US EPA

8451210 

Journal Article 

Terminal oxidation of alkanes: A radically new approach? 

Labinger, JA 

1999 

3 

1 

18-23 

English 

While there have been many advances in the field of selective alkane functionalization over the last decade or two, one important target that has remained frustratingly elusive is selective oxidation at a terminal methyl position. A number of potential applications might be made practical if such methodology were available; the obvious one would be the production of linear terminal alcohols from alkane feedstock, rather than from olefins (via hydroformylation) as currently practiced. The late Derek Barton proclaimed selective methyl oxidation to be among the major unsolved problems of organic chemistry. In response to this challenge J. D. Roberts has put up a prize: 5000 for the first to achieve oxidation (chemical or biochemical) of n-hexane to adipic acid with 85% selectivity[1]. Very recently, J. M. Thomas and coworkers found that reaction of linear alkanes with molecular oxygen, catalyzed by transition metal-substituted molecular sieves, can give unexpectedly high selectivity for terminal oxidation [21]. While the report does not appear to present any immediate threat to Jack Roberts' pocketbook, it does offer considerable encouragement. Perhaps most intriguingly, it takes a quite different approach from what previous common wisdom would seem to suggest. In the following perspective, I will give some background on the terminal oxidation problem, summarize the findings reported, and offer some mechanistic speculation which may indicate some potentially profitable directions for further research. © BALTZER SCIENCE PUBLISHERS .