Download Catalysis by main-group metal - Université Paris-Sud

Taiwan Paris-Sud Scholarship program 2017/2018
PhD project proposal form
Discipline
Chemistry
Doctoral School
571 – Chemistry science
Thesis subject title
Catalysis by main-group metal
Laboratory name
Laboratory web site
Equipe de Catalyse Moléculaire, ICMMO, Université Paris Sud
http://www.ecm.u-psud.fr and www.polycata.u-psud.fr
PhD supervisor (contact person)
 Name
Bour Christophe
 Position
Associate Professor
 Email
[email protected]
 Phone number
0033 1 6915 7651
Thesis proposal (max 1500 words)
The discovery of simple processes and reactions for the formation of C-N bonds represents an important challenge for
synthetic chemists.1 Substituted amines have wide applications in the synthesis of drugs, dyes, detergents, fragrances,
pharmaceuticals, and crop protection agents. Among the various strategies for amine synthesis, the direct amination of
alcohols through borrowing hydrogen catalysis (or hydrogen auto transfer),2 has been recognized as one of the most practical
methods for the industrial production of substituted alkyl amines. The broad availability of alcohols, combined with the fact
that water is the only by-product of such reactions, which fulfills the overarching principles of green chemistry, are the reasons
for its large-scale use. The evolution of the catalytic systems from their discovery to their applicability in this atom economical
and redox-neutral process is particularly interesting. It was first reported with simple 2nd and 3rd row late transition metals
complexes, which were rapidly followed by high-tech well-defined complexes (Ru,3 Rh,4 Ir,5 or Os6). The current trend is to
replace these noble elements by cheaper and more abundant 1st row transition metals. In that respect, significant improvements
have recently been made by using Mn,7 Fe8 and Co-based catalysts.9 However, there is still a strong need for even more active
catalysts that: a) work under milder conditions, b) allow broader substrate scope and, c) improve selectivity and turnover
numbers.
In the past five years, it has been demonstrated that Group 13 metals could be used for facile and tunable redox chemistry. The
redox processes could be achieved using redox-active ligands with a wide range of applications.10 Ligands, that can store and
release electrons, have now been extensively explored and harnessed as electron-reservoirs in catalytic applications. The use of
metal centers in a single fixed oxidation state, for example in the pincer systems of Milstein, suggests that bond activation
processes, as shown below, might be also implemented with complexes of the Lighter main-group metal complexes.11
For instance, an electrophilic group 13 complex bearing a redox-active bis-iminopyridine ligand has been employed to
catalyze the dehydrogenative coupling of benzylamine,12 dehydrogenation of formic acid,13 and to convert CO2 into MgCO3
and CaCO3.14 These results support the view that redox chemistry is possible with redox-silent elements some preconceived
visions in 2-electrons redox processes regarding p-block metals must be revised. Thus, the objective of this project, directed
towards main-group metal catalysis, is to investigate the reactivity of main-group metals bearing redox-active ligands in
various reactions.
PhD student will have opportunities to study molecular synthesis, organometallic chemistry and catalysis, to meet a large
community of chemists and to participate in internal and external meetings and symposiums. This will give them solid and
practical experiences to pursue their careers either in academic or industrial communities.
Université Paris Sud (Shanghai Ranking 2016)= 46th
“A prestigious and multidisciplinary university with a strong science and health science component, Université Paris-Sud
enjoys an outstanding international reputation thanks to the exceptional quality of its research, the appeal of its programs of
study, its fulfilling student life, its multiple partnerships, and the knowledge and skills of its staff.”15
Publications of the laboratory in the field (max 5)
1.
Calcium-Catalyzed Synthesis of Polysubstituted 2-Alkenylfurans from β-Keto Esters Tethered to Propargyl Alcohols.
Morcillo, S. P.; Lebœuf, D.; Bour, C.; Gandon, V. Chem. Eur. J. 2016. Advance Article, DOI: 10.1002/chem.201603929.
2.
Catalytic applications of [IPr-GaX2][SbF6] and related species. Michelet, B.; Tang, S.; Thiery, G.; Monot, J.; Li, H.; Guillot,
R.; Bour, C.; Gandon, V. Org. Chem. Front. 2016, 3, 1603. (Selected for the front cover)
3.
Dibromoindium(III) Cation as -Lewis Acid: Characterization of [IPr·InBr2][SbF6] and Catalytic Activity Towards
Alkynes and Alkenes. Colard-Itté, J. R.; Michelet, B.; Guillot, R.; Bour, C.; Gandon, V. Chem. Commun. 2015, 51, 7401.
4.
Well-Defined Organo-Gallium Complexes as Lewis Acids for Molecular Catalysis: Structure-Stability-Activity
Relationships. Bour, C.; Gandon, V. Coord. Chem. Rev. 2014, 279, 43.
5.
Copper Salts as Additives in Gold(I)-Catalyzed Reactions. Guérinot, A.; Fang, W.; Sircoglou, M.; Bour, C.; BezzenineLafollée, S.; Gandon, V. Angew. Chem. Int. Ed. 2013, 52, 5848.
1
For selected review on C-N bonds formation: Bariwal, J.; Van der Eycken, E. Chem. Soc. Rev. 2013, 42, 9283.
Wang, Q. ; Yu, Z. Chem. Soc. Rev. 2015, 44, 2305.
3
For selected examples of Ru-catalyzed aminations of alcohols, see: Gunanathan, C.; Milstein, D. Angew. Chem. Int. Ed. 2008, 47, 8661.
4
Zweifel, T.; Naubron, J.-V.; Grützmacher, H. Angew. Chem. Int. Ed. 2009, 48, 559.
5
For selected examples of Ir-catalyzed aminations of alcohols, see Kawahara, R.; Fujita, K.-I.; Yamaguchi, R. J. Am. Chem. Soc. 2010, 132,
15108.
6
Bertoli, M.; Choualeb, A.; Lough, A. J.; Moore, B.; Spasyuk, D.; Gusev, D. G. Organometallics 2011, 30, 3479.
7
Elangovan, S.; Neumann, J.; Sortais, J.-B.; Junge, K.; Darcel, C.; Beller, M. Nature Commun. 2015, 7, 12641.
8
Yan, T.; Feringa, B. L.; Barta, K. Nat. Comm. 2014, 5, 5602.
9
Rösler, S.; Ertl, M.; Irrgang, T.; Kempe, R. Angew. Chem. Int. Ed. 2015, 54, 15046.
10
Luca, O. R.; Crabtree, R. H. Chem. Soc. Rev. 2013, 42, 1440.
11
Gunanathan, C.; Milstein, D. Chem. Rev. 2014, 114, 12024.
12
Myers, T. W.; Berben, L. A. J. Am. Chem. Soc. 2013, 135, 9988.
13
Myers, T. W.; Berben, L. A. Chem. Sci. 2014, 5, 2771.
14
Myers, T. W.; Berben, L. A. Chem. Commun. 2013, 49, 4175.
2
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