Hydrohydroxymethylation

However, since the goal of this work was the synthesis of alcohols from olefins via hydrohydroxymethylation (75, 76), little attention was given to developing a shift-catalyst per se. Pettit has recently reexamined some of this work and shown that, by careful control of the pH of the reaction mixture, systems based on either Fe(CO)5 or Cr(CO)6 can be developed for the production of either formic acid or methanol from carbon monoxide and water (77, 78). Each of these latter systems involves the formation of metal hydride complexes consequently, molecular hydrogen is also produced according to the shift reaction [Eq. (16)]. 

Another noncatalytic step proposed by King et al. (18) in iron carbonyl/base catalysis of the WGSR involves the formation of formate ion however, we recently observed that formate formation appears to have little importance in the related rhodium catalysis of hydrohydroxymethylation. We plan to perform studies of the CO + KOH and C02 + KOH reactions independent of catalysis to more fully appreciate the relationship of these reactions to solution pH and thus the catalytic activity. 

Addition of Alcohols (Hydrohydroxymethylation), Ethers, and (2-substituted) 1,3-Dioxolane(s)... 

Hydrogen can be generated from water with carbon monoxide by the water-gas shift reaction (cf. Section V,A). Therefore, water can be used in the place of molecular hydrogen for the oxo synthesis. This modification, which converts olefins predominantly into alcohols, is generally called hydrohydroxymethylation ... 

Hydrohydroxymethylation Including Hydroformylation of Olefins with CO/H2 Catalyzed... 

Kdpfer A, Sam B, Breit B, Krische MI (2013) Regiodivergent reductive coupling of 2-substimted dienes to formaldehyde employing ruthenium or nickel catalysts hydrohydroxymethylation via transfer hydrogenation. Chem Sci 4 1876-1880... 

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