927-61-7Relevant articles and documents
Time-Resolved Study of the Solvent and Temperature Dependence of Singlet Oxygen (1Δg) Reactivity toward Enol Ethers: Reactivity Parameters Typical of Rapid Reversible Exciplex Formation
Gorman, A. A.,Gould, I. R.,Hamblett, I.
, p. 7098 - 7104 (1982)
Pulsed nitrogen laser excitation has been used to examine and compare the reactivities of four enol ethers toward singlet oxygen (1Δg) in five solvents.The experimental values of ΔH (0 +/- 1.0 kcal mol-1), ΔS (-23 to -34 eu), and the overall reaction rate constants (104-108 L mol-1 s-1) are characteristic of excited-state processes involving rapid reversible exciplex formation.Solvent effects are small but in some cases significant.It is concluded that such effects are the result of solvation entropy requirements at the transition state leading from exciplex to product, particularly in the case of dioxetane formation.The possibility is raised that the reversible exciplex mechanism operates generally for O2 (1Δg) reactions.
Stereoselective synthesis of β-C-D-glucopyranosides using the reaction of TMSCN and Grignard reagents with cyclic five-membered sulfonium salt intermediates
Liu, Hui,Smoliakova, Irina P
, p. 2973 - 2980 (2007/10/03)
In the presence of a Lewis acid, ArSCl adducts of tri-O-benzyl-D-glucal react with vinyl ethers to form cyclic five-membered sulfonium salt intermediates. The latter are capable of reacting with TMSCN and Grignard reagents furnishing exclusively 2-S-(aryl)-2-thio-β-C-D-glucopyranosides. The one-pot reaction also proceeds with high stereoselectivity of C-C bond formation in the lateral chain providing exclusively or predominantly C-glycosides with (S)-configuration of the chiral center in the lateral chain.
The reaction of 1-chloro-2-methyl-2-propenyllithium with a selection of organolithiums. The development and synthetic utility of novel base/nucleophile combinations
Nelson, Donna J.,Nagarajan, Ananthanarayanan
, p. 1 - 6 (2007/10/02)
The title compound was generated by and reacted with (1) a series of reagents which have basic as well as nucleophilic properties and (2) a series of base/nucleophile combinations.Product yields of the isobutenyl derivative were generally low to very good, and the best results (89percent) were obtained by using a 1:2 ratio (3 equiv total) of nBuLi:LiPPh2.Synthetic utility of the reaction is optimized as it approaches a situation in which the base/nucleophile combination is composed of one compound which is both a strong base and a poor nucleophile and another compound which is both a weak base and a good nucleophile.
