Highly enantioselective imine cinnamylation with a remarkable diastereochemical switch.

The first general method for the enantioselective cinnamylation of aldimines is reported. The method utilizes a simple chiral cinnamylsilane reagent and is characterized by experimental simplicity and extraordinarily high levels of enantioselectivity. Further, a remarkable and unprecedented diastereochemical reversal has been realized whereby either diastereomer may be accessed from the same trans-cinnamylsilane based upon a subtle change to the imine, thus obviating the usual requirement for both the trans- and cis-cinnamylsilanes.

• Publication year

  2007

• Venue

  Journal of the American Chemical Society

• Publication date

  2007-11-06

• Fields of study

  Medicine, Chemistry

• Identifiers
  DOI 10.1002/CHIN.200814075PMID 17983233
• 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.

• Indium-mediated asymmetric allylation of acylhydrazones using a chiral urea catalyst.

  2007cited by this paper
• Enantioselective imidazole-directed allylation of aldimines and ketimines.

  2007cited by this paper
• Phenol-directed enantioselective allylation of aldimines and ketimines.

  2006cited by this paper
• Discovery of ((4R,5S)-5-amino-4-(2,4,5- trifluorophenyl)cyclohex-1-enyl)-(3- (trifluoromethyl)-5,6-dihydro- [1,2,4]triazolo[4,3-a]pyrazin-7(8H)-yl)methanone (ABT-341), a highly potent, selective, orally efficacious, and safe dipeptidyl peptidase IV inhibitor for the treatment of type 2 diabetes.

  2006cited by this paper
• Highly diastereoselective and enantioselective preparation of homoallylic amines: application for the synthesis of beta-amino acids and gamma-lactams.

  2005cited by this paper
• Stereospecific, enantioselective allylation of alpha-hydrazono esters by using allyltrichlorosilanes with BINAP dioxides as neutral-coordinate organocatalysts.

  2004cited by this paper
• Enantioselective allylation of ketone-derived benzoylhydrazones: practical synthesis of tertiary carbinamines.

  2004cited by this paper
• Asymmetric synthesis of C-aliphatic homoallylic amines and biologically important cyclohexenylamine analogues.

  2004cited by this paper
• Chiral sulfoxides as neutral coordinate-organocatalysts in asymmetric allylation of N-acylhydrazones using allyltrichlorosilanes.

  2003cited by this paper
• Toward a versatile allylation reagent: practical, enantioselective allylation of acylhydrazones using strained silacycles.

  2003cited by this paper
• Catalytic, enantioselective alkylation of alpha-imino esters: the synthesis of nonnatural alpha-amino acid derivatives.

  2002cited by this paper
• Diastereoselective Barbier-type and palladium-mediated allylation of optically active aldimine with allylindium reagents.

  2001cited by this paper

• Carbene-Catalyzed Intramolecular Cyclization to Access Inherently Chiral Saddle-Shaped Lactones: Achiral Bases Alternate Product Chirality.

  2025cites this paper
• Enantio-divergent C–H borylation with two different ligands from a single chiral source

  2024cites this paper
• Sequential Ir‐Catalyzed Allylation/ 2‐aza‐Cope Rearrangement Strategy for the Construction of Chiral Homoallylic Amines †

  2020cites this paper
• A Regio- and Stereodivergent Synthesis of Homoallylic Amines via a One-Pot Cooperative Catalysis-based Allylic Alkylation/Hofmann Rearrangement Strategy.

  2019cites this paper
• 1,2-Amino alcohol-dependent Petasis allylboration for racemic and chiral homoallylamines

  2019cites this paper
• Protecting Group-directed Diastereodivergent Synthesis of Chiral Tetrahydronaphthalene-fused Spirooxindoles via Bifunctional Tertiary Amine Catalysis.

  2019cites this paper
• Silicon Hydrides and a Hydridosilicate Based on a Bulky Amidoalkoxide Ligand

  2018cites this paper
• Asymmetric cinnamylation of N-tert-butanesulfinyl imines with cinnamyl acetates: total syntheses of (+)-lycoricidine and (+)-7-deoxypancratistatin.

  2017cites this paper
• Single or Synergistic Kinetic Resolutions of Chiral Allylalanes: Two Complementary Routes for the Asymmetric Synthesis of Syn Homoallylamines.

  2017cites this paper
• Chiral Auxiliaries and Catalysts

  2017cites this paper
• Formal Allylic C(sp3)-H Bond Activation of Alkenes Triggered by a Sodium Amide.

  2017cites this paper
• Copper-catalyzed enantioselective stereodivergent synthesis of amino alcohols

  2016cites this paper
• Regiodivergent and Diastereoselective CuH-Catalyzed Allylation of Imines with Terminal Allenes.

  2016cites this paper
• Cyclopent-2-enylaluminium as allylzinc precursor for the diastereoselective allylmetallation of non-racemic imines: applications to the synthesis of enantiomerically enriched heterocycles.

  2016cites this paper
• Formaldehyde N,N-dialkylhydrazones as neutral formyl anion equivalents in iridium-catalyzed asymmetric allylic substitution.

  2015cites this paper
• Asymmetric Synthesis of Cyclohexane-Fused Drug-Like Spirocyclic Scaffolds Containing Six Contiguous Stereogenic Centers via Organocatalytic Cascade Reactions

  2015cites this paper
• Organocatalytic and enantioselective Michael reaction between α-nitroesters and nitroalkenes. Syn/anti-selectivity control using catalysts with the same absolute backbone chirality

  2015cites this paper
• Organocatalytic Morita–Baylis–Hillman/Michael/Acetalization Cascade: Procedure-Controlled Diastereodivergence in the Asymmetric Synthesis of Fully Substituted Tetrahydropyrans

  2014cites this paper
• Stereoselective allylboration of imines and indoles under mild conditions. An in situ E/Z isomerization of imines by allylboroxines

  2014cites this paper
• Stereocontrol in synthesis of homoallylic amines. Syn selective direct allylation of hydrazones with allylboronic acids.

  2014cites this paper
• Bifunctional Squaramide Catalysts with the Same Absolute Chirality for the Diastereodivergent Access to Densely Functionalised Cyclohexanes through Enantioselective Domino Reactions. Synthesis and Mechanistic Studies

  2014cites this paper
• Diametric stereocontrol in dynamic catalytic reduction of racemic acyl phosphonates: divergence from α-keto ester congeners.

  2013cites this paper
• Diastereoselective allylation of carbonyl compounds and imines: application to the synthesis of natural products.

  2013cites this paper
• Asymmetric intramolecular oxa-Michael reactions of cyclohexadienones catalyzed by a primary amine salt.

  2013cites this paper
• Divergent synthesis of functionalized carbocycles through organosilane-directed asymmetric alkyne-alkene reductive coupling and annulation sequence.

  2012cites this paper
• Switching diastereoselectivity in proline-catalyzed aldol reactions.

  2012cites this paper
• Selective access to both diastereoisomers in an enantioselective intramolecular Michael reaction by using a single chiral organocatalyst and application in the formal total synthesis of (-)-epibatidine.

  2012cites this paper
• 3.23 Stoichiometric Auxiliary Ligands for Metals and Main Group Elements: Ligands for Silicon

  2012cites this paper
• The effects of solvent on switchable stereoselectivity: copper-catalyzed asymmetric conjugate additions using D2-symmetric biphenyl phosphoramidite ligands.

  2012cites this paper
• (4S,5S)‐2‐Allyl‐2‐chloro‐3,4‐dimethyl‐5‐Phenyl‐1‐oxa‐3‐aza‐2‐Silacyclopentane

  2012cites this paper
• Chiral sulfoxide–olefin ligands: tunable stereoselectivity in Rh-catalyzed asymmetric 1,4-additions

  2012cites this paper
• Diastereodivergent asymmetric sulfa-Michael additions of α-branched enones using a single chiral organic catalyst.

  2011cites this paper
• Chiral sulfoxide-olefin ligands: completely switchable stereoselectivity in rhodium-catalyzed asymmetric conjugate additions.

  2011cites this paper
• Dramatic lithium chloride effect on the reaction stereocontrol in Zn-mediated asymmetric cinnamylation: highly practical synthesis of β-aryl homoallylic amines.

  2010cites this paper
• Asymmetric allylation, crotylation, and cinnamylation of N-heteroaryl hydrazones.

  2010cites this paper
• Highly enantioselective Pictet-Spengler reactions with alpha-ketoamide-derived ketimines: access to an unusual class of quaternary alpha-amino amides.

  2009cites this paper
• Stereoselective cross-coupling between allylic alcohols and aldimines.

  2009cites this paper
• Asymmetric synthesis of homoallylic amines bearing adjacent stereogenic centers by addition of substituted allylic zinc reagents to N-tert-butanesulfinylimines.

  2008cites this paper
• Allylsilane-vinylarene cross-metathesis enables a powerful approach to enantioselective imine allylation.

  2008cites this paper
• Direct allylation of aldimines catalyzed by C2-symmetric N,N'-dioxide-Sc(III) complexes: highly enantioselective synthesis of homoallylic amines.

  2008cites this paper