Benzyl bromide addition to pentafluorobenzaldehyde by Zaitsev-Barbier reaction promoted with complex systems underlain by iron pentacarbonyl

Alkylation of Cymantrene with 1-Bromoadamantane Initiated by Iron Pentacarbonyl

“…The plausible mechanism of alkylation includes the formation of an intermediate complex of Fe(CO) 5 with bromoadamantane that activates alkyl halide [25] and gives rise to a radical, as it was assumed earlier [6][7][8]. The reaction conditions explored are likely to facilitate the formation of a sterically hindered radical or radical ion [26,27].…”

“…The ability of iron pentacarbonyl to initiate a range of С-С bond forming reactions is well known [1][2][3][4][5][6][7][8][9]. Iron pentacarbonyl (Fe(CO) 5 ) was shown to promote the addition of αhalocarboxylic acid esters and nitriles to aldehydes and ketones by the Reformatsky-type reaction [1][2][3].…”

“…Iron pentacarbonyl (Fe(CO) 5 ) was shown to promote the addition of αhalocarboxylic acid esters and nitriles to aldehydes and ketones by the Reformatsky-type reaction [1][2][3]. It was used successfully in diastereoselective hydrodimerization of aromatic aldehydes leading to diols [4], stereoselective reductive dimerization of chiral α-bromoamides resulting in bis(amides) [5], and addition of С 4 F 9 I to pentafluorobenzaldehyde [6] and benzyl bromide by the Zaitsev-Barbier reaction [7,8].…”

Ionic liquids in Barbier-Zaitsev reaction. Synthesis of 1-(perfluorophenyl)-2-phenylethanol in the presence of iron pentacarbonyl

“…These reactions are possible only at the use of metallocomplex initiators [2], for instance, the radical addition to the double C=C bond and the telomerization involving the benzyl bromide proceed under the action of the iron pentacarbonyl only in the presence of nucleophilic additive [3]. We have demonstrated that Fe(CO) 5 is an efficient promotor of the alkyl halides addition to the double bonds [1,3] C=C and C=O, and also of nitriles and esters of halogen-substituted acids to benzaldehydes and perfluorinated ketones by the type of reactions of Reformatsky [4] and Barbier-Zaitsev [5,6]. However benzyl bromide is an exception from this series for its addition to aromatic aldehydes initiated by Fe(CO) 5 along the Barbier-Zaitsev reaction becomes possible only in the presence of nucleophilic additives (HMPA, DMF) [6], and in both cases alongside the addition product forms dibenzyl as a side product.…”

“…We have demonstrated that Fe(CO) 5 is an efficient promotor of the alkyl halides addition to the double bonds [1,3] C=C and C=O, and also of nitriles and esters of halogen-substituted acids to benzaldehydes and perfluorinated ketones by the type of reactions of Reformatsky [4] and Barbier-Zaitsev [5,6]. However benzyl bromide is an exception from this series for its addition to aromatic aldehydes initiated by Fe(CO) 5 along the Barbier-Zaitsev reaction becomes possible only in the presence of nucleophilic additives (HMPA, DMF) [6], and in both cases alongside the addition product forms dibenzyl as a side product. Only in the presence of (S)-N-benzoyl-2-methoxycarbonylpyrrolidine the adduct was obtained without the dibenzyl impurity.…”