444575-92-2Relevant academic research and scientific papers
A chiral sulfoxide-ligated ruthenium complex for asymmetric catalysis: Enantio- and regioselective allylic substitution
Trost, Barry M.,Rao, Meera,Dieskau, Andre P.
, p. 18697 - 18704 (2014/01/06)
The design and synthesis of a novel chiral sulfoxide-ligated cyclopentadienyl ruthenium complex is described. Its utility as an asymmetric variant of [CpRu(MeCN)3]PF6 is demonstrated through its ability to function in the branched-selective asymmetric allylic alkylation of phenols and carboxylic acids. Water has also been shown to act as a competent nucleophile in this reaction to generate branched allyl alcohols with good regio- and enantioselectivities.
(Cyclopentadienyl)ruthenium-catalyzed regio- and enantioselective decarboxylative allylic etherification of allyl aryl and alkyl carbonates
Austeri, Martina,Linder, David,Lacour, Jerome
experimental part, p. 3339 - 3347 (2011/02/23)
(Cyclopentadienyl)tris(acetonitrile)ruthenium hexafluorophosphate {[CpRu(NCMe)3][PF6] or (cyclopentadienyl) (I·6-naphthalene)ruthenium hexafluorophosphate {[CpRu(I·6-naphthalene)][PF6]} in combination with a pyridine oxazoline ligand efficiently catalyze the decarboxylative allylic rearrangement of allyl aryl carbonates. Good levels of regio- and enantioselectivity are obtained. Starting from enantioenriched secondary carbonates, the reaction is stereospecific and the corresponding allylic ethers are obtained with net retention of configuration. An intermolecular version of this transformation was also developed using allyl alkyl carbonates as substrates. Conditions were found to obtain the corresponding products with similar selectivity as in the intramolecular process. Through the use of a hemi-labile hexacoordinated phosphate counterion, a zwitterionic air- and moisture-stable chiral ruthenium complex was synthesized and used in the enantioselective etherification reactions. This highly lipophilic metal complex can be recovered and efficiently reused in subsequent catalysis runs. Copyright
Regio- and enantioselective O-allylation of phenol and alcohol catalyzed by a planar-chiral cyclopentadienyl ruthenium complex
Onitsuka, Kiyotaka,Okuda, Haruki,Sasai, Hiroaki
, p. 1454 - 1457 (2008/12/22)
(Chemical Equation Presented) Design of an asymmetric catalyst: The planar-chiral cyclopentadienyl ruthenium complex shown in the scheme effectively catalyzes the reactions of unsymmetrically substituted allyl halides with phenol and alcohol to give the corresponding branched allyl ethers with high regio- and enantioselectivity.
Regio- and enantioselective iridium-catalyzed intermolecular allylic etherification of achiral allylic carbonates with phenoxides
Lopez, Fernando,Ohmura, Toshimichi,Hartwig, John F.
, p. 3426 - 3427 (2007/10/03)
An enantioselective and regioselective iridium-catalyzed allylic etherification is described. The reaction of sodium and lithium aryloxides with achiral (E)-cinnamyl and terminal aliphatic allylic electrophiles in the presence of 2 mol % of an iridium-phosphoramidite complex provides chiral allylic aryl ethers in high yields and excellent levels of regio- and enantioselectivity. Lithium aryloxides containing a single substituent at an ortho, meta, or para position as well as sterically hindered phenoxides were tolerated. Reactions in THF displayed the most suitable balance of rate, regio-, and enantioselectivity. High ee's were also observed for the products from the reaction of alkyl (E)-allylic carbonates. Copyright
A stereospecific ruthenium-catalyzed allylic alkylation
Trost, Barry M.,Fraisse, Pierre L.,Ball, Zachary T.
, p. 1059 - 1061 (2007/10/03)
Good regioselectivity and chirality transfer for aryl-substituted allyl units is achieved in allylic alkylations with a wide range of nucleophiles by using the highly active ruthenium catalyst 1. This method provides a route to antidepressants such as (-)-fluoxetine from (S)-ephedrine (see scheme; Cp* = η5-C5Me5, TBAT = tetrabutylammonium triphenyldifluorosilicate).
