74153-17-6Relevant articles and documents
Highly S(N)2'-, (E)-, and antiselective alkylation of allylic phosphates. Facile synthesis of coenzyme Q10
Yanagisawa,Nomura,Noritake,Yamamoto
, p. 1130 - 1136 (2007/10/02)
Treatment of secondary allylic chlorides or allylic phosphates in tetrahydrofuran with prenyl Grignard reagent in the presence of CuCN · 2 LiCl gave geraniol or farnesol derivatives with high S(N)2' selectivity. Phosphate leaving groups were highly transstereoselective for the formation of (E,E)-farnesol derivatives. Furthermore, complete anti-S(N)2' selectivity was observed in the alkylation of optically active allylic phosphates. The present method appears to be an excellent carbon-carbon coupling reaction with high regio-, (E)-, and enantioselectivity. Coenzyme Q10 (ubiquinone 10) was efficiently synthesized using this methodology.
Stereochemical Studies on the Nucleophilic Substitution in the Reaction of Allylic Phosphates with Organoaluminum Reagents
Itoh, Akira,Ozawa, Shuji,Oshima, Koichiro,Sasaki, Shizuka,Yamamoto,Hajime,et al.
, p. 2357 - 2362 (2007/10/02)
The reaction of cis- or trans-5-isopropenyl-2-methyl-2-cyclohexenyl diethyl phosphate (1) with Me2AlX (X= OPh, SPh, NHPh) in hexane results in substitution of the -O-PO(OEt)2 group with X under predominant inversion.In contrast, treatment of cis- or trans-1 with trialkylaluminum produces predominantly the allyl-nonallyl coupling products of the same (thermodynamically more stable) configuration.Similar alkylation of endo- and exo-2-acetoxynorcarane gave endo-2-methylnorcarane, exclusively.
