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. 2022 Feb 14;61(8):e202114482.
doi: 10.1002/anie.202114482. Epub 2022 Jan 11.

Controlling Chemoselectivity of Catalytic Hydroboration with Light

Enrico Bergamaschi  1 , Danijela Lunic  1 , Liam A McLean  1 , Melissa Hohenadel  1 , Yi-Kai Chen  1 , Christopher J Teskey  1
Affiliations

Controlling Chemoselectivity of Catalytic Hydroboration with Light

Enrico Bergamaschi et al. Angew Chem Int Ed Engl. .

Abstract

The ability to selectively react one functional group in the presence of another underpins efficient reaction sequences. Despite many designer catalytic systems being reported for hydroboration reactions, which allow introduction of a functional handle for cross-coupling or act as mild method for reducing polar functionality, these platforms rarely deal with more complex systems where multiple potentially reactive sites exist. Here we demonstrate, for the first time, the ability to use light to distinguish between ketones and carboxylic acids in more complex molecules. By taking advantage of different activation modes, a single catalytic system can be used for hydroboration, with the chemoselectivity dictated only by the presence or absence of visible light.

Keywords: Chemoselectivity; Cobalt; Hydroboration; Photochemistry; Reduction.

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Conflict of interest statement

The authors declare no conflict of interests.

Figures

Scheme 1
Scheme 1
Planned divergence of activation mode to allow light‐controlled chemoselective hydroboration.
Scheme 2
Scheme 2
Comparison of conditions for the selective reduction of 1 a and substrate scope of photocontrolled hydroboration. [a] 10 mol% loading of [Co]. Reactions were carried out at 0.1 mmol scale and isolated yields are reported (with yield determined by 1H NMR with an internal standard given in parentheses).
Scheme 3
Scheme 3
Extension to other functionalities. A: [Co] 5 mol%, HBpin 5.0 equiv, 2‐MeTHF (1.0 M); B: [Co] 5 mol%, HBpin 3.0 equiv, 2‐MeTHF (0.1 M); C: [Co] 5 mol%, HBpin 5.0 equiv, EtOAc (1.0 M); D: [Co] 1 mol%, HBpin 1.1 equiv, EtOAc (1.0 M). [Co]=CoH[PPh(OEt)2]4.
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