Direct Preparation of 3-Thienyl Organometallic Reagents:  3-Thienylzinc and 3-Thienylmagnesium Iodides and 3-Thienylmanganese Bromides and Their Coupling Reactions

Abstract

3-Thienylzinc and 3-thienylmagnesium iodides can be generated from the direct oxidative addition of Rieke zinc and magnesium to 3-iodothiophene, respectively. The direct preparation of 3-thienylmanganese bromides from the reaction of Rieke manganese with 3-bromothiophene and 3,4-dibromothiophene is also performed. These 3-thienyl organometallic reagents have been found to be regiostable intermediates and undergo coupling reactions with a variety of versatile electrophiles such as acid chlorides, aryl iodides, aldehydes, and disulfide.

Electrochemical materials science: calculation vs. experiment as predictive tools in tailoring intrinsically conducting polythiophenes

“…The product was recrystallized from pentane at 0 o C with charcoal followed by sublimation. 1 H NMR, 13 C and GC-MS are measured and found to be in agreement with published data [83], with yields in the range of 62 -80 %, (Scheme 2). …”

“…2) were prepared by catalyzed coupling reaction according to literature [83]. The general procedure for their preparation can be summarized in:…”

Synthesis of the Benzo-fused Indolizidine Alkaloid Mimics

“…Encouraged by these results, the reaction of 3-heteroaryl Grignard reagents was also examined (entries 6–9). The 3-furyl [ 16 ] and 3-thienyl [ 17 ] Grignard reagents were prepared from the corresponding 3-bromo compounds and gave 1f and 1g in moderate yields (entries 6,7). The compounds 1h and 1i were prepared in good yield from N -TIPS-3-bromopyrrole [ 18 ] and N -TIPS-3-bromoindole (entries 8,9).…”

Efficient Cobalt‐Catalyzed Formation of Unsymmetrical Biaryl Compounds and Its Application in the Synthesis of a Sartan Intermediate

“…[2] Among the innumerable methods for the construction of aryl-aryl bonds, transition-metal-mediated reactions constitute one of the main strategies used. [3] Generally, such reactions involve the coupling of an organometallic reagent (ArM; M = B, [4] Sn, [5] Si, [6] Zn, [7] Mg, [8] Mn [9] ) with an aryl halide or pseudohalide. They all require the preparation of a stoichiometric organometallic reagent and typically the presence of a Ni or Pd complex as a catalyst.…”