Optically pure ω-halohydrines and oxaheterocycles are attractive starting materials for the synthesis of biologically active compounds and medicinal products. The preparation of a number of pharmaceutically active compounds is dependent on the availability of suitable protocols to provide these compounds in sufficient enantiopurity and frequently relies on expensive and partly toxic noble metal catalysts. Herein, we present a molecularly defined iron alkyl complex (PhboxmiFeCH2SiMe3) as a catalyst for the enantioselective hydroboration of ω-haloketones, providing the corresponding chiral halohydrines or oxaheterocycles with excellent enantioselectivity (up to &gt;99 %ee) and conversion efficiency at low catalyst loadings (as low as 0.5 mol%). The reduction of a broad range of substrates gave rise to chiral substituted oxiranes, oxetanes, tetrahydrofuranes and dioxanes. Turnover frequencies of &gt;40000 h–1 at –30 °C highlight the activity of this earth-abundant metal catalyst which tolerates a large number of functional groups.

Highly enantioselective iron-catalyzed synthesis of oxaheterocycles via reduction of ω-haloketones

256th National Meeting (2018)

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