A rhodium/silver synergistic catalysis has been established, enabling cycloisomerization/cross coupling of keto-vinylidenecyclopropanes (VDCPs) with terminal alkynes toward the regio- and enantioselective formation of diversified tetrahydropyridin-3-ol tethered 1,4-enynes in good yields and high ee values. In this synergistic catalysis, Rh(I) and Ag(I) catalysts selectively activate keto-VDCP substrates and terminal alkynes to generate the π-allyl Rh(III) complex of oxa-rhodacyclic intermediate and Ag alkynyl intermediate, respectively. The rapid transmetalation of alkynyl groups from Ag to Rh is proposed to play a key role in realizing the regioselective cleavage of the distal bond of the three-membered ring in this transformation.
Rh(i)-catalyzed asymmetric [3 + 2] cycloadditions of ene-VDCPs are demonstrated, producing cyclic ring structures with an all-carbon quaternary stereocenter in good yields with excellent enantioselectivities.
The Rh(I) complex catalyzed the dimerization of ene-vinylidenecyclopropanes took place smoothly to construct a series of products containing spiro[4,5]decane skeletons featuring simple operation procedure, mild reaction conditions, and good functional...
A Rh(i)-catalyzed intramolecular [3 + 2] cycloaddition reaction of yne-vinylidenecyclopropanes has been developed, providing fused [6.5]-bicyclic products in moderate to good yields.
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