Efficient and general procedures for the cross-coupling of 1,1-dibromoalkenes N-, O-, P-nucleophiles are reported. Fine-tuning reaction conditions allows either site-selective, double, or alkynylative cross-coupling, therefore providing divergent straightforward entries to numerous building blocks such as bromoenamides, ynamides, ketene N,N-acetals, bromoenol ethers, ynol O,O-acetals, vinylphosphonates further expanding copper catalysis toolbox with useful versatile processes.

A general and efficient access to aryl, heteroaryl, vinyl alkynyl difluoromethylphosphonates is described. The developed methodology using TMSCF2PO(OEt)2, iodonium salts a copper salt provided straightforward manifold reach these highly relevant products. reaction proved be functional group tolerant proceeded under mild conditions, giving the corresponding products in good excellent yields. This method represents first synthetic route this important class of fluorinated scaffolds, which are...

The difluoromethyl phosphonate motif plays a crucial role in the development of bioactive molecules as it is considered phosphate bioisoster. Since 2010, renewal interest to enlarge panel reactions access these difluoromethylated phosphonate-containing has been witnessed. This Concept article charts recent progress that made.

Abstract An unprecedented electrophilic difluoromethylthiolating reagent (MesNHSCF 2 PO(OEt) ) was designed. Under mild and metal‐free conditions, this new reacted with various nucleophiles, thus offering an efficient operationally simple tool for the construction of C−SCF PO(OR) , N−SCF S−SCF bonds. Finally, thanks to methodology, synthesis non‐stereoidal anti‐inflammatory diflumidone achieved.

Abstract Herein, we report a copper salt‐controlled divergent reactivity toward α‐diazocarbonyl compounds. By simple change of the counteranion under identical reaction conditions, reported method allowed an easy access to either ( Z )‐α‐fluorovinylphosphonate or alkyl‐SCF 2 PO(OEt) derivatives in good yields. Mechanistic studies were performed and suggested two different pathways explain formation these products.

An efficient and general copper-catalyzed method is reported for the synthesis of phenol-derived 1-bromoenol ethers, ynol ketene acetals by chemodivergent cross-coupling between readily available 1,1-dibromo-1-alkenes phenols.

Abstract We report the direct introduction of CF 2 CO Et moiety into electron‐rich arenes. The copper‐catalyzed process uses commercially available and inexpensive BrCF as a fluorinated building block. This radical‐free reaction proceeds smoothly to give desired difluoromethylated arenes in modest good yields with Friedel–Crafts‐type regioselectivity. α,α‐difluoromethylated amides was also investigated, this gave corresponding arenes, albeit moderate yields. method represents first...

Abstract Herein, a general procedure to access CF 2 PO(OEt) ‐containing molecules is reported. The reagent CuCF accessible by simple protocol and broad range of substrates can be functionalised. allows the conversion aryl diazonium salts, as well aryl, heteroaryl, vinyl alkynyl iodonium into corresponding fluorinated at room temperature. Mechanistic studies were performed gain better understanding reaction pathway. Under similar conditions, iodides, allyl halides, benzyl bromides also...

Numerical methods generally need analytical solutions as test cases and validations in simplified problems. This work provides Laplace-domain explicit analytic for fluid–structure interaction (FSI) water hammer waves within a pipe. Rather than applying the transfer matrix method (TMM) to FSI four equations, it is transposed equivalent two-wave propagating problem considered instead. Using classical wave diagonalization approach permits decoupling waves' propagation while at same time...

The first non-chiral pool total synthesis of (+)-hyacinthacine A1 is described. This based on an effective [2 + 2] cycloaddition dichloroketene to a Stericol®-based enol ether, diastereoselective dihydroxylation, and efficient Tamao–Fleming oxidation.

Abstract Difluoromethylated arenes are scaffolds of great interest. We report herein a mild and general method for the introduction CF 2 PO(OEt) moiety into arenes. The CuCF species, which is generated in situ from corresponding silylated derivatives, combination with aryl diazonium salts furnished highly valuable difluoromethylphosphonates moderate to good yields. This represents first introduce under conditions.

Abstract A general and efficient access to aryl, heteroaryl, vinyl alkynyl difluoromethylphosphonates is described. The developed methodology using TMSCF 2 PO(OEt) , iodonium salts a copper salt provided straightforward manifold reach these highly relevant products. reaction proved be functional group tolerant proceeded under mild conditions, giving the corresponding products in good excellent yields. This method represents first synthetic route this important class of fluorinated scaffolds,...

We report herein a straightforward access to α‐[(diethoxyphosphoryl)difluoromethyl]thiolated ketones. The methodology, which involves the nucleophilic [Cu]CF 2 PO(OEt) species, has allowed formation of targeted compounds in moderate high yields by using simple procedure. This method represents convenient alternative known approaches for introduction this emergent fluorinated motif.

Abstract Herein, we report a copper salt‐controlled divergent reactivity toward α‐diazocarbonyl compounds. By simple change of the counteranion under identical reaction conditions, reported method allowed an easy access to either ( Z )‐α‐fluorovinylphosphonate or alkyl‐SCF 2 PO(OEt) derivatives in good yields. Mechanistic studies were performed and suggested two different pathways explain formation these products.

Abstract A study of the preparation and reactivity N ‐ tert ‐butanesulfinyl glycosylamines is reported for first time. As they react readily as latent imine equivalents with a variety carbon nucleophiles, these new carbohydrate derivatives constitute very useful precursors diastereoselective synthesis bioactive compounds such iminosugar‐ C ‐glycosides.

Abstract An unprecedented electrophilic difluoromethylthiolating reagent (MesNHSCF 2 PO(OEt) ) was designed. Under mild and metal‐free conditions, this new reacted with various nucleophiles, thus offering an efficient operationally simple tool for the construction of C−SCF PO(OR) , N−SCF S−SCF bonds. Finally, thanks to methodology, synthesis non‐stereoidal anti‐inflammatory diflumidone achieved.

A concise and straightforward synthesis of the fully elaborated macrocyclic core TMC-95A is reported. highly efficient organocatalyzed aldolization between isatin dihydroxyacetone derivatives formation biaryl subunit with concomitant macrocyclization are characteristic features this synthesis.

Fully functionalized medium-sized cyclic ethers, of the type found in fused polyether natural products, have been prepared by sequential ring-closing diene metathesis, conversion resulting enone into an allylic enol carbonate, and Tsuji-Trost allylation using a chiral palladium complex. Very high levels diastereocontrol, favoring diastereomer which there is cis relationship between allyl group at C-2 medium-ring ether substituent C-7/C-8, are obtained cases where catalyst control substrate matched.

Abstract Review: [40 refs.

Abstract The first direct introduction of a functionalized fluorinated moiety into electron‐rich arenes by copper‐catalyzed radical‐free process is reported.

Abstract The reaction of furanose and pyranose derivatives with optically active sulfinamidine (II) gives the title compounds (III) (VII), respectively.

Abstract The CuCF 2 ‐PO(O‐Et) species, generated in situ under optimized mild conditions, reacts with various aryl diazonium salts to produce the synthetically and pharmaceutically important target compounds bearing functionalities at phenyl moiety.