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1.1.1 Hydroformylation of Alkenes

DOI: 10.1055/sos-SD-212-00003

Bronger, R. P. J.; Kamer, P. C. J.; Vogt, D.Science of Synthesis: C-1 Building Blocks in Organic Synthesis, (2014123.

General Introduction

Like many landmark discoveries, hydroformylation was discovered serendipitously and it celebrates its 75th anniversary in 2013. In 1938, while investigating the intermediacy of alkenes in the Fischer–Tropsch reaction, Otto Roelen discovered that alkenes are converted into linear and branched aldehydes by applying a cobalt-containing heterogeneous catalyst under a carbon monoxide and dihydrogen atmosphere (Scheme 1).[‌1‌‌3‌] The actual catalyst turned out to be the in situ generated homogeneous tetracarbonylhydridocobalt(I) complex [CoH(CO)4]. The initial activities and selectivities were quite moderate but major improvements have been accomplished over the years resulting in numerous industrial applications implemented after World War II. This clean and mild method for the functionalization of hydrocarbons has since grown to be among the most important homogeneously catalyzed reactions in industry, with an annual production of 8 million tons of various aldehydes and alcohols for the manufacture of detergents, soaps, and plasticizer alcohols. 2-Ethylhexan-1-ol, produced by linear-selective hydroformylation of propene, followed by aldol condensation, and subsequent reduction, has been the main product of industrial hydroformylation. For higher alkene hydroformylation, linear products are preferred over the branched ones because of their better biodegradability;[‌4‌‌6‌] however, highly branched products are also sometimes desirable for their properties, for example as lubricating-oil additives in order to depress the freezing point of the oil.[‌7‌]

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