56674-69-2Relevant articles and documents
Stereodivergence in the Ireland-Claisen Rearrangement of α-Alkoxy Esters
Podunavac, Ma?a,Lacharity, Jacob J.,Jones, Kerry E.,Zakarian, Armen
supporting information, p. 4867 - 4870 (2018/08/24)
A systematic investigation into the Ireland-Claisen rearrangement of α-alkoxy esters is reported. In all cases, the use of KN(SiMe3)2 in toluene gave rearrangement products corresponding to a Z-enolate intermediate with excellent diastereoselectivity, presumably because of chelation control. On the other hand, chelation-controlled enolate formation could be overcome for most substrates through the use of lithium diisopropylamide (LDA) in tetrahydrofuran (THF).
The reactions of ethyl-, vinyl-, and ethynyl(trichloromethyl)carbinols with aqueous amd methanolic potassium hydroxide, thiourea, and cyanamide
Reeve, Wilkins,Steckel, Thomas F.
, p. 2784 - 2788 (2007/10/02)
The reactions of ethyl(trichloromethyl)carbinol, dimethyl(trichloromethyl)carbinol. (trichloromethyl)vinylcarbinol, ethynyl(trichloromethyl)carbinol, and 1,1,1-trichloro-3-nonyn-2-ol have been studied with the following reagents.Methanolic potassium hydroxide: α-methoxy acids are formed in 70 and 79 percent yields with the ethyl- and vinylcarbinols respectively.Double bond migration to the conjugated position was observed with the vinylcarbinol.Thiourea: substituted 2-imino-4-thiazolidinones are formed in 27 to 66 percent yield with the first three carbinols with double bond migration in the case of the vinylcarbinol.Cyanamide: the saturated carbinols were converted to substituted ethyl 2-imino-4-oxo-1-imidazolidinecarboximidates in 30 to 60 percent yield.Aqueous potassium hydroxide: α-chloro acids were formed from the ethyl- and vinylcarbinols in 23 and 24 percent yields respectively, again with double bond migration in the case of the vinylcarbinol.The results are discussed in terms of the known parallel reactions with phenyl(trichloromethyl)carbinol, and provide information which illustrates the usefulness and defines the limits of certain known synthetic reactions when applied to the alkyl, alkenyl, and alkynyl trichloromethylcarbinols.
