An enantioselective chemical synthesis of arene cis‐dihydrodiols has been realized from 2‐pyrones through sequential ytterbium‐catalyzed asymmetric inverse‐electron‐demand Diels–Alder (IEDDA) reaction of 2‐pyrones and retro‐Diels–Alder extrusion of CO2. By using this strategy, a series of substituted arene cis‐dihydrodiols can be obtained efficiently with high enantioselectivity (>99 % ee in many cases). Based on this strategy, efficient and concise asymmetric total syntheses of (+)‐MK7607 and 1‐epi‐(+)‐MK7607 were accomplished.

A novel strategy for the synthesis of cis-decalins by an ytterbium-catalyzed asymmetric inverse-electron-demand Diels-Alder reaction of 2-pyrones and silyl cyclohexadienol ethers is reported here. A broad range of synthetically important cis-decalin derivatives with multiple contiguous stereogenic centers and functionalities are obtained in good yields and stereoselectivities. A full set of diastereomeric substituted cis-decalin motifs are readily accessible by tuning the absolute configurations of substituted silyl cyclohexadienol ethers (R or S) as well as the ligands (R or S). The synthetic potential is showcased by the enantioselective total synthesis of 4-amorphen-11-ol, and further demonstrated by the first total synthesis of cis-crotonin. Scheme 1. Enantioselective synthesis of cis-decalin motifs by inverseelectron-demand Diels-Alder reaction of 2-pyrones.

The incorporation of a perfluoroalkyl group (R F ) into drug candidates has become an increasingly important strategy in drug molecule design. In this study, the silver-mediated perfluoroalkylation reaction based on the addition−elimination process of terminal alkynes which was initiated by a perfluoroalkyl radical to form a C(sp)−R F bond has been developed. The reaction proceeds under mild conditions using readily available, low-cost perfluoroalkyl iodides as the sources of the R F group. This method allows access to a variety of perfluoroalkylated alkynes.

A novel dehydrogenative dicarbofunctionalization of vinyl arenes with polyfluoroarenes and unactivated alkanes enabled by copper catalysis has been accomplished under mild conditions. This transformation provides a regioselective route to highly functionalized polyfluoroaryl compounds that occur as structural scaffolds in a variety of pharmaceuticals and materials. Preliminary mechanistic studies indicate that the carbon-based radical and copper intermediate are involved in the reaction, and the reaction pathway is dominated by the bond dissociation energy (BDE) of C(sp 3 )−H bonds. Letter pubs.acs.org/OrgLett

A palladium‐catalyzed monofluoroalkylation of aryl iodides and aryl bromides was developed using nucleophilic ethyl 2‐fluoro‐2‐(trimethylsilyl)acetate as a monofluoroalkyl source. The transformation proceeded with excellent substrate scope to afford a range of monofluoroalkylated products in good yields under mild conditions, and it proved feasible in a gram‐scale reaction. This protocol was successfully used in late‐stage modification of an estrone derivative, providing a facile route for research on the discovery of biologically active compounds and high‐performance materials.