Rhodium-catalyzed Hydroarylation and -Alkenylation of Alkynes with Silanediols. A Crucial Role of the Hydroxy Group for the Catalytic Reaction

Abstract

Aryl- and alkenylsilanediols, which possess two hydroxy groups on the silicon atom, undergo the rhodium-catalyzed addition of an organic group on silicon to internal alkynes. Treatment of several internal alkynes with aryl- or alkenylsilanediols in the presence of 3 mol% of [Rh(OH)(cod)]₂ affords the hydroarylated or hydroalkenylated products in good yields. A crucial role of the hydroxy group of silanediol for the catalytic reaction is also discussed with the related aryltin reagent.

Key words

silanediol - rhodium complex - hydroarylation - hydroalkenylation - internal alkyne

References

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All products were identical with authentic samples (ref. [4] ).

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Although Hayashi reported that 98% of alkenylrhodium rearrange to arylrhodium in the reaction of PhB(OH)₂ with Rh(acac)(C₂H₄)₂/dppb (ref. [4] ), the reaction of 2 with 1a in toluene-D₂O (10:1) showed 28% deuterium incorporation at the vinylic position and 68% at the ortho position of the aromatic ring.