115420-22-9Relevant articles and documents
Dependence of the reactivities of titanium enolates on how they are generated: Diastereoselective coupling of phenylacetic acid esters using titanium tetrachloride
Matsumura, Yoshihiro,Nishimura, Maiko,Hiu, Hiroyuki,Watanabe, Mitsuaki,Kise, Naoki
, p. 2809 - 2812 (2007/10/03)
Oxidative coupling of phenylacetic acid esters was easily achieved by treating the esters with TiCl4 and then adding Et3N to the resulting solution. The products consisted of dl- and meso-2,3-diphenylsuccinic acid esters with the Claisen condensation product, and the ratio of these products depended on the reaction conditions. Reaction conditions suitable for high dl selectivity were determined, and a dimer of titanium enolate was postulated as an intermediate responsible for the high dl selectivity. The selectivities were compared with those in known oxidative couplings in which titanium enolate intermediates are prepared through lithium enolates and silyl enol ethers. The results suggest that the reactivities of titanium enolates intermediates depend on how they are generated.
Reaction of Dilithiated Carboxylic Acids with Iodine: Evidence for the Formation of a Radical Anion Intermediate
Renaud, Philippe,Fox, Marye Anne
, p. 3745 - 3752 (2007/10/02)
The mechanism for oxidative dimerization of carboxylic acid dianions involves single electron transfer to iodine, producing an organic anion radical.Rearrangement of this species was observed with suitable substrates at a rate competitive with intermolecular reactions.The radical anion can dimerize or react with iodine.The iodide thus generated can be isolated (reaction with excess of iodine) or can participate in a polar SN2-type reaction sequence leading to dimeric products (reaction with 1/2 equiv of iodine).The interference by free amines (liberated during the metalation with lithium amides) is rationalized by the formation of a charge-transfer complex with iodine which decomposes, liberating protons.