• Aucun résultat trouvé

Highly chemoselective catalytic transfer hydrosilylation of aldehydes

N/A
N/A
Protected

Academic year: 2021

Partager "Highly chemoselective catalytic transfer hydrosilylation of aldehydes"

Copied!
2
0
0

Texte intégral

(1)

HAL Id: cea-02341556

https://hal-cea.archives-ouvertes.fr/cea-02341556

Submitted on 31 Oct 2019

HAL is a multi-disciplinary open access

archive for the deposit and dissemination of sci-entific research documents, whether they are pub-lished or not. The documents may come from teaching and research institutions in France or abroad, or from public or private research centers.

L’archive ouverte pluridisciplinaire HAL, est destinée au dépôt et à la diffusion de documents scientifiques de niveau recherche, publiés ou non, émanant des établissements d’enseignement et de recherche français ou étrangers, des laboratoires publics ou privés.

Highly chemoselective catalytic transfer hydrosilylation

of aldehydes

Clément Chauvier, Thibault Cantat

To cite this version:

Clément Chauvier, Thibault Cantat. Highly chemoselective catalytic transfer hydrosilylation of alde-hydes. 3rd International Green Catalysis Symposium, Mar 2017, Rennes, France. �cea-02341556�

(2)

International Green Catalysis Symposium, 2017, Rennes, France

HIGHLY CHEMOSELECTIVE CATAL YTIC TRANSFER

HYDROSIL YLATION OF ALDEHYDES

Clément Chauvier,a Thibault Cantat*

1 NIMBE, CEA, CNRS, Université Paris-Saclay, Gif-sur-Yvette, France

clement.chauvier@cea.fr

Catalytic hydrosilylation has found widespread applications in the silicon industry and in synthetic organic chemistry owing to its ability to induce both reduction (hydro) and functionalization (silylation) of uns~turated bonds such as C=C or c=o bonds in an atom-economical manner.1 Nevertheless,' the preparation of hydrasilanes (R3SiH) relies on energy-intensive pracesses based either on costly redox-manipulation of Si or on the reduction of chlorasilanes with highly reactive metal hydrides such as LiAIH4 •

To circumvent these limitations, we have developed a conceptual alternative consisting in the utilization of silyl formates (R3SiOC(O)H), readily prepared fram formic acid and chlorasilanes, as surragates of hydrasilanes in hydrasilylation reactions.2 The key feature of this endeavor stems fram the renewability of the hydridic counterpart in the silyl formates since formic acid can be obtained by 2e- electrareduction of CO2•3

The viability of the aforementioned concept has been demonstrated with the catalytic transfer hydrasilylation of aldehydes. In the presence of a well-defined ruthenium catalyst, various aldehydes are efficiently and chemoselectively reduced to silyl ethers with the concomitant release of CO2 . Mechanistic insights were gained by both experimental

observations and DFT calculations and they highlight the pivotai raie of a transmetallation step to rationalize the outstanding chemoselectivity of the pracess.4

j

Si-CI

- HCI

2 e-+ 2 H+ 2e" electroreduction

[Si'oJLJ

[Ru] ca!.

~Si-H-surrogate

\ . . - - - - -...

, - - - _

... )

Y

Recyclabte

Transfer Hydrosilylation

1 B. Marciniec, H. Maciejewski, C. Pietraszuk, P. Pawluc, Hydrosilylation: A Comprehensive Review on Recent Advances, Vol. 1 (Ed.: B. Marciniec), Springer, Berlin, 2009.

2 For conceptually related works, see: a) C. Chauvier, P. Thuéry, T. Cantat, Chem. Sei. 2016, 7,5680; b) M.

Oestreich, Angew. Chem., Int. Ed. 2016, 55, 494.

3 A. S. Agarwal, Y. Zhai, D. Hill, N. Sridhar, ChemSusChem, 2011, 4, 1301.

Références

Documents relatifs

L’archive ouverte pluridisciplinaire HAL, est destinée au dépôt et à la diffusion de documents scientifiques de niveau recherche, publiés ou non, émanant des

Lucile Etienne, Abdelkarim Daoud, Gérard Beltrando.. To cite

Pour la théorie des graphes, un graphe simple est constitué d’un seul ensemble de sommets et ne comprend ni boucle - lien d’un sommet vers lui- même (loop, reflexive tie ou self-tie)

In the present paper, trade-o ff studies focused on technology modules are reported including the in fluence of some design-driving assumptions on the reactor performances and

With low catalytic loading, the efficient hydrosilylation of aldehydes in the presence of diphenylsilane led to the synthesis of dialkoxydiphenylsilanes.. Other studies on

For the multi-resource allocation problem in network slicing, we provide two scheduling algorithms that take into account SLA requirements in terms of minimum and nominal

All species in all phylogenies were coded as present or absent in 10 Neotropical regions (Fig. 1): two predominantly forested/wet regions (Amazonia and Atlantic Forests),

Centre International de Mathématiques Pures et Appliquées), an interna- tional organization helping to promote the mathemati- cal sciences in developing countries supported by