Science of Synthesis

Mortreux, A.; Sauthier, M.; Monflier, E.; Tilloy, S., Science of Synthesis: C-1 Building Blocks in Organic Synthesis, (2014) 1, 174.

Far fewer examples are known in the literature that relate to the use of platinum/tin-based catalysts for hydroformylation. Among the reasons is the lack of selectivity for the linear aldehyde product, as well as the use of rather high temperatures and pressures, which leads to some hydrogenation of the substrate. Nevertheless, interesting results have been reported when using electrochemically synthesized catalysts, starting from well-defined platinum catalyst ‌26‌ or [1,4-bis(diphenylphosphino)butane]dichloroplatinum(0) complexes using a tin[‌31‌] or iron[‌32‌] anode to produce unusual chelated bridged platinum dihydride cationic species {i.e., [(Diop)Pt(H)(µ-Diop)Pt(H)(Diop)]2+; Diop = [2,3-O-isopropylidene-2,3-dihydroxy-1,4-bis(diphenylphosphino)butane]}. The polar propylene carbonate (4-methyl-1,3-dioxolan-2-one) was used initially as cosolvent in these reactions to favor the electrochemical process. Remarkably, high linear/branched product ratios (up to 57:1) are obtained when using hex-1-ene as the substrate. Furthermore, 90% selectivity for the linear aldehyde is obtained from the hydroformylation of styrene (‌Scheme 12‌).

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References