Enantioselective C—C Bond Formation Enhanced by Self-Assembly of Achiral Surfactants

The use of achiral surfactant assemblies as a reaction platform for an alkylation reaction resulted in a high enantiomeric excess. Dilauryldimethylammonium bromide (DDAB) vesicles were modified with cholesterol to promote alkylation of N-(diphenylmethylene)glycine tert-butyl ester (DMGBE) with benzyl bromide, resulting in high conversion (∼90%) and high enantioselectivity (up to 80%). The R-enantiomer was formed on using the DDAB vesicles, whereas the use of phospholipid liposomes prepared from 1,2-dioleoyl-sn-glycero-3-phosphocholine (DOPC) produced an excess of the S-enantiomer. Considering the chemical structures of the reaction substrates and amphiphiles as well as the membrane structures and properties of DDAB vesicles and DOPC liposomes, it is suggested that the enantiomeric excesses result from the location of the quaternary amine of the amphiphiles and the DMGBE at the outer surface of the membrane. We show that the enantioselective reaction at the surface of the self-assembly could be regulated by adjusting the chemical structures and resulting membrane properties of the self-assembly.

• Publication year

  2017

• Venue

  ACS Omega

• Publication date

  2017-04-12

• Fields of study

  Medicine, Materials Science, Chemistry

• Identifiers
  DOI 10.1021/ACSOMEGA.7B00034PMID 31457516PMCID 6641137
• External record

  Open on Semantic Scholar

• Source metadata

  Semantic Scholar, PubMed

• No claims are published for this paper.

• No concepts are published for this paper.

• Characterization of DDAB/Cholesterol Vesicles and Its Comparison with Lipid/Cholesterol Vesicles.

  2018cited by this paper
• Liposomes Can Achieve Enantioselective C–C Bond Formation of an α-Amino Acid Derivative in Aqueous Media

  2017cited by this paper
• An Insoluble Copper(II) Acetylacetonate-Chiral Bipyridine Complex that Catalyzes Asymmetric Silyl Conjugate Addition in Water.

  2015cited by this paper
• Pseudo-Interphase of Liposome Promotes 1,3-Dipolar Cycloaddition Reaction of Benzonitrile Oxide and N-Ethylmaleimide in Aqueous Solution.

  2015cited by this paper
• Chiral Recognition of L-Amino Acids on Liposomes Prepared with L-Phospholipid.

  2015cited by this paper
• An overview of Zn-catalyzed enantioselective aldol type C–C bond formation

  2015cited by this paper
• Highly enantioselective rhodium(I)-catalyzed carbonyl carboacylations initiated by C-C bond activation.

  2014cited by this paper
• Efficient Polymerization of the Aniline Dimer p-Aminodiphenylamine (PADPA) with Trametes versicolor Laccase/O2 as Catalyst and Oxidant and AOT Vesicles as Templates

  2014cited by this paper
• Phase-transfer-catalysed asymmetric synthesis of tetrasubstituted allenes.

  2013cited by this paper
• Detection of nanosized ordered domains in DOPC/DPPC and DOPC/Ch binary lipid mixture systems of large unilamellar vesicles using a TEMPO quenching method.

  2013cited by this paper
• Effects of temperature on micellar-assisted bimolecular reaction of methylnaphtalene-2-sulphonate with bromide and chloride ions.

  2013cited by this paper
• Role of the alkyl chain number and head groups location on surfactants self-assembly in aqueous solutions

  2010cited by this paper
• Powerful Chiral Phase‐Transfer Catalysts for the Asymmetric Synthesis of α‐Alkyl‐ and α,α‐Dialkyl‐α‐amino Acids

  2005cited by this paper
• Unusual rate enhancement of bimolecular dehydrocondensation to form amides at the interface of micelles of fatty acid salts.

  2005cited by this paper
• Powerful chiral phase-transfer catalysts for the asymmetric synthesis of alpha-alkyl- and alpha,alpha-dialkyl-alpha-amino acids.

  2005cited by this paper
• Highly enantioselective conjugate addition of malonate and beta-ketoester to nitroalkenes: asymmetric C-C bond formation with new bifunctional organic catalysts based on cinchona alkaloids.

  2004cited by this paper
• Carbon nanotube aqueous sol-gel composites: enzyme-friendly platforms for the development of stable biosensors.

  2004cited by this paper
• Vesicles from Salt-Free Cationic and Anionic Surfactant Solutions

  2003cited by this paper
• Enantioselective Synthesis of α‐Hydroxy Ketones via Benzaldehyde Lyase‐Catalyzed C−C Bond Formation Reaction

  2002cited by this paper
• Efficient activation of aromatic C-H bonds for addition to C-C multiple bonds

  2000cited by this paper
• The discovery of novel reactivity in the development of C-C bond-forming reactions: in situ generation of zinc acetylides with Zn(II)/R(3)N.

  2000cited by this paper
• Quantitation of lipid phases in phospholipid vesicles by the generalized polarization of Laurdan fluorescence.

  1991cited by this paper
• PHASE – TRANSFER CATALYSIS. I. HETEROGE NEOUS REACTIONS INVOLVING ANION TRANSFER BY QUATERNARY AMMONIUM AND PHOSPHONIUM SALTS

  1971cited by this paper

• Vesicles as a Multifunctional Microenvironment for Electrochemiluminescence Signal Amplification.

  2023cites this paper
• Pore expanding effect of hydrophobic agent on 100 nm-sized mesoporous silica particles estimated based on Hansen solubility parameters

  2021cites this paper
• Soft and dispersed interface-rich aqueous systems that promote and guide chemical reactions

  2018cites this paper