Making Fe(BPBP)-catalyzed C-H and C[double bond, length as m-dash]C oxidations more affordable

The limited availability of catalytic reaction components may represent a major hurdle for the practical application of many catalytic procedures in organic synthesis. In this work, we demonstrate that the mixture of isomeric iron complexes [Fe(OTf)2(mix-BPBP)] (mix-1), composed of Λ-α-[Fe(OTf)2(S,S...

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Bibliographic Details
Published in:	Organic & biomolecular chemistry Vol. 12; no. 13; p. 2062
Main Authors:	Yazerski, Vital A, Spannring, Peter, Gatineau, David, Woerde, Charlotte H M, Wieclawska, Sara M, Lutz, Martin, Kleijn, Henk, Gebbink, Robertus J M Klein
Format:	Journal Article
Language:	English
Published:	England 01-01-2014
Subjects:	Biological Products - chemistry Catalysis Epoxy Compounds - chemical synthesis Epoxy Compounds - chemistry Ferrous Compounds - chemistry Hydrocarbons - chemistry Hydrogen Peroxide - chemistry Molecular Structure Oxidation-Reduction Pyridines - chemistry Pyrrolidines - chemistry
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Summary:	The limited availability of catalytic reaction components may represent a major hurdle for the practical application of many catalytic procedures in organic synthesis. In this work, we demonstrate that the mixture of isomeric iron complexes [Fe(OTf)2(mix-BPBP)] (mix-1), composed of Λ-α-[Fe(OTf)2(S,S-BPBP)] (S,S-1), Δ-α-[Fe(OTf)2(R,R-BPBP)] (R,R-1) and Δ/Λ-β-[Fe(OTf)2(R,S-BPBP)] (R,S-1), is a practical catalyst for the preparative oxidation of various aliphatic compounds including model hydrocarbons and optically pure natural products using hydrogen peroxide as an oxidant. Among the species present in mix-1, S,S-1 and R,R-1 are catalytically active, act independently and represent ca. 75% of mix-1. The remaining 25% of mix-1 is represented by mesomeric R,S-1 which nominally plays a spectator role in both C-H and C[double bond, length as m-dash]C bond oxidation reactions. Overall, this mixture of iron complexes displays the same catalytic profile as its enantiopure components that have been previously used separately in sp(3) C-H oxidations. In contrast to them, mix-1 is readily available on a multi-gram scale via two high yielding steps from crude dl/meso-2,2'-bipyrrolidine. Next to its use in C-H oxidation, mix-1 is active in chemospecific epoxidation reactions, which has allowed us to develop a practical catalytic protocol for the synthesis of epoxides.
ISSN:	1477-0539
DOI:	10.1039/c3ob42249f