Ruthenium-catalyzed allylic substitution of cyclic allyl carbonates with nucleophiles. Stereoselectivity and scope of the reaction

Authors
Morisaki, Y Kondo, T Mitsudo, TA
Citation
Y. Morisaki et al., Ruthenium-catalyzed allylic substitution of cyclic allyl carbonates with nucleophiles. Stereoselectivity and scope of the reaction, ORGANOMETAL, 18(23), 1999, pp. 4742-4746
Citations number
73
Categorie Soggetti
Organic Chemistry/Polymer Science
Journal title
ORGANOMETALLICS
ISSN journal
02767333 → ACNP
Volume
18
Issue
23
Year of publication
1999
Pages
4742 - 4746
Database
ISI
SICI code
0276-7333(19991108)18:23<4742:RASOCA>2.0.ZU;2-K
Abstract
CpRuCl(cod)/NH4PF6 (Cp = cyclopentadienyl, cod = 1,5-cyclooctadiene) is an effective catalyst system for the allylic substitution of cyclic allyl carb onates with nucleophiles. This catalyst system enables the first investigat ion of the stereochemical course of the ruthenium-catalyzed allylic substit ution reaction, in which the reaction proceeds with an overall retention of configuration. The stoichiometric reaction of trans-5-(methoxycarbonyl)cyc lohex-2-enyl chloride with Cp*RuCl(cod) (Cp* = pentamethylcyclopentadienyl) gave the unexpected complex Cp*Ru(eta(6)-C6H5CO2Me)(+) by the rapid dehydr ohalogenation/dehydrogenation of the desired Cp*RuCl2-(eta(3)-C6H8CO2Me) co mplex.