Ni-catalyzed activation of α-chloroesters: a simple method for the synthesis of α-arylesters and β-hydroxyesters

Nickel-Catalyzed Reductive Couplings

“…Therein, oxidative addition of ArX to Bn-Ni I results in the key Ar-Ni III (X)-Bn intermediate [52]. While electrochemical arylation and vinylation of a-chloroketones and esters, as well as allyl acetates are well established [35], the equivalent chemical reduction methods have been documented for arylation of a-chloroesters (Scheme 21) [60] and allylic acetates [37,61]. The allylation of aryl halides is generally efficient for both electron-deficient and -rich arenes, which display excellent regioselectivities by the addition of aryl groups to the less-hindered allylic terminals (Scheme 22) [37,61].…”

Formation and electrochemical behavior characterizations of dibromo 2,2′-bipyridine manganese(II) systems in DMF solution

“…Furthermore, we recently developed chemical reactions catalyzed by iron(II) [5], nickel(II) [6] or cobalt(II) [7] bipyridine complexes, which were reduced by manganese metal to generate in situ the bas-valent catalyst. Particularly, we wanted to elucidate the mechanism of the crosscoupling between aryl halides and a-chloroesters, leading to aryl propanoic ester [6].…”

“…Particularly, we wanted to elucidate the mechanism of the crosscoupling between aryl halides and a-chloroesters, leading to aryl propanoic ester [6]. So we have undertaken voltammetric studies to understand the role of manganese metal, since it seems to have another function than a simple reducing agent [8].…”

Nickel-Catalyzed Asymmetric Reductive Cross-Coupling between Heteroaryl Iodides and α-Chloronitriles

“…1 These transformations forge C–C bonds between two organic electrophiles, employing a stoichiometric reductant (usually Zn 0 or Mn 0 ) to turn over the Ni catalyst. An appealing aspect of this chemistry is that sec -alkyl electrophiles are competent reaction partners, 2 and in some cases, these reactions can be rendered enantioselective by use of an appropriate chiral ligand. 3 However, the scope of C(sp 3 ) electrophiles used in these asymmetric transformations has so far been limited to α-substituted benzyl chlorides.…”