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. 2012 May 16;48(39):4692-4.
doi: 10.1039/c2cc31743e. Epub 2012 Apr 4.

Consecutive iridium catalyzed C-C and C-H bond forming hydrogenations for the diastereo- and enantioselective synthesis of syn-3-fluoro-1-alcohols: C-H (2-fluoro)allylation of primary alcohols

Abbas Hassan  1 , T Patrick Montgomery, Michael J Krische
Affiliations

Consecutive iridium catalyzed C-C and C-H bond forming hydrogenations for the diastereo- and enantioselective synthesis of syn-3-fluoro-1-alcohols: C-H (2-fluoro)allylation of primary alcohols

Abbas Hassan et al. Chem Commun (Camb). .

Abstract

Commercially available (2-fluoro)allyl chloride serves as an efficient allyl donor in highly enantioselective iridium catalyzed carbonyl (2-fluoro)allylations from the alcohol or aldehyde oxidation level via transfer hydrogenation. Diastereoselective Crabtree hydrogenation of the resulting homoallylic alcohols provides syn-3-fluoro-1-alcohols.

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Figures

Scheme 1
Scheme 1
Synthesis of syn-3-fluoro-1-alcohols via consecutive C–C and C–H bond forming hydrogenations.
Scheme 2
Scheme 2
More reactive chloride leaving groups compensate for decreased stability of π-complex.
Scheme 3
Scheme 3
Preparation of iridium complex Ir-Cat-I.
Scheme 4
Scheme 4
Synthesis of syn-3-fluoro-1-alcohols 6a–c and 6g via Crabtree hydrogenation of vinyl fluorides 4a–c and 4g, respectively.
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