Heteroaryl manganese reagents: direct preparation and reactivity studies

Efficient homocoupling reactions of halide compounds catalyzed by manganese (II) chloride

“…[15,16] Rieke developed benzylic manganese reagents undergoing cross-coupling reactions with a variety of electrophiles in high yields. [17,18] Hoffmann determined the stereochemistry of the transmetalation of Grignard reagents to manganese (II). [19] Recently Rueping developed the cross-coupling reaction of heterocyclic chlorides with aryl magnesium halides using manganese (II) catalyst.…”

Synthetic Techniques and Applications of Activated Nanostructurized Metals: Highlights up to 2008

“…At present, Rieke metals have got a lot of applications in various areas of organic and organometallic chemistry [223][224][225][226][227][228][229][230], in particular for metal phthalocyanine synthesis [231], for hydrogen storage [232], creation of alloys or intermetalics [233]. Even uranium and thorium were prepared [234] in this activated form and further used in organic synthesis.…”

TFAA/H3PO4‐Mediated C‐2 Acylation of Thiophene: A Direct Synthesis of Known and Novel Thiophene Derivatives of Pharmacological Interest

“…An impressive number of methods have been reported for the synthesis of 2‐aroyl thiophenes. Some of these include the reaction of the following: (a) thiophene with benzoic anhydride , (trichloromethyl)benzene , t ‐butylbenzoate , pyridin‐2‐yl benzoate , (1 H ‐imidazol‐1‐yl)(phenyl)methanone , or PhCO 2 POF 2 ; (b) thiophene‐2‐boronic acid with benzoic anhydride ; (c) 2‐iodothiophene with carbon monoxide and phenyl boronic acid or PhLi ; (d) tributyl(thiophen‐2‐yl)stannane with Ph 2 TeCl 2 or Ph 2 IBF 4 and carbon monoxide ; (e) thiophen‐2‐boronic acid with benzoyl chloride ; (f) thiophene‐2‐carbonyl chloride with phenyl boronic acid , Ph 3 Bi , or Ph 4 BiNa ; (g) thiophene‐2‐carbonyl fluoride with Ph 2 Zn ; (h) 2‐bromothiophene or thiophen‐2‐ylmagnesium bromide or trimethyl(thiophen‐2‐yl)stannane or dithiophen‐2‐ylmercury with benzoyl chloride; (i) thiophen‐2‐aldehyde with iodobenzene ; and (j) 1‐methyl‐3‐( N ‐methylthiophene‐2‐carboxamido)‐1 H ‐imidazol‐3‐ium iodide with PhMgBr . Most of these methods, however, require the use of a transition metal or other catalyst and cumbersome preparation of unstable or moisture‐sensitive starting materials or special reagents.…”