Some insertion reactions of the Mn–C bond of cyclomanganated triphenylphosphine chalcogenides

Manganese-Mediated C-C Bond Formation via C-H Activation: From Stoichiometry to Catalysis

“…Second, both MnBr(CO) 5 and Cy 2 NH are commercially available. In contrast, the MnBn(CO) 5 reagent generally used in stoichiometric cyclomanganation reactions was tediously prepared from stepwise reactions employing Mn 2 (CO) 10 , Na/Hg amalgam, and benzyl chloride. 23…”

“…The group of Nicholson further investigated the reaction of cyclomanganated triphenylphosphine chalcogenide 18 with activated olefins (Scheme 4). 10 Given the low susceptibility of the P=S group to the nucleophilic attack as in the carbonyl-containing manganacycles, it was not so surprising that the alkylated product 19 rather than annulated compounds were obtained in varied yields. Of note, three-component-coupled products 20 and 21 arising from subsequent reactions with the solvent of acetonitrile were also observed when methyl acrylate and acrylonitrile were used as olefin substrates, respectively.…”

“…In a related work, the same group also demonstrated the successful isolation of seven-membered manganacycles 43 and 44 derived from triphenylphosphine sulfides. 10 Scheme 9 Isolation of seven-membered manganacycles by Nicholson and Main et al…”

An orthomanganation route to 2-substituted derivatives of N-methyl-1,8-naphthalimide

“…For examples with acyl groups there is insertion into the MneC bond followed by a cyclisation reaction involving the acyl groups to form indenols and related species [14,15,28,29]. In the case of orthomanganated P(OPh) 3 or Ph 3 P]S, insertion reactions with alkynes led to products with enlarged metallocyclic rings [30,31]. In other cases multiple insertions and cyclisations led to (h 5 -cyclohexadienyl)Mn(CO) 3 compounds with the arene attached to the new ring [14].…”

Amine-accelerated manganese-catalyzed aromatic C–H conjugate addition to α,β-unsaturated carbonyls

“…7 Then, the group of Nicholson further showed the addition of cyclomanganated triphenylphosphine chalcogenide to activated olefins (Scheme 1c). 8 It should be noted that these manganacycles were generally accessed from arenes and Mn(CH 2 Ph)(CO) 5 , which was made wearily by reactions of Mn 2 (CO) 10 , Na/Hg amalgam, and benzylchloride. 9 Also, stoichiometric amounts of promoters such as Li 2 PdCl 4 and Me 3 N + O À were often required to enhance the rather low reactivity of the manganacycles.…”