Abstract
A new benzyne transformation is described that affords versatile biaryl structures without recourse to transition‐metal catalysis or stoichiometric amounts of organometallic building blocks. Aryl sulfonamides add to benzyne upon fluoride activation, and then undergo an aryl Truce–Smiles rearrangement to afford biaryls with sulfur dioxide extrusion. The reaction proceeds under simple reaction conditions and has excellent scope for the synthesis of sterically hindered atropisomeric biaryl amines.
Highlights
A new benzyne transformation is described that affords versatile biaryl structures without recourse to transition-metal catalysis or stoichiometric amounts of organometallic building blocks
The biaryl motif is fundamental to chemistry, as it is widely represented in natural products, materials, pharmaceuticals, and agrochemicals
Synthesis of these ubiquitous structures is often carried out using transition-metal catalysis and stoichiometric amounts of metallated arenes, which enable the coupling of two sp2-carbon centers via organometallic intermediates.[1]
Summary
A new benzyne transformation is described that affords versatile biaryl structures without recourse to transition-metal catalysis or stoichiometric amounts of organometallic building blocks. A seminal report from Pütter and Waldau described an aryl Truce–Smiles reaction for stabilized phenolate anions, and more recent work from Quayle and co-workers described a Truce–Smiles rearrangement of a-silyl-phenylsulfonate esters.[10] Further encouragement for the idea came from the Motherwell biaryl synthesis, which demonstrates an analogous process under a radical manifold.[11] Treatment of the haloaryl sulfonamides 5 with nBu3SnH affords 2-amino biaryls through radical ipso substitution and SO2 extrusion (Scheme 1 c).
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