Tsuji-Trost Reaction of Non-Derivatized Allylic Alcohols was written by Akkarasamiyo, Sunisa;Sawadjoon, Supaporn;Orthaber, Andreas;Samec, Joseph S. M.. And the article was included in Chemistry – A European Journal in 2018.Application In Synthesis of 4-Iodo-1,2-dimethoxybenzene This article mentions the following:
Palladium-catalyzed allylic substitution of non-derivatized enantioenriched allylic alcs. with a variety of uncharged N-, S-, C- and O-centered nucleophiles using a bidentate BiPhePhos ligand is described. A remarkable effect of the counter ion (X) of the XPd[κ2-BiPhePhos][η3-C3H5] was observed When ClPd[κ2-BiPhePhos][η3-C3H5] was used as catalyst, non-reproducible results were obtained. Study of the complex by X-ray crystallog., 31P NMR spectroscopy, and ESI-MS showed that a decomposition occurred where one of the phosphite ligands was oxidized to the corresponding phosphate, generating ClPd[κ1-BiPhePhosphite-phosphate][η3-C3H5] species. When the chloride was exchanged to the weaker coordinating OTf– counter ion the more stable Pd[κ2-BiPhePhos][η3-C3H5]++[OTf] – was formed. The complex Pd[κ2-BiPhePhos][η3-C3H5]++[OTf] – performed better and gave higher enantiospecificities in the substitution reactions. The complex Pd[κ2-BiPhePhos][η3-C3H5]++[OTf] – was evaluated in Tsuji-Trost reactions of stereogenic non-derivatized allylic alcs. The desired products were obtained in good to excellent yields (71-98 %) and enantiospecificities (73-99 %) for both inter- and intramol. substitution reactions with only water generated as a byproduct. The methodol. was applied to key steps in total synthesis of (S)-cuspareine (I) and (+)-lentiginosine (II). A reaction mechanism involving a palladium hydride as a key intermediate in the activation of the hydroxyl group is proposed in the overall transformation. In the experiment, the researchers used many compounds, for example, 4-Iodo-1,2-dimethoxybenzene (cas: 5460-32-2Application In Synthesis of 4-Iodo-1,2-dimethoxybenzene).
4-Iodo-1,2-dimethoxybenzene (cas: 5460-32-2) belongs to iodide derivatives. In general, organic iodides are light-sensitive and turn yellow during storage, owing to the formation of iodine. Alkyl iodides react at a faster rate than alkyl fluorides due to the weak C-I bond.Application In Synthesis of 4-Iodo-1,2-dimethoxybenzene
Referemce:
Iodide – Wikipedia,
Iodide – an overview | ScienceDirect Topics – ScienceDirect.com