Ru(II)-catalysed oxidative (4 + 2) annulation of chromene and coumarin-3-carboxylic acids with alkynes/propargylic alcohols sp C-H bond activation is reported. While the reaction with alkynes affords highly substituted pyrano-chromones in good to excellent yields, the use of methyl-tethered propargylic alcohols in place of alkynes leads to novel Ru(0)-metal complexes in moderate to good yields; these complexes were stable in MeCOH/O. The generality of the reaction with alkynes is illustrated in the case of both symmetrical and unsymmetrical internal alkynes with excellent regioselectivity in the case of unsymmetrical alkynes.
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