Mathieu Sauthier

New synthesis of 1,4-diketones via rhodium-catalysed 1,4 carbonylative addition of arylboronic acids to α,β-unsaturated ketones

The reaction of various arylboronic acids with α,β-unsaturated ketones under CO pressure and in the presence of rhodium catalyst yields 1,4-diketones.

Carbonylative 1,4-addition of potassium aryltrifluoroborates to vinyl ketones

Potassium aryltrifluoroborates have proven to be useful reagents for the carbonylative aroylation of vinyl ketones; this study broadens the scope of potassium aryltrifluoroborates in homogeneous catalysis and shows that the solvent can act as the proton source for this family of reactions.

Telomerisation of 1,3‐Butadiene with 1,4:3,6‐Dianhydrohexitols: An Atom‐Economic and Selective Synthesis of Amphiphilic Monoethers from Agro‐Based Diols

The telomerisation of 1,3-butadiene with a Pd/TPPTS catalytic system in water or an organic solvent was used for the synthesis of C8 ethers from isosorbide, an agro-based diol. The use of water/oil biphasic reaction conditions allowed the selective synthesis of monoethers with improved rates upon using inorganic bases as promotors. As isosorbide is a non-symmetric diol, the two hydroxyl groups display different reactivities. 2-O-substituted-monoethers were preferentially obtained if water was used as the solvent, whereas in DMSO 5-O-substituted monoethers were the major products. Complete conversions of isosorbide with up to 94% monoether selectivities were obtained. The optimized reaction conditions were successfully applied to isomannide and isoidide for the selective synthesis of the derived ethers. An improved reactivity of the endo-hydroxy groups of isosorbide and isomannide versus the exo-hydroxy groups of isosorbide and isoidide was observed if the reaction was performed in DMSO instead of water.

Synthesis of isosorbide: an overview of challenging reactions

Isosorbide is a diol derived from sorbitol and obtained through dehydration reactions that has raised much interest in the literature over the past few decades. Thus, this platform chemical is a biobased alternative to a number of petrosourced molecules that can find applications in a large number of technical specialty fields, such as plasticizers, monomers, solvents or pharmaceuticals. The synthesis of isosorbide is still a technical challenge, as several competitive reactions must be simultaneously handled to promote a high molar yield and avoid side reactions, like degradation and polymerization. In this purpose, many studies have proposed innovative and varied methods with promising results. This review gives an overview of the synthesis strategies and catalysts developed to access this very attractive molecule, pointing out both the results obtained and the remaining issues connected to isosorbide synthesis.

Nickel‐Catalysed Hydroalkoxylation Reaction of 1,3‐Butadiene: Ligand Controlled Selectivity for the Efficient and Atom‐Economical Synthesis of Alkylbutenyl Ethers

The nickel-catalysed hydroalkoxylation of butadiene is promoted by a nickel(0)/dppb catalyst (dppb = 1,4-bis(diphenylphosphino)butane; see scheme). By following this new synthetic procedure, alkylbutenyl ethers are readily obtained from an alcohol and 1,3-butadiene with exclusion of dimerisation and telomerisation products.

Synthesis of α-alkylated β-ketoesters by alkoxycarbonylation/Michael addition domino reaction.

The palladium-catalyzed alkoxycarbonylation of an α-chloro ketone can be efficiently combined to a Michael addition reaction in a new two-step domino reaction, allowing the synthesis of original highly functionalized α-alkylated β-ketoesters. The scope of the reaction was extended to several α-chloro ketones and Michael acceptors with moderate to very good yields.

Synthesis of 1,4:3,6-Dianhydrohexitols Diesters from the Palladium-Catalyzed Hydroesterification Reaction

The hydroesterification of alpha olefins has been used to synthesize diesters from bio-based secondary diols: isosorbide, isomannide, and isoidide. The reaction was promoted by 0.2% palladium catalyst generated in situ from palladium acetate/triphenylphosphine/para-toluene sulfonic acid. Optimized reaction conditions allowed the selective synthesis of the diesters with high yields and the reaction conditions could be scaled up to the synthesis of hundred grams of diesters from isosorbide and 1-octene with solvent-free conditions.

Effect of Chain Unsaturation on the Self-Association of Tri- and Tetraethylene Glycol Octyl Ethers Obtained by Butadiene Telomerization

2,7-Octadienyl ethers of tri- and tetraethylene glycol (C(8:2)E(3) and C(8:2)E(4)) have been synthesized by the atom-economical butadiene telomerization of the corresponding poly(ethylene glycols). On one hand, this synthetic path is attractive because it is expeditious and environmentally benign, and on the other hand, it provides unconventional amphiphiles for which the lipophilic chains possess two double bonds. These two unsaturations increase the global hydrophilicity of the compound, which is also highlighted by the modelization of the compounds using the conductor-like screening model for real solvents (COSMO-RS). The behavior of C(8:2)E(3) and C(8:2)E(4) in binary amphiphile/water and ternary amphiphile/oil/water systems is therefore greatly modified compared to that of the conventional fully saturated homologues (C(8)E(3) and C(8)E(4)) that are easily obtained after hydrogenation. This results in a lowered efficiency of the unsaturated compounds for oil solubilization. The usual Winsor-type microemulsion systems are formed, and for the same oil, the DLS investigation of the microstructure of the Winsor I microemulsion does not highlight any difference in the self-association between the unsaturated and saturated compounds.

The Palladium-Catalyzed Carbonylative Telomerization Reaction with Phenols, Polyphenols and Kraft Lignin

An efficient carbonylative coupling reaction of two equivalents of 1,3-butadiene, yielding aryl nona-3,8-dienoate esters, is performed with phenols as nucleophile, and promoted by palladium-based catalysts. Optimization study reveals the key role of benzoic acid as a cocatalyst. The suggested catalyst combination enables the conversion of a wide scope of variously substituted phenols into corresponding esters with a high yield. Further tests were performed with diphenols, naturally-occurring phenols and an industrial grade Kraft lignin, thus, indicating the scope of this reaction for transforming industrially relevant polyphenolic structures.