Preparation and synthetic applications of aryl tetraflates (ArOSO2CF2CF2H)

We have recently developed an improved synthetic route to 1,1,2,2-tetrafluoroethanesulfonic acid (HCF2CF2SO3H, TFESA) and explored the applications of this newly available superacid in catalysis. Low volatility, ease of handling, and a convenient 1H NMR handle make this acid an attractive alternative to triflic acid. TFESA can also be converted to several of its derivatives: anhydride, sulfonyl chloride, and sulfonyl fluoride, which provide a good entry point for the synthesis of aryl sulfonates. We prepared several aryl esters of 1,1,2,2-tetrafluoroethanesulfonic acid (aryl tetraflates) and showed that they can be used in a number of palladium-catalyzed coupling reactions (Suzuki, Heck, and Buchwald-Hartwig couplings). While the reactivity of tetraflates lies between that of triflates and chlorides, tetraflates appear to be more thermally stable. Additionally, the presence of a hydrogen atom in the tetraflate group facilitates monitoring of reactions and characterization of derivatives.     

An Elementary Method on a Minimization Problem

一、ＴｈｅＰｒｏｂｌｅｍ .Ｌｅｔｆ(ｘ) =ａｘ2 ｂｘ ｃ ａｘ2 ｐｘ ｑ,ｗｈｅｒｅａ >0 ,ｂ2 - 4ａｃ≤ 0ａｎｄｐ2 - 4ａｑ≤ 0 .ＯｕｒＰｒｏｂｌｅｍｉｓ“Ｗｈｅｔｈｅｒｄｏｅｓｍｉｎｘ∈Ｒｆ(ｘ)ｅｘｉｓ?Ｍｏｒｅｏｖｅｒ ,,ｉｆｍｉｎｘ∈Ｒｆ(ｘ)ｅｘｉｓｔｓ,ｔｈｅｎｍｉｎｘ∈Ｒｆ(ｘ)=?ａｎｄｉｎｔｈｉｓｃａｓｅｘ =?” .Ｎａｔｕｒａｌｌｙ ,ｗｅｋｎｏｗｔｈａｔｍｉｎｘ∈Ｒｆ(ｘ)ｅｘｉｓｔｓｆｒｏｍｔｈｅｋｎｏｗｌｅｄｇｅｏｆｍａｔｈｅｍａｔｉｃａｌａｎａｌｙｓｉｓ.Ａｌｓｏ,ｗｅｃａｎｇｉｖｅｔｈｅ…     

The Synthesis and Properties of New Metal-free and Metallophthalocyanines Containing Four Diloop Macrocyclic Moieties

The synthesis and characterization of new metal-free (9) and metal-containing (Zn, Ni or Cu 10, 11, 12) derivatives of a symmetrically octasubstituted phthalocyanine derived from 21,22-dicyano-2,3,5,6,8,9,11,12,15,17,18,25,26,28-tetradecahydro[1,4,7,12] benzodioxadithiacyclotetradeceno[6,7-b][1,4,7,10,13]benzopentaoxacyclopentadecene (7), which was synthesized in a multi-step reaction sequence, have been described. The novel compouds have been characterized by a combination of elemental analysis, ¹H and ¹³C NMR, IR, UV–vis and MS spectral data.