Towards Selective Syntheses of Octadienylethers from the Butadiene Palladium‐catalyzed Telomerization with Polyols in Aqueous Biphasic Medium

Abstract

The palladium catalyzed telomerization of butadiene with polyols has been efficiently performed under aqueous and biphasic medium leading to the corresponding octadienylethers. Depending on the choice of the organic co-solvent and nature of the catalyst employed to promote the reaction, mono-to fully substituted ethers could be obtained with high selectivities and yields. Particularly, pentaerythritol was telomer-ized for the first time allowing the selective synthesis of the corresponding monotelomers by using methylethylketone as organic co-solvent and the water soluble ligand TPPTS associated to a simple palladium precursor. Polyethers of sorbitol could be efficiently obtained by using a mixture of TPPTS and PPh 3 ligands.

Controlling the pH-response of branched copolymer nanoprecipitates synthesised by transfer-dominated branching radical telomerisation (TBRT) through telogen chemistry and spatial distribution of tertiary amine functionality

“…29,30 Such approaches have been recently utilised to combine unsaturated natural product taxogens, such as terpenes, into a range of useful chemical building blocks using telogens such as alcohols, amines, thiols, carbon dioxide and carbon monoxide. [31][32][33][34] In summary, TBRT uses similar free radical conditions that have been reported many times for the synthesis of linear telomers from mono-vinyl taxogens; [35][36][37][38][39][40][41][42] however, the use of multi-vinyl taxogens (MVTs) in the presence of sufficient amounts of telogen to maintain a number average telomer length of <2 vinyl units, allows TBRT to generate very high molecular weight polymers from the homopolymerisation of MVTs, at full conversion of vinyl functional groups, without the formation of crosslinked gels. 25,[43][44][45] We have recently demonstrated new strategies to form novel statistical copolymers through TBRT chemistry.…”

“…29,30 Such approaches have been recently utilised to combine unsaturated natural product taxogens, such as terpenes, into a range of useful chemical building blocks using telogens such as alcohols, amines, thiols, carbon dioxide and carbon monoxide. 31–34…”