A step-for-step main-group replica of the Fischer carbene synthesis at a borylene carbonyl

Marcel Härterich, Alexander Matler, Rian D. Dewhurst, Andreas Sachs, Kai Oppel, Andreas Stoy and Holger Braunschweig ()
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Marcel Härterich: Julius-Maximilians-Universität Würzburg, Am Hubland
Alexander Matler: Julius-Maximilians-Universität Würzburg, Am Hubland
Rian D. Dewhurst: Julius-Maximilians-Universität Würzburg, Am Hubland
Andreas Sachs: Julius-Maximilians-Universität Würzburg, Am Hubland
Kai Oppel: Julius-Maximilians-Universität Würzburg, Am Hubland
Andreas Stoy: Julius-Maximilians-Universität Würzburg, Am Hubland
Holger Braunschweig: Julius-Maximilians-Universität Würzburg, Am Hubland

Nature Communications, 2023, vol. 14, issue 1, 1-7

Abstract: Abstract The Fischer carbene synthesis, involving the conversion of a transition metal (TM)-bound CO ligand to a carbene ligand of the form [=C(OR’)R] (R, R’ = organyl groups), is one of the seminal reactions in the history of organometallic chemistry. Carbonyl complexes of p-block elements, of the form [E(CO)n] (E = main-group fragment), are much less abundant than their TM cousins; this scarcity and the general instability of low-valent p-block species means that replicating the historical reactions of TM carbonyls is often very difficult. Here we present a step-for-step replica of the Fischer carbene synthesis at a borylene carbonyl involving nucleophilic attack at the carbonyl carbon followed by electrophilic quenching at the resultant acylate oxygen atom. These reactions provide borylene acylates and alkoxy-/silyloxy-substituted alkylideneboranes, main-group analogues of the archetypal transition metal acylate and Fischer carbene families, respectively. When either the incoming electrophile or the boron center has a modest steric profile, the electrophile instead attacks at the boron atom, leading to carbene-stabilized acylboranes – boron analogues of the well-known transition metal acyl complexes. These results constitute faithful main-group replicas of a number of historical organometallic processes and pave the way to further advances in the field of main-group metallomimetics.

Date: 2023
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DOI: 10.1038/s41467-023-36251-3

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