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A novel substrate-regulated [4+1] annulation of α-imidoyl sulfoxonium ylides with diazoketones under catalyst-free conditions is described. The reaction proceeds through a coupling of sulfoxonium ylides and in situ-generated ketenes to form the key reactive zwitterionic intermediates, followed by selective formation of C-C or C-O bonds to achieve five-membered ring systems. The cascade reaction permits the direct synthesis of synthetically useful 2-indanones and 3(2 H )-furanones, which expands the reaction pattern of sulfoxonium ylides in annulation transformation.

We report a step-economic strategy for the direct synthesis of bridged polycyclic skeletons by merging oxidative C-H annulation and cascade cycloaddition. In the protocol, spiro[cyclopentane-1,3'-indoline]-2,4-dien-2'-ones were first synthesized by oxidative C-H annulation of ethylideneoxindoles with alkynes. Subsequent cascade [4 + 2] cycloaddition with dienophiles gave the bridged bicyclo[2.2.1]quinolin-2(1 H )-ones and enabled the one-pot construction of two quaternary carbon centers and three C-C bonds. Mechanistic investigations of the latter suggest a cascade ring-opening, 1,5-sigmatropic rearrangement, and [4 + 2] cycloaddition process.

A novel copper-catalyzed radical cyanotrifluoromethylation has been achieved through a multicomponent reaction of isocyanides, Togni's reagent, and trimethylsilyl cyanides, affording trifluoroacetimidoyl nitriles in good yields. This reaction demonstrates a unique feature of merging two valuable functional groups-trifluoromethyl (CF 3 ) and cyan (CN)-onto the same C atom. The transformation proceeds by the initial addition of the CF 3 radical to isocyanide and the subsequent intermolecular C-CN formation. The products can be successfully transformed to a series of CF 3 -containing amines and imines that may serve in the synthesis of valuable pharmaceuticals and agrochemicals.

As the first cascade C-H activation directed by a transient group, reaction of alkynols and 7-oxabenzonorbornadienes has been achieved via synergistic rhodium and scandium catalysis to afford spirocyclic dihydrobenzo[a]fluorenefurans. This transformation proceeds by a transient hemiketal group directed C-H activation, dehydrative naphthylation, and intramolecular Prins-type cyclization. Mechanistic studies and density functional theory calculations indicate that the rate-determining step is C-H bond cleavage and both the transient hemiketal group and synergistic Rh III /Sc III catalysis play key roles.

[reaction: see text] Chiral Ru-TsDPEN [N-(p-toluenesulfonyl)-1,2-diphenylethylenediamine]-derived catalysts were first successfully immobilized onto amorphous silica gel and mesoporous silicas of MCM-41 and SBA-15 by an easily accessible approach. The catalyst immobilized on silica gel demonstrated remarkably high catalytic activities and excellent enantioselectivities (up to >99% ee) for the heterogeneous asymmetric transfer hydrogenation of various ketones. Particularly, the catalyst could be readily recovered and reused in multiple consecutive catalytic runs (up to 10 uses) with the completely maintained enantioselectivity.