Copper(I)-Catalyzed Enantioselective Addition of Enynes to Ketones.

@article{Wei2017CopperICatalyzedEA,
  title={Copper(I)-Catalyzed Enantioselective Addition of Enynes to Ketones.},
  author={Xiao-Feng Wei and Xiao-Wei Xie and Yohei Shimizu and Motomu Kanai},
  journal={Journal of the American Chemical Society},
  year={2017},
  volume={139 13},
  pages={
          4647-4650
        }
}
A copper(I)-catalyzed enantioselective addition of enynes to ketones was developed. The method allows facile construction of enantiomerically enriched tertiary alcohols using skipped enynes as stable hydrocarbon pronucleophiles. The combination of a soft copper(I)-conjugated Brønsted base catalyst with a chiral diphosphine ligand, (S,S)-Ph-BPE, enabled chemoselective deprotonation of the skipped enynes in the presence of ketones bearing intrinsically more acidic α-protons. The catalytically… 
View on PubMed
doi.org
50 Citations
Highly Influential Citations
2
Background Citations
2
Methods Citations
1
Results Citations
1

Tables from this paper

50 Citations

Citation Type

Citation Type

Catalytic Regio- and Enantioselective Proton Migration from Skipped Enynes to Allenes
Asymmetric Borylative Propargylation of Ketones Catalyzed by a Copper(I) Complex.
TLDR
The synthetic utility of the methodology was showcased by the asymmetric synthesis of a chiral piperidine derivative, which served as a suitable cross-coupling partner in a palladium-catalyzed Suzuki-Miyaura reaction.
Cu(i)-Catalyzed asymmetric intramolecular addition of aryl pinacolboronic esters to unactivated ketones: enantioselective synthesis of 2,3-dihydrobenzofuran-3-ol derivatives.
TLDR
This protocol showcases a broad substrate tolerance and allows access to various chiral 2,3-dihydrobenzofuran-3-ol derivatives in generally good yields with excellent enantioselectivities.
Construction of Chiral 2,3-Allenols through Copper(I)-Catalyzed Asymmetric Direct Alkynylogous Aldol Reaction.
TLDR
The developed methodology was successfully applied in the rapid synthesis of three chiral intermediates toward the synthesis of two pharmaceutically active compounds, which are known for the treatment of neurological disorders.
Copper-catalyzed functionalization of enynes
TLDR
Copper-catalyzed transformations of enynes, such as boro- and hydrofunctionalizations, copper-mediated radical difunctionalizations, and cyclizations are reviewed, with particular attention to the regiodivergent functionalization of 1,3-enynes.
Copper(I)-catalyzed asymmetric 1,6-conjugate allylation
TLDR
The phenolic hydroxyl group in NHC ligands is found to be pivotal to obtain the desired products and the synthetic utility of the products is demonstrated in several transformations by means of the versatile terminal olefin and dioxinone groups.
Copper-Catalyzed Asymmetric Reductive Allylation of Ketones with 1,3-Dienes.
TLDR
This method provides a straightforward and alternative avenue to synthesize chiral homoallylic tertiary alcohols with 1,3-dienes as the latent allylic nucleophiles and avoids the traditional reliance on stoichiometric quantities of allylmetal reagents.
Theoretical Calculations on the Mechanism of Enantioselective Copper(I)-Catalyzed Addition of Enynes to Ketones
Computational investigations on the bisphospholanoethane (BPE)-ligated Cu-catalyzed enantioselective addition of enynes to ketones were performed with the density functional theory (DFT) method. Two…
Bi(OAc)3/Chiral Phosphoric Acid-Catalyzed Enantioselective 1,2- and Formal 1,4-Allylation Reaction of β,γ-Unsaturated α-Ketoesters.
TLDR
A highly efficient asymmetric 1,2-allylation reaction of β,γ-unsaturated α-ketoesters was realized by using a Bi(OAc)3/chiral phosphoric acid catalyst system under mild conditions and the asymmetric formal 1,4-allylated reaction was achieved by a one-pot process.
Enantio‐ and Diastereoselective Synthesis of Homopropargyl Amines by Copper‐Catalyzed Coupling of Imines, 1,3‐Enynes, and Diborons
Abstract An efficient, enantio‐ and diastereoselective, copper‐catalyzed coupling of imines, 1,3‐enynes, and diborons is reported. The process shows broad substrate scope and delivers complex, chiral…
...
1
2
3
4
5
...

References

SHOWING 1-10 OF 56 REFERENCES
Lithium binaphtholate-catalyzed enantioselective enyne addition to ketones: access to enynylated tertiary alcohols.
A new catalytic enantioselective enyne addition to ketones has been developed. In the presence of chiral lithium binaphtholate, the addition reaction proceeded smoothly to produce a series of…
Enantioselective copper-catalyzed reductive coupling of alkenylazaarenes with ketones.
TLDR
The enantioselective reductive coupling of alkenylazaarenes with ketones has been developed, which is tolerant of a wide variety of azaarenes and ketones, and provides aromatic heterocycles bearing tertiary-alcohol-containing side chains with high levels of diastereo- andEnantioselection.
Highly enantioselective direct reductive coupling of conjugated alkynes and alpha-ketoesters via rhodium-catalyzed asymmetric hydrogenation.
TLDR
These studies represent the first highly enantioselective direct catalytic reductive couplings of alkynes to ketones to afford dienylated alpha-hydroxy esters 1b-7b and 3c-3f with exceptional levels of regio- and enantiocontrol.
Enantioselective Alkynylation of 2-Trifluoroacetyl Imidazoles Catalyzed by Bis-Cyclometalated Rhodium(III) Complexes Containing Pinene-Derived Ligands.
Chiral rhodium(III) complexes containing two cyclometalating 2-phenyl-5,6-(S,S)-pinenopyridine ligands and two additional acetonitriles are introduced as excellent catalysts for the highly…
Identification of modular chiral bisphosphines effective for Cu(i)-catalyzed asymmetric allylation and propargylation of ketones.
TLDR
New modular chiral phosphines effective for two distinct Cu(I)-catalyzed asymmetric tetrasubstituted-carbon-forming reactions, namely, allylation and propargylation of ketones, were identified and readily synthesized on a gram scale in high yield via three facile transformations.
Highly regioselective, catalytic asymmetric reductive coupling of 1,3-enynes and ketones.
TLDR
These couplings represent the first examples of catalytic, intermolecular reductive coupling of alkynes and ketones, enantioselective or otherwise, and afford synthetically useful 1,3-dienes possessing a quaternary carbinol stereogenic center in up to 70% ee.
Highly enantioselective alkynylation of alpha-keto ester: an efficient method for constructing a chiral tertiary carbon center.
The asymmetric addition of terminal alkynes to alpha-keto ester was carried out using a catalytic amount of…
Copper(I) alkoxide-catalyzed alkynylation of trifluoromethyl ketones.
A general method for direct alkynylation of trifluoromethyl ketones was developed by using CuO(t)Bu-xantphos or phenanthroline complexes as catalysts. The ligands significantly enhanced the catalyst…
Enantioselective Synthesis of 3-Alkynyl-3-hydroxyindolin-2-ones by Copper-Catalyzed Asymmetric Addition of Terminal Alkynes to Isatins.
TLDR
A highly efficient copper-catalyzed asymmetric addition of terminal alkynes to isatins has been developed and the synthetic utility of the present protocol was further demonstrated by the transformation of chiral alkynylation products.
Copper-catalyzed asymmetric addition of olefin-derived nucleophiles to ketones
TLDR
A copper-catalyzed strategy for the stereoselective nucleophilic addition of propargylic and other alkyl groups to ketones, using easily accessible (poly)unsaturated hydrocarbons as latent carbanion equivalents, allowing for the effective construction of highly substituted stereochemical dyads with excellent stereocontrol.
...
1
2
3
4
5
...