89922-39-4Relevant articles and documents
A Ball-Milling-Enabled Reformatsky Reaction
Cao, Qun,Stark, Roderick T.,Fallis, Ian A.,Browne, Duncan L.
, p. 2554 - 2557 (2019/06/17)
An operationally simple one-jar one-step mechanochemical Reformatsky reaction using in situ generated organozinc intermediates under neat grinding conditions has been developed. Notable features of this reaction protocol are that it requires no solvent, no inert gases, and no pre-activation of the bulk zinc source. The developed process is demonstrated to have good substrate scope (39–82 % yield) and is effective irrespective of the initial morphology of the zinc source.
Indium trichloride-promoted tin-mediated carbonyl allylation in water: High simple diastereo- and diastereofacial selectivity
Li, Xu-Ran,Loh, Teck-Peng
, p. 1535 - 1538 (2007/10/03)
Tin-mediated additions of allylic bromides to aldehydes and aldoses leads to adduct with high diastereo- and diastereofacial selectivity in the presence of indium trichloride in water.
Anion-Catalyzed Reactions of Silyl Ester Polyenolates with Electrophiles
Hertler, Walter R.,Reddy, Gade S.,Sogah, Dotsevi Y.
, p. 3532 - 3539 (2007/10/02)
The stereochemical assignments for the trimethylsilyl ester polyenolates 1, 2, and 3 have been made.Unlike simple silyl ketene acetals, 1, 2, and 3 are obtained predominantly as the thermodynamic Z isomers.Bifluoride-catalyzed equilibration studies showed the equilibrium compositions of 1, 2, and 3 to be 89percent Z, 67percent Z, and 95percent 1-Z,3-E, respectively.The regiochemistry of the bifluoride-catalyzed Reformatsky-type reaction of benzaldehyde with 1, 2, and 4 was determined.Regiochemical control of the condensation of 1 with benzaldehyde by reaction temperature was demonstrated, with 95percent α reaction at -95 deg C and 99percent γ-reaction at +34 deg C.Mechanism studies are consistent with a dissociative process in which a dienolate reacts with benzaldehyde at the α position to give the kinetic-controlled product, and as the reaction temperature increases, increasing amounts of the thermodynamic γ product are formed.A nondissociative cyclic process leading to α product may occur at low temperatures.The naked ester dienolate prepared by reaction of 1 with TASF and removal of the resulting fluorotrimethylsilane was alkylated by benzyl bromide exclusively at the α position at -100 deg C.The bifluoride-catalyzed reverse reaction of 1 with benzaldehyde is much slower than the processes that determine the regiochemistry in the forward reaction.
