Rh(I)-Catalyzed Carbene Migration/Carbonylation/Cyclization: Straightforward Construction of Fully Substituted Aryne Precursors

The Rh­(I)-catalyzed cascade formation
of carbenoid followed by
a carbonylative cyclization of silyl diynes has been established to
achieve diverse ortho silyl-substituted phenolics,
enabling access to fully substituted aryne precursors via a one-step
fluorosulfurylation. The silyl mask on the termini of alkynes is demonstrated
not only to suppress the undesired oxidation but also to control the
selectivity of CO insertion. Straightforward access to fully substituted
arynes was comprehensively established and applied for the efficient
construction of polycyclic aromatic molecules.