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Enantioselective iron-catalysed O–H bond insertions

Nature Chemistry volume 2, pages 546–551 (2010)Cite this article

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Abstract

The ready availability, low price and environmentally benign character of iron mean that it is an ideal alternative to precious metals in catalysis. Recent growth in the number of iron-catalysed reactions reported reflects an increasing demand for sustainable chemistry. Only a limited number of chiral iron catalysts have been reported and these have, in general, proven less enantioselective than other transition-metal catalysts, thus limiting their appeal. Here, we report that iron complexes of spiro-bisoxazoline ligands are highly efficient catalysts for asymmetric O–H bond insertion reactions. These complexes catalyse insertions into the O–H bond of a wide variety of alcohols and even water, with exceptional enantioselectivities under mild reaction conditions. The selectivities surpass those obtained with other transition-metal catalysts. This study should inspire and encourage the use of iron instead of traditional precious metals in the development of greener catalysts for catalytic asymmetric synthesis.

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Figure 1: Transition-metal-catalysed insertion reactions starting with diazo compounds.
Figure 2: Synthetic applications of the O–H insertion products.

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Acknowledgements

The authors wish to thank the National Natural Science Foundation of China, the National Basic Research Program of China (973 Program, nos 2006CB806106, 2010CB833300), the Ministry of Health (grant no. 2009ZX09501-017) and the ‘111’ Project of the Ministry of Education of China (grant no. B06005) for financial support.

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Authors and Affiliations

  1. State Key Laboratory and Institute of Elemento-organic Chemistry, Nankai University, Tianjin, 300071, China

    Shou-Fei Zhu, Yan Cai, Hong-Xiang Mao, Jian-Hua Xie & Qi-Lin Zhou

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  1. Shou-Fei Zhu
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  2. Yan Cai
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Contributions

S.-F.Z., J.-H.X. and Q.-L.Z. designed the project. C.Y. and H.-X.M. carried out the experimental work. S.-F.Z. and Q.-L.Z. wrote the paper. All authors analysed the data, discussed the results and commented on the manuscript.

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Correspondence to Qi-Lin Zhou.

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The authors declare no competing financial interests.

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Zhu, SF., Cai, Y., Mao, HX. et al. Enantioselective iron-catalysed O–H bond insertions. Nature Chem 2, 546–551 (2010). https://doi.org/10.1038/nchem.651

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