Reversal of Enantioselectivity in the Conjugate Addition Reaction of Cyclic Enones with the CuOTf/Azolium Catalytic System

Overview

Journal Molecules

Publisher MDPI

Specialty Biology

Date 2021 Jul 2

PMID 34199812

Authors

Yuki Nakano

Satoki Shimizu

Chihiro Takeda

Satoshi Sakaguchi

Affiliations

Soon will be listed here.

Abstract

Hydroxyamide-functionalized azolium salt (NHC•HI ) was evaluated for dual enantioselective control in a Cu-catalyzed asymmetric conjugate addition (ACA) reaction. This investigation was based on our previously reported ACA reaction catalyzed using CuOTf combined with NHC•AgI complex . It was revealed that the stereocontrol of the catalytic ACA reaction depended on the order of the addition of the substrates. Additionally, the chiral NHC ligand precursors, substrates, the relationship between the catalyst ee (ee) and product ee (ee), and halogen counter anion were completely evaluated. These results suggested that the catalytic performance of the CuOTf/ system was comparable with that of the CuOTf/ system. Furthermore, to gain knowledge of the Cu species generated using CuOTf and NHC ligand precursor, the reaction of CuOTf with was investigated. Although obtaining the corresponding NHC•CuX species failed, the corresponding NHC•AuCl complex could be synthesized by allowing to react with AuCl•SMe.

References

Escorihuela J, Isabel Burguete M, Luis S . New advances in dual stereocontrol for asymmetric reactions. Chem Soc Rev. 2013; 42(12):5595-617. DOI: 10.1039/c3cs60068h. View

Garrison J, Youngs W . Ag(I) N-heterocyclic carbene complexes: synthesis, structure, and application. Chem Rev. 2005; 105(11):3978-4008. DOI: 10.1021/cr050004s. View

Shibata N, Yoshimura M, Yamada H, Arakawa R, Sakaguchi S . Hydroxy-amide functionalized azolium salts for Cu-catalyzed asymmetric conjugate addition: stereocontrol based on ligand structure and copper precatalyst. J Org Chem. 2012; 77(8):4079-86. DOI: 10.1021/jo300472r. View

Lin J, Huang R, Lee C, Bhattacharyya A, Hwang W, Lin I . Coinage metal-N-heterocyclic carbene complexes. Chem Rev. 2009; 109(8):3561-98. DOI: 10.1021/cr8005153. View

Cervantes-Reyes A, Rominger F, Hashmi A . Sterically Demanding Ag and Cu N-Heterocyclic Carbene Complexes: Synthesis, Structures, Steric Parameters, and Catalytic Activity. Chemistry. 2020; 26(24):5530-5540. PMC: 7216994. DOI: 10.1002/chem.202000600. View

Cesar V, Bellemin-Laponnaz S, Gade L . Chiral N-heterocyclic carbenes as stereodirecting ligands in asymmetric catalysis. Chem Soc Rev. 2004; 33(9):619-36. DOI: 10.1039/b406802p. View

Janssen-Muller D, Schlepphorst C, Glorius F . Privileged chiral N-heterocyclic carbene ligands for asymmetric transition-metal catalysis. Chem Soc Rev. 2017; 46(16):4845-4854. DOI: 10.1039/c7cs00200a. View

Jerphagnon T, Pizzuti M, Minnaard A, Feringa B . Recent advances in enantioselective copper-catalyzed 1,4-addition. Chem Soc Rev. 2009; 38(4):1039-75. DOI: 10.1039/b816853a. View

Bartok M . Unexpected inversions in asymmetric reactions: reactions with chiral metal complexes, chiral organocatalysts, and heterogeneous chiral catalysts. Chem Rev. 2009; 110(3):1663-705. DOI: 10.1021/cr9002352. View

10.

Walsh P . Titanium-catalyzed enantioselective additions of alkyl groups to aldehydes: mechanistic studies and new concepts in asymmetric catalysis. Acc Chem Res. 2003; 36(10):739-49. DOI: 10.1021/ar0300219. View

11.

Marion N, Nolan S . N-heterocyclic carbenes in gold catalysis. Chem Soc Rev. 2008; 37(9):1776-82. DOI: 10.1039/b711132k. View

12.

Blanco V, Leigh D, Marcos V . Artificial switchable catalysts. Chem Soc Rev. 2015; 44(15):5341-70. DOI: 10.1039/c5cs00096c. View

13.

Hahn F, Jahnke M . Heterocyclic carbenes: synthesis and coordination chemistry. Angew Chem Int Ed Engl. 2008; 47(17):3122-72. DOI: 10.1002/anie.200703883. View

14.

Li D, Ollevier T . Synthesis of Imidazolidinone, Imidazolone, and Benzimidazolone Derivatives through Oxidation Using Copper and Air. Org Lett. 2019; 21(10):3572-3575. DOI: 10.1021/acs.orglett.9b00973. View

15.

Beletskaya I, Najera C, Yus M . Stereodivergent Catalysis. Chem Rev. 2018; 118(10):5080-5200. DOI: 10.1021/acs.chemrev.7b00561. View

16.

Alexakis A, Backvall J, Krause N, Pamies O, Dieguez M . Enantioselective copper-catalyzed conjugate addition and allylic substitution reactions. Chem Rev. 2008; 108(8):2796-823. DOI: 10.1021/cr0683515. View

17.

Yoon T, Jacobsen E . Privileged chiral catalysts. Science. 2003; 299(5613):1691-3. DOI: 10.1126/science.1083622. View

18.

Satyanarayana T, Abraham S, Kagan H . Nonlinear effects in asymmetric catalysis. Angew Chem Int Ed Engl. 2008; 48(3):456-94. DOI: 10.1002/anie.200705241. View

19.

Johnson A, Gimeno M . An efficient and sustainable synthesis of NHC gold complexes. Chem Commun (Camb). 2016; 52(62):9664-7. DOI: 10.1039/c6cc05190a. View

20.

Magrez M, Wencel-Delord J, Alexakis A, Crevisy C, Mauduit M . Significant asymmetric amplification in enantioselective Cu/DiPPAM-catalyzed 1,6- and 1,4-conjugate additions of diethylzinc to (di)enones. Org Lett. 2012; 14(14):3576-9. DOI: 10.1021/ol300866p. View