Asymmetric alkylation reactions using non-cross-linked polystyrene (NCPS)-supported 2-imidazolidinone chiral auxiliaries were successfully investigated with excellent diastereocontrol (>99% de). The recovery and the recycling of this soluble polymer-supported chiral auxiliary were achieved in order to produce highly optical pure carboxylic acids.
Download full-text PDF |
Source |
---|---|
http://www.ncbi.nlm.nih.gov/pmc/articles/PMC3817508 | PMC |
http://dx.doi.org/10.3762/bjoc.9.248 | DOI Listing |
Macromol Rapid Commun
December 2015
Department of Molecular Design and Engineering, Graduate School of Engineering, Nagoya University, Nagoya, 464-8603, Japan.
A series of optically active helical copolymers of phenylacetylenes are prepared by the rhodium-catalyzed copolymerization of the imidazolidinone-linked, catalytically active achiral phenylacetylenes and catalytically inactive chiral phenylacetylenes. The obtained chiral/achiral copolymers exhibit an induced circular dichroism in the UV-vis regions of the copolymer backbones resulting from a preferred-handed helical conformation biased by the chiral imidazolidinone units incorporated in the copolymers. The copolymers are found to catalyze the asymmetric Diels-Alder reaction and produce the products with a moderate enantioselectivity in spite of the fact that the catalytically active units of the copolymers are achiral, indicating that the observed enantioselectivity totally originates from the helical chirality dynamically induced by the optically active, but catalytically inactive imidazolidinone units incorporated in the copolymers.
View Article and Find Full Text PDFJ Org Chem
January 2015
Department of Chemistry, University of Cape Town, Rondebosch 7701, South Africa.
A new stereoselective alkylation methodology is presented for formation of chiral, nonracemic quaternary centers via a chiral auxiliary protocol involving α-alkylated malonate imidazolidinones. Based on two X-ray structures of quaternized products, the diastereoselectivity observed may be rationalized via a transition-state involving an s-transC-N conformation of the C-N bond of the auxiliary, with the metal cation (K(+)) chelated into the malonate six-membered hole as a Z-enolate. A deprotection protocol involving ethanethiolate exchange of the imide to the corresponding thioester, followed by a standard Fukuyama reduction and a borohydride reduction, furnishes α,α'-quaternized β-hydroxypropionates in high ee overall.
View Article and Find Full Text PDFBeilstein J Org Chem
November 2013
School of Applied Chemistry and Center for Functional Nano Fine Chemicals, Chonnam National University, Gwangju 500-757, Republic of Korea.
Asymmetric alkylation reactions using non-cross-linked polystyrene (NCPS)-supported 2-imidazolidinone chiral auxiliaries were successfully investigated with excellent diastereocontrol (>99% de). The recovery and the recycling of this soluble polymer-supported chiral auxiliary were achieved in order to produce highly optical pure carboxylic acids.
View Article and Find Full Text PDFJ Org Chem
December 2001
Department of Chemistry and Biochemistry, University of Regina, Regina, Saskatchewan, S4S 0A2, Canada.
(-)- and (+)-Geissman-Waiss lactone, 4b, was efficiently prepared via the intramolecular C-H insertion reaction of the chiral nonracemic diazoacetates (-)-5a and (+)-5b catalyzed by dirhodium(II) tetrakis[methyl (5R and 5S)-3-phenylpropanoyl-2-imidazolidinone-5-carboxylate]. The cyclization was found to proceed with excellent regioselectivity and cis-diastereoselectivity. The bicyclic lactone (-)-4b was successfully used in the synthesis of the necine base, (-)-turneforcidine 2.
View Article and Find Full Text PDFEnantiomer
March 2000
Department of Chemistry, University of Arizona, Tucson 85721-0041, USA.
Chiral dirhodium(II) complexes constructed from 2-oxopyrrolidine, 2-oxazolidinone, N-acyl-2-imidazolidinone, or 2-azetidinone ligands are exceptional catalysts for enantioselective metal carbene transformations which provide lactones and lactams via cyclopropanation, cyclopropenation, C-H insertion, and ylide reactions with enantiomeric excesses greater than 90% and, usually, in very high yields. These chiral catalysts present high diastereo-, regio- and chemoselectivities, turnover numbers up to 1000, as well as recoverability and reuse.
View Article and Find Full Text PDFEnter search terms and have AI summaries delivered each week - change queries or unsubscribe any time!