59376-65-7

Upstream product

• 18178-59-1 (E)-1,2-bis(trimethylsilyl)ethene 
• 107-30-2 chloromethyl methyl ether 
• 75-36-5 acetyl chloride 
• 2200-53-5 penta-3,4-dien-2-one 
• 82777-76-2 iodure d'ethylenedioxy-2,2 methoxy-5 pentyl-4 triphenylphosphonium 
• 82777-75-1 1-<(2-Methyl-1,3-dioxolan-2-yl)methyl>ethenyltriphenylphosphonium iodide 
• 82777-77-3 iodure d'oxo-2 methoxy-5 pentyl-4 triphenylphosphonium 

Relevant academic research and scientific papers

Carbonylation of allylic ethers to esters

A method is disclosed for the production of esters by reaction of an allylic ether with carbon monoxide in the presence of a catalytically effective amount of a Group VIII noble metal catalyst and halide compound to obtain esters. The halide compound is present in an amount sufficient to prevent the catalyst from being converted into a Group VIII metal during the reaction. When the reaction is conducted in the presence of a quaternary ammonium salt the ester may be extracted by solvent extraction to minimize catalyst decomposition caused when extractive distillation is used to separate the ester.

Inversion de polarite par les groupes phosphore: inversion de regioselectivite dans l'addition des nucleophiles sur les allenes actives par des groupes attracteurs

Change in the regioselectivity of the addition of nucleophilic compounds YH (ROH, RSH, RNH2) on α-allenic ketones and esters can be effected by using the triphenylphosphonio group as an umpolung agent.In this way α,β-unsaturated ketones and esters are obtained with heteroatomic substituents in the γ position.The umpolung scheme of the activated allene is characterized by a vinylphosphonium salt 7 or 10 as a synthetic equivalent of the a4 synthon .CH2-CH=CH-Z.The synthetic process requires three (Z = COCH3) or two (Z = CO2CH3) distinct manipulations and gives good overall yields (63 to 71percent).This umpolung method can also be applied to binucleophilic compounds as a new synthesis for functional heterocycles such as the substituted dioxan 15c or pyrrole 16d.Two separate side reactions of the intermediary phosphonium salts were found to occur: a) the isomerization of the vinylphosphonium salts with migration of the double bond, and, b) for β-substituted phosphonium salts, exchange of heteroatomic groups Y through elimination-addition.Both side reactions can however be completely controlled.