2525-41-9Relevant academic research and scientific papers
Trifluoromethyl Nonaflate: A Practical Trifluoromethoxylating Reagent and its Application to the Regio- and Stereoselective Synthesis of Trifluoromethoxylated Alkenes
Hammond, Gerald B.,Kumon, Tatsuya,Lu, Zhichao,Umemoto, Teruo
supporting information, p. 16171 - 16177 (2021/06/27)
The trifluoromethoxy group has elicited much interest among drug and agrochemical discovery teams because of its unique properties. We developed trifluoromethyl nonafluorobutanesulfonate (nonaflate), TFNf, an easy-to-handle, bench-stable, reactive, and scalable trifluoromethoxylating reagent. TFNf is easily and safely prepared in a simple process in large scale and the nonaflyl part of TFNf can easily be recovered as nonaflyl fluoride after usage and recycled. The synthetic potency of TFNf was showcased with the underexplored synthesis of various trifluoromethoxylated alkenes, through a high regio- and stereoselective hydro(halo)trifluoromethoxylation of alkyne derivatives such as haloalkynes, alkynyl esters, and alkynyl sulfones. The synthetic merits of TFNf were further underscored with a high-yielding and smooth nucleophilic trifluoromethoxylation of alkyl triflates/bromides and primary/secondary alcohols.
Cu(OAc)2 Mediated Synthesis of 3-Sulfonyl Chromen-4-ones
Chang, Meng-Yang,Chen, Yu-Hsin,Wang, Heui-Sin
, p. 2361 - 2368 (2018/02/23)
Copper acetate mediated (4 + 2) annulation of sulfonylacetylenes with salicylic acids provides sulfonyl chromen-4-ones in the presence of benzotriazol-1-yloxy tri(dimethylamino)phosphonium hexafluorophosphate (BOP, Castro's reagent) and 4-dimethylaminopyridine (DMAP) in MeNO2 at reflux for 3 h. The uses of various metal complexes and activating reagents are investigated for facile and efficient transformation. A plausible mechanism is proposed.
Electrotelluration: A new approach to tri- and tetrasubstituted alkenes
Marino, Joseph P.,Nguyen, Hanh Nho
, p. 6291 - 6296 (2007/10/03)
A novel electrotelluration process is described in which a Michael addition of an alkyl or aryl tellurolate anion occurs onto an activated alkyne with subsequent trapping of a vinyl anion with electrophiles (aldehydes and ketones) other than a proton. This process provides an efficient regio-and stereospecific route to tri- and tetrasubstituted alkenes. Methodologically significant examples of this chemistry were studied in which aryl and alkyl tellurolate anions were added to ω-keto alkynyl esters in a Michael reaction, and the incipient vinyl anions were trapped intramolecularly by the internal aldehydes. The reactive centers were tethered by different lengths of alkyl chains to form highly functionalized five-, six-, seven-, and eight-membered rings in modest to good yields.
Sulfone reagents in organic synthesis. VI. Sulfonyl- and silyl-substituted hydrocarbons as versatile carbanion precursors in organic synthesis
Eisch, John J.,Behrooz, Mohammad,Dua, Suresh K.
, p. 121 - 136 (2007/10/02)
The basic organometallic chemistry of β-silyl-substituted acetylenic, vinylic and alkyl sulfones has been investigated, with attention being given to metallation, carbometallation and the chemical reduction of carbon-carbon unsaturation. 2-Trimethylsilylvinyl and 2-trimethylsilylalkyl sulfones underwent smooth and stereoselective lithiation with RLi on the carbon α to the sulfonyl group. Carbometallation of vinyl sulfones could be achieved with RMgX or LiCuR2, but acetylenic sulfones carbometallated smoothly only with LiCuR2; with RMgX or RLi, these acetylenes underwent alkyldesulfonylation. The utility in synthesis of these metallo derivatives of sulfonyl-silyl-hydrocarbons is discussed and their value in elaborating carbon skeletons is illustrated for the preparation of alkenes, allenes, carbocycles and stereo-defined vinyl sulfones.
