microstructure of Metal Catalyzed Cyclopentene
Co-Norbornene Polymers by Spectral Methods.........................................355
Sevil Çetinkaya, Solmaz Karabulut, Yavuz İmamoğlu
ADMET Polymerization Activities of Electrochemically Reduced
W-Based Active Species for Ge and Sn Containing Dienes.......................361
Solmaz Karabulut, Cemil Aydogdu, Bülent Düz
and Yavuz İmamoğlu
A Study on the Reactivity of WCl –e––Al–CH Cl
6 2 2
with the Silicon-Containing Dienes............................................................367
Solmaz Karabulut, Cemil Aydogdu, Bülent Düz and Yavuz İmamoğlu
PART IV. ADVANCED MATERIALS VIA METATHESIS
AND RELATED CHEMISTRY
Catalytic Cycloisomerization of Enynes Involving Various Activation
Processes.....................................................................................................375
Christian Bruneau
ROMP, ROP, and Addition Polymerization of Silicon-Containing
Cyclic Monomers as a Way to New Membrane Materials.........................395
Maria L. Gringolts, Nikolai V. Ushakov, Yulia.V. Rogan,
Kiryll L. Makovetskii, Yuri P. Yampolskii, Eugene Sh. Finkelshtein
Polydiphenylacetylene with Schiff Base End Groups: Synthesis
and Characterization...................................................................................413
Radostina Kalinova, Christo Jossifov
viii Tableofcontents
Two-Way Intramolecular Transfer of Chirality
in Organocobalt Complexes........................................................................421
Claudia Zucchi, Davide Turrini, Roland Boese, Lajos Bencze,
Robert Kurdi, Georg Fráter, Luciano Caglioti, Gyula Pályi

Nanomolecular Switches Operated by Clockwork Mechanism.................441
Lajos Bencze, Robert Kurdi
Copolymerization of Ethylene with Norbornene and its Functional
Derivatives Catalyzed by Nickel Complexes with Phosphorylide
Ligands.......................................................................................................453
Victor I. Bykov, Vitalii A. Dronov, Tamara A. Butenko,
Eugene Sh. Finkelshtein and Kiryl L. Makovetskii
Carbonyl–Olefin Exchange Reaction: Present State
and Outlook.................................................................................................461
Christo Jossifov, Radostina Kalinova
Immobilization of Metal Nanoparticles in Surface Layer of Silica
Matrices......................................................................................................471
Kseniia Katok, Valentin Tertykh, Victor Yanishpolskii
Catalytic Alkene Metathesis in Ionic Liquids............................................483
Cédric Fischmeister
Subject Index..............................................................................................503
PREFACE
Following the fruitful tradition of the previous NATO Advanced Study Institute
(ASI) meetings held on metathesis chemistry in Akcay, Turkey (1989, 1995),
Polanica-Zdroj, Poland (2000), and Antalya, Turkey (2002), the new event on this
fascinating topic of chemistry (Nobel Prize, 2005), organized again in Antalya
during 4–16 September 2006, was devoted again to a hot subject in this field,
“New Frontiers in Metathesis Chemistry: From Nanostructure Design to Sustainable
Technologies for Synthesis of Advanced Materials”.
Olefin metathesis, one of the most efficient transition metal-mediated C–C bond-
forming reactions, asserted itself during the last few years as a powerful synthetic
strategy for obtaining fine chemicals, biologically active compounds, architecturally
complex assemblies, novel functionalized materials, and polymers tailored for speci-
fic utilizations (e.g. sensors, semiconductors, microelectronic devices), etc. Metathesis
reactions such as ring-closing metathesis (RCM), enyne metathesis, cross-metathesis
(CM), acyclic diene metathesis (ADMET), and ring-opening metathesis polymeri-
zation (ROMP) have gone far beyond 20th-century boundaries resulting in broad
diversification towards sustainable technologies and perspectives for industrial appli-
cations covering a wide range, from production of smart, nanostructured materials to
the manufacture of new pharmaceuticals.
As should have been expected for this timely NATO ASI meeting, seminal
contributions on catalyst-related topics highlighted the newest advances in ruthenium-
based complexes of high activity, selectivity, and robustness, popular for their excellent
tolerance towards a variety of functional groups. A whole range of alkylidene–Ru
complexes, both neutral and ionic, recoverable and recyclable, inclusive of prepa-
ration and selected applications, have been extensively illustrated by Pierre Dixneuf
(University of Rennes, France). Elaborating on the essential role played by
N-heterocyclic carbene (NHC) ligands in most effective Ru metathesis catalysts,
Steven P. Nolan (University of Tarragona, Spain) successfully reported on the concept
of incorporating this valuable moiety into other late transition metal complexes.
Deeper insights into catalyst design have been provided by Deryn Fogg (University
of Ottawa, Canada) and Natalya Bespalova (United Research & Development
Centre, Russia). Fogg clearly demonstrated how Ru catalysts containing electron-
deficient aryloxide (“pseudohalide”) ligands confer high activity at low catalyst
loadings, while also expanding the structural diversity of the ligand set and the
capacity for steric and electronic tuning of activity and selectivity. She pointed out
that by using the matrix-assisted laser desorption ionization mass spectrometry
(MALDI-MS) analysis technique distinctions in the behaviour of the Grubbs vs.
pseudohalide catalysts could be revealed providing further insights into the mecha-
nism of RCM reaction. Bespalova dwelt on modification of well-defined Ru–carbene
catalysts by changing the carbenoid moiety and the imidazole ligand which allows
variation of catalytic properties; a comparison of the new types of the catalysts with
ill-defined catalysts based on tungsten in CM was also presented.

ix
x Preface
Further, the concept of NHC utilization in catalysis has been extensively
developed by Lionel Delaude (University of Liege, Belgium), Karol Grela (Polish
Academy of Sciences, Poland), Francis Verpoort (University of Ghent, Belgium),
and Didier Astruc (University of Bordeaux, France). Poster presentations brought
additional information in support to the role of NHC ligands in Ru-based metathesis
pre-catalysts or the striking activating role of HCl in Ru complexes with O,N-bidentate
ligands. The newest trends evolved in the present research on heterogeneous
catalysis have been critically and selectively discussed by Hyniek Balcar (Czech
Academy of Sciences).
An original topic on combining simple arene activation with Ru-catalysed olefin
metathesis for the assembly and funtionalization of nano-objects has been dealt with
by Didier Astruc offering convenient access to the synthesis and chemistry of supra-
molecular structures. CM of vinyl-substituted organosilicon derivatives with olefins
in the presence of Grubbs catalysts presented by Cesar Pietraszuk (University of
Pozanan, Poland) evidenced how Ru-mediated metathesis can be fruitfully used in
synthesis of a novel class of silicon-containing advanced materials. New applications
of Ru-mediated metathesis reactions in tandem metathesis or non-metathesis process-
ses have been further fully documented by Deryn Fogg in an interesting presentation
on tandem ROMP-hydrogenation catalysis in tissue engineering applications, whereas
the contribution on the catalytic cycloisomerization of enynes involving various
activation processes by Christian Bruneau (University of Rennes, France) extended
the scope of Ru-based metathesis chemistry to a variety of initiating systems of
fundamental relevance for catalytic processes.
Beautiful contributions coming from Ken Wagener’s group (University of
Florida, USA) showed definitely how ADMET induced by Grubbs Ru catalysts can
rigorously control the polymer microstructure and ultimately the product properties.
Using efficient Ru-based initiators, new pathways for manufacture of high-molecular
weight polymers with well-defined architectures and particular properties have been
revealed. On this line, Eugene Finkelshtein (Russian Academy of Sciences, Russia)
evidenced the potential of producing specialty polymers by ROMP and other ring-
opening processes. Addition polymerization of selected monomers induced by the
late transition metal catalysts provided new materials having special properties as it
was convincingly shown in this section. Furthermore, synthesis and characterization
of poly(phenylacetylene) with Schiff base end groups, polymers endowed with electri-
cal properties, is dealt with by Christo Jossifov (Bulgarian Academy of Sciences).
Furthermore, nanostructured materials and how they could be used in nanomachines
and molecular clockworks and transfer of chirality in organometallic complexes
have been attractively highlighted by Lajos Bencze (Panonia University of Veszprem,
Hungary), in two complementary contributions. Going beyond metathesis, but in tight
correlation with this type of reaction, comprehensive presentations fully illustrated
the high potential of precisely controlled macromolecular structures obtained by
atom transfer radical polymerization (ATRP) to be assembled in smart materials,
sensors, and various molecular devices. Finally, the successful combination of ROMP
with ATRP to produce new materials with valuable properties has also been discussed.
Preface xi
In addition to the scientific sessions, the social programme was organized in a
friendly and warm style in order to facilitate more informal scientific discussions
between lecturers and young researchers, and to strengthen contacts and exchange of
ideas and information between research groups of different nationalities. Overall,
this outstanding international event organized under the generous sponsorship of the
NATO Public Diplomacy Division successfully surveyed the latest achievements in
this fascinating area of synthetic chemistry and uncovered new ways of developments
for industrial-scale applications.

Yavuz İmamoğlu Valerian Dragutan

January 2007
CO-DIRECTORS:

PROF. İMAMOĞLU YAVUZ Department of Chemistry,
Hacettepe University Beytepe,
Ankara 06800, Turkey
[email protected]

PROF. VALERIAN DRAGUTAN Institute of Organic Chemistry,
Romanian Academy, Bucharest,
Romanıa
[email protected]

ORGANISING COMMITTEE:

PROF. Y. İMAMOĞLU Department of Chemistry,
Hacettepe University Beytepe,
Ankara 06800, Turkey
PROF. VALERIAN DRAGUTAN Institute of Organic Chemistry,
Romanian Academy, Bucharest,
Romanıa

PROF. L. BENCZE Department of Organic
Chemist ry, Univers ity of
Veszprem , H-8200 , POB 158
Veszprem, Hungary

PROF. K.B. WAGENER Department of Chemistry,
Universit y o f Florida , POB
117200, Gainsville, FL 32611-
7200, USA

DR. E. KHOSRAVI IRC in Polymer Science and
Technology, Universi ty of
Durham , South Road Durham
DHI 3LE, UK
xiii