Atomic Energy and Alternative Energies Commission (CEA)

Iramis Institute, SIS2M CEA/CNRS Research Unit

91191 Gif-sur-Yvette (France)

thibault.cantat@cea.fr

While greenhouse gases emissions are reaching alarming levels, fossil fuels still represent 80% of the world energy portfolio and 95% of our chemical commodities rely on non-renewable resources, namely hydrocarbons. In this context, utilizing CO₂ as a C₁ building block to produce platform chemicals as an alternative to petrochemistry has a double advantage of reusing CO₂ while sparing fossil resources and avoiding CO₂ emissions from their use. We have developed a strategy relying on the simultaneous use of a functionalizing reagent and a reductant that can be independently adjusted to perform the reductive functionalization of CO₂. The so-called diagonal approach will be discussed and exemplified with novel catalytic processes to convert CO₂ to formamides, N-heterocycles and methylamines, using organosilanes and amines.^[1-8] These new catalytic reactions rely on the use of simple organocatalysts or Zn and Fe organometallic complexes and therefore circumvent the use of toxic and expensive metals for the formylation of a variety N–H bonds (in amines, imines, hydrazines and N-heterocycles). This strategy enables an efficient co-recycling of CO₂ with polymethylhydrosiloxane (PMHS), a by-product from the silicone industry.^[1-8]

Figure 1 Co-recycling of CO₂ and polymethylhydrosiloxane (PMHS) for the formylation of N–H bonds

[1] C. Das Neves Gomes, O. Jacquet, C. Villiers, P. Thuéry, M. Ephritikhine, T. Cantat, Angew. Chem. Int. Ed. 2012, 51, 187.

[2] O. Jacquet, C. Das Neves Gomes, M. Ephritikhine, T. Cantat, J. Am. Chem. Soc. 2012,134, 2934.

[3] O. Jacquet, C. Das Neves Gomes, M. Ephritikhine, T. Cantat, ChemCatChem 2013, 5, 117.

[4] O. Jacquet, X. Frogneux, C. Das Neves Gomes, T. Cantat, Chemical Science 2013, DOI:10.1039/C3SC22240C.

[5] O. Jacquet, C. Gomes, T. Cantat, Process for the preparation of formamides, patent application FR1154246, filed May 16-2011.

[6] O. Jacquet, C. Gomes, T. Cantat, Process for the preparation of nitrogen compounds, patent application FR1255238, filed May 5-2012.

[7] O. Jacquet, C. Gomes, T. Cantat, Process for the preparation of formamidines, patent application FR1259757, filed October 12-2012.

[8] O. Jacquet, C. Gomes, T. Cantat, Process for the preparation of methylamines, patent application FR1255234, filed May 5-2012.