Computationally guided design of a readily assembled phosphite-thioether ligand for a broad range of pd-catalyzed asymmetric allylic substitutions
Maria Biosca, Jèssica Margalef, Xisco Caldentey, Maria Besora, Carles Rodríguez-Escrich, Joan Saltó, Xacobe C. Cambeiro, Feliu Maseras, Oscar Pàmies, Montserrat Diéguez, Miquel A. Pericàs
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© 2018 American Chemical Society. A modular approach employing indene as common starting material, has enabled the straightforward preparation in three reaction steps of P-thioether ligands for the Pd-catalyzed asymmetric allylic substitution. The analysis of a starting library of P-thioether ligands based on rational design and theoretical calculations has led to the discovery of an optimized anthracenethiol derivative with excellent behavior in the reaction of choice. Improving most approaches reported to date, this ligand presents a broad substrate and nucleophile scope. Excellent enantioselectivities have been achieved for a range of linear and cyclic allylic substrates using a large number of C-, N-, and O-nucleophiles (40 compounds in total). The species responsible for the catalytic activity have been further investigated by NMR in order to clearly establish the origin of the enantioselectivity. The resulting products have been derivatized by means of ring-closing metathesis or Pauson-Khand reactions to further prove the synthetic versatility of the methodology for preparing enantiopure complex structures.
https://doi.org/10.1021/acscatal.7b04192
10.1021/acscatal.7b04192
Dive into the research topics of 'Computationally guided design of a readily assembled phosphite-thioether ligand for a broad range of pd-catalyzed asymmetric allylic substitutions'. Together they form a unique fingerprint.
Sulfide Chemistry 100%
Thioether Biochemistry, Genetics and Molecular Biology 33%
Substitution Reaction Chemistry 22%
Nucleophile Chemistry 22%
Asymmetry Chemistry 22%
Enantioselectivity Chemistry 22%
Chemical Reaction Chemistry 22%
Enantiopurity Chemistry 11%
Biosca, M., Margalef, J., Caldentey, X., Besora, M., Rodríguez-Escrich, C., Saltó, J., Cambeiro, X. C., Maseras, F., Pàmies, O., Diéguez, M., & Pericàs, M. A. (2018). Computationally guided design of a readily assembled phosphite-thioether ligand for a broad range of pd-catalyzed asymmetric allylic substitutions. ACS Catalysis, 8(4), 3587-3601. https://doi.org/10.1021/acscatal.7b04192
Biosca, Maria ; Margalef, Jèssica ; Caldentey, Xisco et al. / Computationally guided design of a readily assembled phosphite-thioether ligand for a broad range of pd-catalyzed asymmetric allylic substitutions. In: ACS Catalysis. 2018 ; Vol. 8, No. 4. pp. 3587-3601.
@article{055ad60d5fe64e8b8f5d3ce948f7a08c,
title = "Computationally guided design of a readily assembled phosphite-thioether ligand for a broad range of pd-catalyzed asymmetric allylic substitutions",
abstract = "{\textcopyright} 2018 American Chemical Society. A modular approach employing indene as common starting material, has enabled the straightforward preparation in three reaction steps of P-thioether ligands for the Pd-catalyzed asymmetric allylic substitution. The analysis of a starting library of P-thioether ligands based on rational design and theoretical calculations has led to the discovery of an optimized anthracenethiol derivative with excellent behavior in the reaction of choice. Improving most approaches reported to date, this ligand presents a broad substrate and nucleophile scope. Excellent enantioselectivities have been achieved for a range of linear and cyclic allylic substrates using a large number of C-, N-, and O-nucleophiles (40 compounds in total). The species responsible for the catalytic activity have been further investigated by NMR in order to clearly establish the origin of the enantioselectivity. The resulting products have been derivatized by means of ring-closing metathesis or Pauson-Khand reactions to further prove the synthetic versatility of the methodology for preparing enantiopure complex structures.",
author = "Maria Biosca and J{\`e}ssica Margalef and Xisco Caldentey and Maria Besora and Carles Rodr{\'i}guez-Escrich and Joan Salt{\'o} and Cambeiro, {Xacobe C.} and Feliu Maseras and Oscar P{\`a}mies and Montserrat Di{\'e}guez and Peric{\`a}s, {Miquel A.}",
doi = "10.1021/acscatal.7b04192",
journal = "ACS Catalysis",
Biosca, M, Margalef, J, Caldentey, X, Besora, M, Rodríguez-Escrich, C, Saltó, J, Cambeiro, XC, Maseras, F, Pàmies, O, Diéguez, M & Pericàs, MA 2018, 'Computationally guided design of a readily assembled phosphite-thioether ligand for a broad range of pd-catalyzed asymmetric allylic substitutions', ACS Catalysis, vol. 8, no. 4, pp. 3587-3601. https://doi.org/10.1021/acscatal.7b04192
Computationally guided design of a readily assembled phosphite-thioether ligand for a broad range of pd-catalyzed asymmetric allylic substitutions. / Biosca, Maria; Margalef, Jèssica; Caldentey, Xisco et al.
In: ACS Catalysis, Vol. 8, No. 4, 06.04.2018, p. 3587-3601.
T1 - Computationally guided design of a readily assembled phosphite-thioether ligand for a broad range of pd-catalyzed asymmetric allylic substitutions
AU - Biosca, Maria
AU - Margalef, Jèssica
AU - Caldentey, Xisco
AU - Besora, Maria
AU - Rodríguez-Escrich, Carles
AU - Saltó, Joan
AU - Cambeiro, Xacobe C.
AU - Maseras, Feliu
AU - Pàmies, Oscar
AU - Diéguez, Montserrat
AU - Pericàs, Miquel A.
N2 - © 2018 American Chemical Society. A modular approach employing indene as common starting material, has enabled the straightforward preparation in three reaction steps of P-thioether ligands for the Pd-catalyzed asymmetric allylic substitution. The analysis of a starting library of P-thioether ligands based on rational design and theoretical calculations has led to the discovery of an optimized anthracenethiol derivative with excellent behavior in the reaction of choice. Improving most approaches reported to date, this ligand presents a broad substrate and nucleophile scope. Excellent enantioselectivities have been achieved for a range of linear and cyclic allylic substrates using a large number of C-, N-, and O-nucleophiles (40 compounds in total). The species responsible for the catalytic activity have been further investigated by NMR in order to clearly establish the origin of the enantioselectivity. The resulting products have been derivatized by means of ring-closing metathesis or Pauson-Khand reactions to further prove the synthetic versatility of the methodology for preparing enantiopure complex structures.
AB - © 2018 American Chemical Society. A modular approach employing indene as common starting material, has enabled the straightforward preparation in three reaction steps of P-thioether ligands for the Pd-catalyzed asymmetric allylic substitution. The analysis of a starting library of P-thioether ligands based on rational design and theoretical calculations has led to the discovery of an optimized anthracenethiol derivative with excellent behavior in the reaction of choice. Improving most approaches reported to date, this ligand presents a broad substrate and nucleophile scope. Excellent enantioselectivities have been achieved for a range of linear and cyclic allylic substrates using a large number of C-, N-, and O-nucleophiles (40 compounds in total). The species responsible for the catalytic activity have been further investigated by NMR in order to clearly establish the origin of the enantioselectivity. The resulting products have been derivatized by means of ring-closing metathesis or Pauson-Khand reactions to further prove the synthetic versatility of the methodology for preparing enantiopure complex structures.
U2 - 10.1021/acscatal.7b04192
DO - 10.1021/acscatal.7b04192
JO - ACS Catalysis
JF - ACS Catalysis
Biosca M, Margalef J, Caldentey X, Besora M, Rodríguez-Escrich C, Saltó J et al. Computationally guided design of a readily assembled phosphite-thioether ligand for a broad range of pd-catalyzed asymmetric allylic substitutions. ACS Catalysis. 2018 Apr 6;8(4):3587-3601. doi: 10.1021/acscatal.7b04192