Molecules 2010, 15(4), 2631-2650; doi:10.3390/molecules15042631
Article

New Chiral Phosphoramidite Complexes of Iron as Catalytic Precursors in the Oxidation of Activated Methylene Groups

1 University of Missouri - St. Louis, Department of Chemistry and Biochemistry, One University Boulevard, St. Louis, MO 63121, USA 2 Department of Chemistry and Biochemistry and Center for Nanoscience, University of Missouri - St. Louis, One University Boulevard, St. Louis, MO 63121, USA
* Author to whom correspondence should be addressed.
Received: 21 February 2010; in revised form: 31 March 2010 / Accepted: 6 April 2010 / Published: 12 April 2010
(This article belongs to the Special Issue Organometallic Chemistry)
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Abstract: New phosphoramidite complexes of iron were synthesized and structurally characterized. Reaction of the known chiral phosphoramidites (RO)2PNR’2 (R = binaphthyl, R’ = CH3, 1a; R = binaphthyl, R’ = benzyl, 1b) with [FeBr(Cp)(CO)2] afforded the title compounds [FeBr(Cp)(CO)(1a,b)] (4a,b) in 34 and 65 % isolated yields as mixtures of diastereomers, since both the metal and the ligand are stereogenic. Similarly, reaction of 1b with [Fe(Cp)I(CO)2] in the presence of catalytic [Fe(Cp)(CO)2]2 afforded [Fe(Cp)I(CO)(1b)] (5b) in 81% yield as a mixture of diastereomers. The molecular structures of 4a, 4b and 5 were determined, revealing a pseudo octahedral coordination geometry about the iron center. The new metal complexes are catalytically active in the oxidation of benzylic methylene groups to the corresponding ketones, utilizing t-BuOOH as oxidant (2 mol% catalyst, 36 h, room temperature, 31−80% yield).
Keywords: iron; phosphoramidites; X-ray; chiral at metal; benzylic oxidations

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MDPI and ACS Style

Shejwalkar, P.; Rath, N.P.; Bauer, E.B. New Chiral Phosphoramidite Complexes of Iron as Catalytic Precursors in the Oxidation of Activated Methylene Groups. Molecules 2010, 15, 2631-2650.

AMA Style

Shejwalkar P, Rath NP, Bauer EB. New Chiral Phosphoramidite Complexes of Iron as Catalytic Precursors in the Oxidation of Activated Methylene Groups. Molecules. 2010; 15(4):2631-2650.

Chicago/Turabian Style

Shejwalkar, Pushkar; Rath, Nigam P.; Bauer, Eike B. 2010. "New Chiral Phosphoramidite Complexes of Iron as Catalytic Precursors in the Oxidation of Activated Methylene Groups." Molecules 15, no. 4: 2631-2650.

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