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Iron-catalysed, general and operationally simple formal hydrogenation using Fe(OTf)3 and NaBH4.

MacNair AJ, Tran MM, Nelson JE, Sloan GU, Ironmonger A, Thomas SP - Org. Biomol. Chem. (2014)

Bottom Line: An operationally simple and environmentally benign formal hydrogenation protocol has been developed using highly abundant iron(iii) salts and an inexpensive, bench stable, stoichiometric reductant, NaBH4, in ethanol, under ambient conditions.This reaction has been applied to the reduction of terminal alkenes (22 examples, up to 95% yield) and nitro-groups (26 examples, up to 95% yield).Deuterium labelling studies indicate that this reaction proceeds via an ionic rather than radical mechanism.

View Article: PubMed Central - PubMed

Affiliation: School of Chemistry, University of Edinburgh, Joseph Black Building, West Mains Road, Edinburgh EH9 3JJ, UK. stephen.thomas@ed.ac.uk.

ABSTRACT
An operationally simple and environmentally benign formal hydrogenation protocol has been developed using highly abundant iron(iii) salts and an inexpensive, bench stable, stoichiometric reductant, NaBH4, in ethanol, under ambient conditions. This reaction has been applied to the reduction of terminal alkenes (22 examples, up to 95% yield) and nitro-groups (26 examples, up to 95% yield). Deuterium labelling studies indicate that this reaction proceeds via an ionic rather than radical mechanism.

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Iron-catalysed reductions and reductive functionalisations. TTP = tetraphenylporphyrinato. [Fe] = iron phenanthroline complex pyrolysed onto a carbon support.
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sch1: Iron-catalysed reductions and reductive functionalisations. TTP = tetraphenylporphyrinato. [Fe] = iron phenanthroline complex pyrolysed onto a carbon support.

Mentions: Ashby used LiAlH4 in conjunction with stoichiometric amounts of transition metal halides, including FeCl3 and FeCl2, to reduce 1-octene.10 Kano reported a biomimetic reduction of styrene derivatives using an iron-porphinato complex and NaBH4 however reductive homocoupling of radical species was a major side-reaction.11 Recently, Boger reported the hydrofunctionalisation of alkenes mediated by superstoichiometric iron(iii) salts and NaBH4.12 In the absence of an electrophile, it was found that tertiary alkenes were hydrogenated (Scheme 1).12a


Iron-catalysed, general and operationally simple formal hydrogenation using Fe(OTf)3 and NaBH4.

MacNair AJ, Tran MM, Nelson JE, Sloan GU, Ironmonger A, Thomas SP - Org. Biomol. Chem. (2014)

Iron-catalysed reductions and reductive functionalisations. TTP = tetraphenylporphyrinato. [Fe] = iron phenanthroline complex pyrolysed onto a carbon support.
© Copyright Policy - open-access
Related In: Results  -  Collection

License
Show All Figures
getmorefigures.php?uid=PMC4295815&req=5

sch1: Iron-catalysed reductions and reductive functionalisations. TTP = tetraphenylporphyrinato. [Fe] = iron phenanthroline complex pyrolysed onto a carbon support.
Mentions: Ashby used LiAlH4 in conjunction with stoichiometric amounts of transition metal halides, including FeCl3 and FeCl2, to reduce 1-octene.10 Kano reported a biomimetic reduction of styrene derivatives using an iron-porphinato complex and NaBH4 however reductive homocoupling of radical species was a major side-reaction.11 Recently, Boger reported the hydrofunctionalisation of alkenes mediated by superstoichiometric iron(iii) salts and NaBH4.12 In the absence of an electrophile, it was found that tertiary alkenes were hydrogenated (Scheme 1).12a

Bottom Line: An operationally simple and environmentally benign formal hydrogenation protocol has been developed using highly abundant iron(iii) salts and an inexpensive, bench stable, stoichiometric reductant, NaBH4, in ethanol, under ambient conditions.This reaction has been applied to the reduction of terminal alkenes (22 examples, up to 95% yield) and nitro-groups (26 examples, up to 95% yield).Deuterium labelling studies indicate that this reaction proceeds via an ionic rather than radical mechanism.

View Article: PubMed Central - PubMed

Affiliation: School of Chemistry, University of Edinburgh, Joseph Black Building, West Mains Road, Edinburgh EH9 3JJ, UK. stephen.thomas@ed.ac.uk.

ABSTRACT
An operationally simple and environmentally benign formal hydrogenation protocol has been developed using highly abundant iron(iii) salts and an inexpensive, bench stable, stoichiometric reductant, NaBH4, in ethanol, under ambient conditions. This reaction has been applied to the reduction of terminal alkenes (22 examples, up to 95% yield) and nitro-groups (26 examples, up to 95% yield). Deuterium labelling studies indicate that this reaction proceeds via an ionic rather than radical mechanism.

Show MeSH
Related in: MedlinePlus