Diastereoselective and Enantioselective Synthesis of Unsymmetric β,β-Diaryl-α-Amino Acid Esters via Organocatalytic 1,6-Conjugate Addition of para-Quinone Methides.

@article{Zhang2016DiastereoselectiveAE,
  title={Diastereoselective and Enantioselective Synthesis of Unsymmetric $\beta$,$\beta$-Diaryl-$\alpha$-Amino Acid Esters via Organocatalytic 1,6-Conjugate Addition of para-Quinone Methides.},
  author={Xiang‐Zhi Zhang and Yuhua Deng and Xu Yan and Ke‐Yin Yu and Fang-Xin Wang and Xiao-Yan Ma and Chun‐An Fan},
  journal={The Journal of organic chemistry},
  year={2016},
  volume={81 13},
  pages={
          5655-62
        }
}
A novel strategy based on phase transfer catalysis for the diastereoselective and enantioselective direct assembly of unsymmetric β,β-diaryl-α-amino acid esters via 1,6-conjugate addition of para-quinone methides and glycine derivatives is described. This protocol also provides an alternative route to the synthetically interesting functionalized chiral tetrahydroisoquinoline and its analogues. 
View on PubMed
doi.org
72 Citations

Figures and Tables from this paper

72 Citations

Highly Stereoselective Construction of β,β-Diaryl-α-Branched Ketones by the Chiral Primary Amine-Catalyzed Asymmetric Retro-Claisen Reaction.

Highly diastereo- and enantioselective retro-Claisen reaction of β-diketones with o-quinone methides has been developed by chiral primary amine catalysis. This reaction allows for efficient synthesis…

Stereodivergent entry to β-branched β-trifluoromethyl α-amino acid derivatives by sequential catalytic asymmetric reactions

A one-pot approach to these important α-amino acids, grounded on the reduction – ring opening of Erlenmeyer–Plöchl azlactones, is presented, where the configurations of the two chirality centers of the products are established during each of theTwo catalytic steps, enabling a stereodivergent process.

Construction of highly enantiopure β,β-diaryl substituted glycine containing two contiguous stereocenters via asymmetric 1,6-conjugate addition

Quaternary β2,2-amino acid derivatives by asymmetric addition of isoxazolidin-5-ones to para-quinone methides.

The highly enantioselective (>99.5% ee) synthesis of a new class of densely functionalized β2,2-amino acid derivatives by reacting isoxazolidin-5-ones with para-quinone methides in the presence of…

Isothiourea-Catalyzed Enantioselective α-Alkylation of Esters via 1,6-Conjugate Addition to para-Quinone Methides

The isothiourea-catalyzed enantioselective 1,6-conjugate addition of para-nitrophenyl esters to 2, 6-disubstituted para-quinone methides is reported, and the diastereoisomeric ester products are separable and formed with high enantiocontrol.

Enantioselective Rauhut-Currier-Type 1,6-Conjugate Addition of Methyl Vinyl Ketone to para-Quinone Methides.

An unprecedented Rauhut-Currier-type 1,6-conjugate addition has been developed to produce chiral diarylmethine compounds in excellent yields and enantioselectivities.

Asymmetric Cycloaddition of ortho-Hydroxyphenyl-Substituted para-Quinone Methides and Enamides Catalyzed by Chiral Phosphoric Acid.

A BINOL-based chiral phosphoric acid was employed as an efficient catalyst in enantioselective cycloaddition of ortho-hydroxyphenyl-substituted para-quinone methides and enamides, which gave rise to…

Enantio- and diastereoselective diarylmethylation of 1,3-dicarbonyl compounds†

A Cu-catalyzed enantio- and diastereoselective diarylmethylation of 1,3-dicarbonyl compounds is described. It is a successful example of constructing all-carbon quaternary stereocenters from 3 °C–H…

Asymmetric 1,6‐Conjugate Addition of para‐Quinone Methides for the Synthesis of Chiral β,β‐Diaryl‐α‐Hydroxy Ketones

A direct asymmetric 1,6-conjugated addition of α-hydroxy ketone to para-quinone methides has been developed. It is an efficient approach to the synthesis of chiral β,β-diaryl-α-hydroxy ketones. The…

Cinchona Alkaloid Catalyzed Enantioselective [4 + 2] Annulation of Allenic Esters and in Situ Generated ortho-Quinone Methides: Asymmetric Synthesis of Functionalized Chromans.

This chiral amine-catalyzed reaction provides an alternative route to asymmetric catalytic construction of synthetically interesting, highly functionalized chiral chromans in good to excellent enantioselectivities.
...

References

SHOWING 1-10 OF 75 REFERENCES

Highly diastereo- and enantioselective synthesis of syn-β-substituted tryptophans via asymmetric Michael addition of a chiral equivalent of nucleophilic glycine and sulfonylindoles.

The asymmetric synthesis of syn-β-substituted tryptophan derivatives was carried out by the Michael addition of chiral equivalent of nucleophilic glycine with sulfonylindoles, and high diastereo- and…

Direct Asymmetric Synthesis of β-Bis-Aryl-α-Amino Acid Esters via Enantioselective Copper-Catalyzed Addition of p-Quinone Methides

The first enantioselective 1,6-conjugate addition of glycine Schiff bases to para-quinone methides was achieved using a Cu(CH3CN)4BF4/Ph-Foxap catalytic system, and enantiopure unnatural amino alcohols were utilized for the synthesis of novel chiral ligands.

Copper-catalyzed enantioselective 1,6-boration of para-quinone methides and efficient transformation of gem-diarylmethine boronates to triarylmethanes.

This is the first enantioselective copper-catalyzed 1,6-conjugate addition of bis(pinacolato)diboron to para-quinone methides, and provides an attractive approach to the construction of optically active gem-diarylmehtine boronic esters.

Ag-Catalyzed diastereo- and enantioselective synthesis of beta-substituted tryptophans from sulfonylindoles.

The asymmetric catalytic synthesis of beta-substituted tryptophan derivatives was realized in high diastereo- and enantioselectivity by the reaction of glycine derivatives with sulfonylindoles in the…

Copper-Catalyzed Borylative Aromatization of p-Quinone Methides: Enantioselective Synthesis of Dibenzylic Boronates

It is established that DM-Segphos copper(I) complexes are efficient catalysts for the enantioselective borylation of para-quinone methides, with enantiomeric ratios up to 96:4, using a commercially available chiral phosphine.

Bis(amino)cyclopropenylidene-Catalyzed 1,6-Conjugate Addition of Aromatic Aldehydes to para-Quinone Methides: Expedient Access to α,α'-Diarylated Ketones.

This unprecedented organocatalytic protocol offers access to a wide range of α,α'-diarylated ketones in moderate to excellent yields under mild conditions through umpolung of aldehydes followed by 1,6-conjugate addition with para-quinone methides.

Asymmetric Organocatalytic Synthesis of 3-Diarylmethine-Substituted Oxindoles Bearing a Quaternary Stereocenter via 1,6-Conjugate Addition to para-Quinone Methides

A highly stereoselective organocatalytic 1,6-conjugate addition of 3-substituted oxindoles to para-quinone methides to construct all-carbon quaternary stereocenters is described, providing an efficient approach to a series of oxindole derivatives containing the diarylmethine motif attached to an all- carbon quaternARY stereogenic center.

Organocatalyzed Asymmetric 1,6-Conjugate Addition of para-Quinone Methides with Dicyanoolefins.

A chiral thiourea catalyzed asymmetric 1,6-conjugate addition of para-quinone methides with dicyanoolefins has been developed and the preliminary mechanistic study showed that the remote stereocontrol was achieved through intermolecular hydrogen-bond interaction for the first time.

Catalytic Asymmetric 1,6-Conjugate Addition of para-Quinone Methides: Formation of All-Carbon Quaternary Stereocenters.

Benefiting from chiral Brønsted acid catalysis, this reaction expands the scope to general p-QMs with various substitution patterns and enables efficient intermolecular formation of all-carbon quaternary stereocenters with high enantioselectivity.

Catalytic, asymmetric, and stereodivergent synthesis of non-symmetric β,β-diaryl-α-amino acids.

High yields and excellent enantioselectivities were obtained for a variety of N-acetyl, N-methoxycarbonyl, and N-Boc β,β-diaryldehydroamino acids, containing a diverse and previously unreported series of heterocyclic and aryl substituted groups and allowing access to all four stereoisomers of these valuable building blocks.
...