Catalytic Dimerization of Alkyl Acrylates∗

N-Heterocyclic Carbene-Catalyzed Cyclotetramerization of Acrylates

“…Catalytic oligomerizations of unsaturated compounds are important bond-forming reactions because they provide access to valuable chemicals such as higher olefins and cyclic products from simple chemical feedstocks. Among the activated olefins, methyl acrylate (MA) has been one of the most studied substrates due to its high reactivity toward nucleophiles or transition-metal complexes . Indeed, the Rauhut–Currier reaction, i.e., the head-to-tail dimerization, of MA is catalyzed by the trialkyl phosphines or the metal complexes to give the vinylidene dimer or trimer, which can be used as monomers for radical polymerizations .…”

Tail‐To‐Tail Stereoselective Dimerization of Acrylate Derivatives via Iridium‐Catalyzed Vinylic sp2 C−H Activation

“…Therefore, there is a high demand for the development of a facile and general synthesis of adipic acid derivatives. Dimerization of acrylate derivatives is a straightforward method and has been studied for a long time [2] . In recent years, while NHC‐catalyzed [3] and radical reactions [4] have been reported as a new protocol, transition metal‐mediated or ‐catalyzed dimerization of acrylates has also been investigated, and can be categorized into three types: head‐to‐head, [5] head‐to‐tail, [6] and tail‐to‐tail dimerization (Scheme 1).…”

“…Dimerization of acrylate derivatives is a straightforward method and has been studied for a long time. [2] In recent years, while NHC-catalyzed [3] and radical reactions [4] have been reported as a new protocol, transition metal-mediated or -catalyzed dimerization of acrylates has also been investigated, and can be categorized into three types: head-to-head, [5] head-totail, [6] and tail-to-tail dimerization (Scheme 1). Regarding tail-to-tail dimerization, which gives adipic acid derivatives, Ru, [7] Rh, [8] Pd, [9] Co, [10] and Ni [11] complexes have been reported as active catalysts, but the formation of 2,3-unsaturated products as byproducts via double-bond isomerization is often problematic (Scheme 1c).…”

Catalytic tail-to-tail dimerization of methyl acrylate using bis(triphenylphosphine)tricarbonyl ruthenium(0)

“…1). Various catalyst systems based on Pd, Ru, Rh and Ni have been reported for the dimerization of alkyl acrylates [1]. However, catalysis by ruthenium has not been thoroughly explored as compared to that by palladium [1].…”