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. 2019 Mar 13;141(10):4235-4240.
doi: 10.1021/jacs.9b00594. Epub 2019 Mar 5.

Bi(I)-Catalyzed Transfer-Hydrogenation with Ammonia-Borane

Feng Wang  1 , Oriol Planas  1 , Josep Cornella  1
Affiliations

Bi(I)-Catalyzed Transfer-Hydrogenation with Ammonia-Borane

Feng Wang et al. J Am Chem Soc. .

Abstract

A catalytic transfer-hydrogenation utilizing a well-defined Bi(I) complex as catalyst and ammonia-borane as transfer agent has been developed. This transformation represents a unique example of low-valent pnictogen catalysis cycling between oxidation states I and III, and proved useful for the hydrogenation of azoarenes and the partial reduction of nitroarenes. Interestingly, the bismuthinidene catalyst performs well in the presence of low-valent transition-metal sensitive functional groups and presents orthogonal reactivity compared to analogous phosphorus-based catalysis. Mechanistic investigations suggest the intermediacy of an elusive bismuthine species, which is proposed to be responsible for the hydrogenation and the formation of hydrogen.

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Conflict of interest statement

The authors declare no competing financial interest.

Figures

Figure 1
Figure 1
(A) Catalytic redox-activity of pnictogens. (B) Typical reactivity of Bi(III) in catalysis. (C) Bi(I)/Bi(III) redox catalysis.
Scheme 1
Scheme 1. (A) Dehydrogenation of AB with Bi(I) and (B) Transfer Hydrogenation Using Different Amine Borane Complexes
Scheme 2
Scheme 2. (A) Kinetic Isotope Effect Experiments; (B) Competition Experiment between Two Electronically Different Azoarenes
Scheme 3
Scheme 3. (A) Stoichiometric and (B and C) Mass Spectrometry Studies
2.0 equiv of reducing agent.
See this image and copyright information in PMC

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