QSAR analysis of the catalytic asymmetric ethylation of ketone using physical steric parameters of chiral ligand substituents

Abstract We have demonstrated that a validated QSAR (quantitative structure–activity relationship) model can be constructed between sterimol steric parameters of the N-substituents of chiral 1,2-amino-phosphoramide ligands and the enantiomeric ratios of alcohol products produced in the asymmetric additions of diethylzinc to acetophenone, which is powerful for predicting the steric effects of ligand substituents on enantioselectivities and instructive for ligand optimization.

[1]  Scott J. Miller,et al.  Linear free-energy relationship analysis of a catalytic desymmetrization reaction of a diarylmethane-bis(phenol). , 2010, Organic letters.

[2]  M. Yus,et al.  FIRST ENANTIOSELECTIVE ADDITION OF DIALKYLZINC TO KETONES PROMOTED BY TITANIUM(IV) DERIVATIVES , 1998 .

[3]  Matthew S Sigman,et al.  Predicting and optimizing asymmetric catalyst performance using the principles of experimental design and steric parameters , 2011, Proceedings of the National Academy of Sciences.

[4]  P. Walsh,et al.  A practical catalytic asymmetric addition of alkyl groups to ketones. , 2002, Journal of the American Chemical Society.

[5]  E. Jacobsen,et al.  Mechanism of amido-thiourea catalyzed enantioselective imine hydrocyanation: transition state stabilization via multiple non-covalent interactions. , 2009, Journal of the American Chemical Society.

[6]  S. Denmark,et al.  A systematic investigation of quaternary ammonium ions as asymmetric phase-transfer catalysts. Synthesis of catalyst libraries and evaluation of catalyst activity. , 2011, The Journal of organic chemistry.

[7]  A. Alex,et al.  Theoretical prediction of the enantiomeric excess in asymmetric catalysis. An alignment-independent molecular interaction field based approach. , 2005, The Journal of organic chemistry.

[8]  C. Pittman,et al.  Chiral ligands derived from Abrine 8. An experimental and theoretical study of free ligand conformational preferences and the addition of diethylzinc to benzaldehyde. , 2005, Journal of Organic Chemistry.

[9]  Scott E Denmark,et al.  A systematic investigation of quaternary ammonium ions as asymmetric phase-transfer catalysts. Application of quantitative structure activity/selectivity relationships. , 2011, The Journal of organic chemistry.

[10]  M. Sigman,et al.  Quantitatively correlating the effect of ligand-substituent size in asymmetric catalysis using linear free energy relationships. , 2008, Angewandte Chemie.

[11]  B. Feringa,et al.  Catalytic enantioselective Reformatsky reaction with ketones. , 2008, Chemical communications.

[12]  M. Charton.  STERIC EFFECTS. 10. SUBSTITUENTS AT NITROGEN IN CARBONYL COMPOUNDS , 1977 .

[13]  H. Kubinyi.  QSAR : Hansch analysis and related approaches , 1993 .

[14]  M. Kozlowski,et al.  Quantum Molecular Interaction Field Models of Substrate Enantioselection in Asymmetric Processes. , 2010, Journal of molecular catalysis. A, Chemical.

[15]  Robert W. Taft,et al.  Linear Steric Energy Relationships , 1953 .

[16]  Paul Ha-Yeon Cheong,et al.  Computational prediction of small-molecule catalysts , 2008, Nature.

[17]  C. Bolm,et al.  New insights into the stereoselectivity of the aryl zinc addition to aldehydes. , 2005, Journal of the American Chemical Society.

[18]  M. Sigman,et al.  Systematically probing the effect of catalyst acidity in a hydrogen-bond-catalyzed enantioselective reaction. , 2007, Angewandte Chemie.

[19]  M. Yus,et al.  Toward the continuous-flow synthesis of chiral tertiary alcohols by enantioselective addition of organozinc reagents to ketones using nanosize isoborneol ligands , 2008 .

[20]  Gadi Rothenberg,et al.  Predictive modeling in homogeneous catalysis: a tutorial. , 2010, Chemical Society reviews.

[21]  M. Charton,et al.  Steric effects. I. Esterification and acid-catalyzed hydrolysis of esters , 1975 .

[22]  S. L. Dixon,et al.  Quantum mechanical models correlating structure with selectivity: predicting the enantioselectivity of beta-amino alcohol catalysts in aldehyde alkylation. , 2003, Journal of the American Chemical Society.

[23]  L. Pu.  Asymmetric Alkynylzinc Additions to Aldehydes and Ketones , 2003 .

[24]  M. Sigman,et al.  Three-Dimensional Correlation of Steric and Electronic Free Energy Relationships Guides Asymmetric Propargylation , 2011, Science.

[25]  A. Minnaard,et al.  Asymmetric copper-catalyzed addition of Grignard reagents to aryl alkyl ketones. , 2012, Angewandte Chemie.

[26]  P. Cozzi.  A catalytic, Me2Zn-mediated, enantioselective reformatsky reaction with ketones. , 2006, Angewandte Chemie.

[27]  M. Yus,et al.  Synthesis of new C2-symmetrical bis(hydroxycamphorsulfonamide) ligands and their application in the enantioselective addition of dialkylzinc reagents to aldehydes and ketones , 2003 .

[28]  K. Ishihara,et al.  Commercially available neat organozincs as highly reactive reagents for catalytic enantioselective addition to ketones and aldehydes under solvent free conditions , 2011 .

[29]  K. Ishihara,et al.  Catalytic enantioselective organozinc addition toward optically active tertiary alcohol synthesis. , 2009, Chemical record.

[30]  Roberto Todeschini,et al.  Handbook of Molecular Descriptors , 2002 .

[31]  Jiang-Hua Chen,et al.  Calculation on enantiomeric excess of catalytic asymmetric reactions of diethylzinc addition to aldehydes with topological indices and artificial neural network , 2006 .

[32]  M. Yus,et al.  First enantioselective addition of diethylzinc and dimethylzinc to prostereogenic ketones catalysed by camphorsulfonamide-titanium alkoxide derivatives , 1998 .

[33]  M. Yus,et al.  Highly enantioselective addition of dialkylzinc reagents to ketones promoted by titanium tetraisopropoxide , 2002 .

[34]  Matthew S Sigman,et al.  Prediction of catalyst and substrate performance in the enantioselective propargylation of aliphatic ketones by a multidimensional model of steric effects. , 2013, Journal of the American Chemical Society.

[35]  M. Yus,et al.  (−)-Frontalin: Synthesis using the Catalytic Enantioselective Addition of Dimethylzinc to a Ketone , 2003 .

[36]  B. Shen,et al.  Highly efficient asymmetric additions of diethylzinc to aldehydes triply activated by chiral phosphoramide-Zn(II) complexes derived from cinchona alkaloids. , 2013, Chirality.

[37]  M. Sigman,et al.  Advancing the mechanistic understanding of an enantioselective palladium-catalyzed alkene difunctionalization reaction. , 2010, Journal of the American Chemical Society.

[38]  D. Avnir,et al.  Quantitative chirality analysis of molecular subunits of bis(oxazoline)copper(II) complexes in relation to their enantioselective catalytic activity. , 2003, Chemistry.

[39]  T. Miyamoto,et al.  Highly active chiral phosphoramide-Zn(II) complexes as conjugate acid-base catalysts for enantioselective organozinc addition to ketones. , 2007, Organic letters.

[40]  M. Sigman,et al.  Examination of the role of Taft-type steric parameters in asymmetric catalysis. , 2009, The Journal of organic chemistry.

[41]  Manuel Urbano-Cuadrado,et al.  New Quantum Mechanics-Based Three-Dimensional Molecular Descriptors for Use in QSSR Approaches: Application to Asymmetric Catalysis , 2007, J. Chem. Inf. Model..

[42]  E. Corey,et al.  The Catalytic Enantioselective Construction of Molecules with Quaternary Carbon Stereocenters. , 1998, Angewandte Chemie.

[43]  Scott J. Miller.  Asymmetric catalysis: Correlating sterics in catalysis. , 2012, Nature chemistry.

[44]  R. Hsung,et al.  De novo chiral amino alcohols in catalyzing asymmetric additions to aryl aldehydes. , 2006, Organic letters.

[45]  Matthew S Sigman,et al.  Using physical organic parameters to correlate asymmetric catalyst performance. , 2013, The Journal of organic chemistry.

[46]  Per-Ola Norrby,et al.  Steric Influences on the Selectivity in Palladium-Catalyzed Allylation , 1997 .

[47]  M. Charton.  Steric effects. 7. Additional V constants , 1976 .

[48]  M. Yus,et al.  Chiral tertiary alcohols made by catalytic enantioselective addition of unreactive zinc reagents to poorly electrophilic ketones? , 2004, Angewandte Chemie.

[49]  Robert W. Taft,et al.  Linear Free Energy Relationships from Rates of Esterification and Hydrolysis of Aliphatic and Ortho-substituted Benzoate Esters , 1952 .

[50]  K. Ishihara,et al.  Catalytic enantioselective alkyl and aryl addition to aldehydes and ketones with organozinc reagents derived from alkyl Grignard reagents or arylboronic acids , 2011 .

[51]  Per-Ola Norrby,et al.  Prediction of enantioselectivity in rhodium catalyzed hydrogenations. , 2009, Journal of the American Chemical Society.

[52]  K. Fuji.  Asymmetric creation of quaternary carbon centers , 1993 .

[53]  P. Walsh,et al.  A green chemistry approach to a more efficient asymmetric catalyst: solvent-free and highly concentrated alkyl additions to ketones. , 2005, Journal of the American Chemical Society.

[54]  M. Kozlowski,et al.  A priori theoretical prediction of selectivity in asymmetric catalysis: design of chiral catalysts by using quantum molecular interaction fields. , 2006, Angewandte Chemie.

[55]  M. Yus,et al.  Chiral tertiary alcohols from a trans-1-arenesulfonyl-amino-2-isoborneolsulfonylaminocyclohexane-catalyzed addition of organozincs to ketones , 2005 .

[56]  Hua Zong,et al.  Constructing a quantitative correlation between N-substituent sizes of chiral ligands and enantioselectivities in asymmetric addition reactions of diethylzinc with benzaldehyde. , 2012, The Journal of organic chemistry.

[57]  M. Kozlowski,et al.  Understanding Stereoinduction in Catalysis via Computer: New Tools for Asymmetric Synthesis , 2003 .

[58]  M. Sigman,et al.  Evaluation of catalyst acidity and substrate electronic effects in a hydrogen bond-catalyzed enantioselective reaction. , 2010, The Journal of organic chemistry.

[59]  P. Walsh,et al.  Catalytic asymmetric addition of alkylzinc and functionalized alkylzinc reagents to ketones. , 2005, The Journal of organic chemistry.

[60]  Matthew S Sigman,et al.  Multidimensional steric parameters in the analysis of asymmetric catalytic reactions. , 2012, Nature chemistry.