Reactions of diborenes with terminal alkynes: mechanisms of ligand-controlled anti-selective hydroalkynylation, cycloaddition and C <svg xmlns='http://www.w3.org/2000/svg' version='1.0' width='23.636364pt' height='16.000000pt' viewBox='0 0 23.636364 16.000000' preserveAspectRatio='xMidYMid meet'><metadata> Created by potrace 1.16, written by Peter Selinger 2001-2019 </metadata><g transform='translate(1.000000,15.000000) scale(0.015909,-0.015909)' fill='currentColor' stroke='none'><path d='M80 600 l0 -40 600 0 600 0 0 40 0 40 -600 0 -600 0 0 -40z M80 440 l0 -40 600 0 600 0 0 40 0 40 -600 0 -600 0 0 -40z M80 280 l0 -40 600 0 600 0 0 40 0 40 -600 0 -600 0 0 -40z'/></g></svg> C triple bond scission†

The reactions of terminal acetylenes with doubly Lewis base-stabilised diborenes resulted in different outcomes depending on the nature of the ligands at boron and the conformation of the diborene (cyclic versus acyclic). N-heterocyclic carbene (NHC)-stabilised diborenes tended to undergo anti-selective hydroalkynylation at room temperature, whereas [2 + 2] cycloaddition was observed at higher temperatures, invariably followed by a C–N bond activation at one NHC ligand, leading to the ring-expansion of the initially formed BCBC ring and formation of novel boron-containing heterocycles. For phosphine-stabilised diborenes only [2 + 2] cycloaddition was observed, followed by a rearrangement of the resulting 1,2-dihydro-1,2-diborete to the corresponding 1,3-isomer, which amounts to complete scission of both the B Created by potrace 1.16, written by Peter Selinger 2001-2019 B double and CC triple bonds of the reactants. The elusive 1,2-isomer was finally trapped by using a cyclic phosphine-stabilised diborene, which prevented rearrangement to the 1,3-isomer. Extensive density functional theory (DFT) calculations provide a rationale for the selectivity observed.
The outcome of reactions between diborenes and terminal alkynes can be tuned by varying the stabilising Lewis base and/or reaction conditions, to yield either the anti-hydroalkynylation product or [2 + 2] cycloaddition-derived boron heterocycles.