Beilstein J. Org. Chem.2023,19, 325–348, doi:10.3762/bjoc.19.28
transfer one or more groups from one group 13 element to another, through σ-bond metathesis; where boron is both of the group 13 elements, this is termed transborylation. These redox-neutral processes are increasingly being used to render traditionally stoichiometric group 13-mediated processes catalytic
and develop new catalytic processes, examples of which are the focus of this review.
Keywords: catalysis; group 13 exchange; hydroboration; main group; transborylation; Introduction
Group 13 compounds have found widespread use in stoichiometric organic transformations, typically in the
review will explore the use of group 13 exchange reactions as a general method for catalytic turnover, and serves to expand on the previously published review on transborylation-enabled boron catalysis to include a broader range of catalysts and turnover reagents [47].
Review
Boron catalysis
The borane
Beilstein J. Org. Chem.2022,18, 1332–1337, doi:10.3762/bjoc.18.138
of a double B–N/B–H transborylation mechanism.
Keywords: boron; catalysis; hydroboration; nitrile; transborylation; Introduction
Primary amines are prevalent throughout organic synthesis, finding regular application in materials chemistry, pharmaceuticals, and agrochemicals (Scheme 1a) [1][2][3
transborylation (a σ-bond metathesis turnover method) has been used for borane-catalysed reductions of N-heteroarenes [28][29], and the borane-catalysed cyanation of enones [30]. Applying B–N/B–H transborylation to the hydroboration of nitriles would enable the development of a borane-catalysed hydroboration of
essential medicines with over 28 million prescriptions per annum, in one step [40].
The reaction is proposed to proceed through a hydroboration and B–N/B–H transborylation mechanism, supported by computational analyses (Scheme 3a). The nitrile undergoes hydroboration with H3B·SMe2 to form an N-borylimine
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Graphical Abstract
Scheme 1:
a) Derivatives of primary amines in materials chemistry, pharmaceuticals, and agrochemicals; b) thi...