Compared with the ripenesso fo lefin metathesis, exploration of the construction of carbon-carbon double bonds through the catalytic carbonyl-olefin metathesis reactionr emainss tagnant and has received scant attention. Herein, ah ighlye fficient AuCl 3 -catalyzed intramolecular ring-closing carbonyl-olefin metathesis reaction is described. This method features easily accessible starting materials, simple operation,good functional-group tolerance and short reaction times, and providest he target cyclopentenes, polycycles, benzocarbocycles, and N-heterocycle derivatives in good to excellent yields.Carbon-carbon double-bond formation is one of the useful and fundamentalr eactions in synthetic organic chemistry,p articularly in the synthesis of complex natural products, bioactive molecules, synthetic drugs, and functional organic materials. [1] Generally,c onventional wisdom states that the construction of the carbon-carbond ouble bond mostly relies on the olefination of carbonyl compounds ando lefin metathesis. Since the pioneering work by Wittig, Horner,a nd Emmons,t he synthesis of alkenes by the olefination of carbonyl compounds has evolveda so ne of the most efficient methods, whichu ses phosphorus, sulfur,a nd silicon ylides as highly polarizedn ucleophilic components to add to carbonyl derivatives. [2] Olefin metathesis is another more important approach to obtain olefins andh as brought about ah uge development of many applicationsi ns ynthetic organic chemistry,s ince the discovery of second-generationc atalysts consisting of well-defined metalcarbene complexes, which are mostly based on stable molybdenum or ruthenium. [3] Compared with the ripenesso fo lefin metathesis and Horner-Wadsworth-Emmons reactions, other double-bond metathesis reactions are much less developed, [4] but these metathesis reactions should hold great potential for complex molecular synthesis through one-step synthetict ransformation.Amongt hem, the hitherto elusive carbonyl-olefin metathesis may be the mostp owerful alternative to have appeared in some applications for the total synthesis of naturalp roducts and construction of complex molecules, as usually these molecules are difficult to synthesis by other methods. [5] However, the historical early reports based on photoinduced, stoichiometrica mounts of transition-metal-promotedand even metalalkylidene-mediated carbonyl-olefin metathesish ampered the practicality because of limitations for substrates bearing chromophores, harsh reaction conditions, competing polymerization,h igh cost, and environmental pollution. [6] The fundamental cause of the stagnancy aboutc arbonyl-olefin metathesis lies in:1 )the difficulties in establishing ac atalytic version due to the formation of ak inetically inert metal-oxo complex duringt he cycloreversion step;2 )potential side reactions such as polymerization, ene reaction, alkylation, and Prins reaction etc.;3)regenerationofs tartingc arbonyl-olefinpairs.Recently,t he real breakthrough has begun to dawn because of strategies and catalysts, such...

Herein, the first example using commercially available 2-bromo-3,3,3-trifluoropropene (BTP) as a radical acceptor has been reported. Taking advantage of this strategy, a wide range of secondary trifluoromethylated alkyl bromides were synthesized in good to excellent yields with broad functional group tolerance by using redox-active esters as a radical precursor. The practicality of this protocol was further demonstrated by diverse derivations and direct modification of biologically active molecules.

3-Alkylated coumarins have many applications in medicinal chemistry, however, methods access to such structures are still limited. Herein, we report a site-selective photocatalytic deaminative alkylation of coumarins utilizing pyridinium-activated aliphatic primary amines as alkylation reagents. The protocol was highlighted by its mild reaction conditions, operational simplicity, and broad functional group compatibility. Moreover, this strategy enables late-stage modification of some pharmaceuticals and natural products, thus providing an appealing approach to valuable molecules in medicinal chemistry.

Iron-catalyzed functionalization of inert bonds has scarcely been documented. Herein, we report an iron-catalyzed method for the silylation and borylation of (hetero)aromatic fluorides. This protocol features a wide range of...

We describe a decarboxylative coupling reaction of N‐hydroxyphthalimide esters with bromopolyfluorobenzene enabled by the synergetic action of Hantzsch ester, photoredox catalyst, and nickel catalyst. This method readily converts primary and secondary alkyl carboxylic acids into the corresponding polyfluoroaryl compounds with broad scope and excellent functional group compatibility. The practicality of this method was further demonstrated by the direct modification of amino acids and biologically active molecules