Ion-paired Chiral Ligands for Asymmetric Palladium Catalysis

Overview

Journal Nat Chem

Specialty Chemistry

Date 2012 May 23

PMID 22614382

Citations 32

Authors

Kohsuke Ohmatsu

Mitsunori Ito

Tomoatsu Kunieda

Takashi Ooi

Affiliations

Soon will be listed here.

Abstract

Conventional chiral ligands rely on the use of a covalently constructed, single chiral molecule embedded with coordinative functional groups. Here, we report a new strategy for the design of a chiral ligand for asymmetric transition-metal catalysis; our approach is based on the development of an achiral cationic ammonium-phosphine hybrid ligand paired with a chiral binaphtholate anion. This ion-paired chiral ligand imparts a remarkable stereocontrolling ability to its palladium complex, which catalyses a highly enantioselective allylic alkylation of α-nitrocarboxylates. By exploiting the possible combinations of the achiral onium entities with suitable coordinative functionalities and readily available chiral acids, this approach should contribute to the development of a broad range of metal-catalysed, stereoselective chemical transformations.

Citing Articles

Enantioselective Nitrene Transfer to Hydrocinnamyl Alcohols and Allylic Alcohols Enabled by Systematic Exploration of the Structure of Ion-Paired Rhodium Catalysts.

Hodson N, Takano S, Fanourakis A, Phipps R J Am Chem Soc. 2024; 146(32):22629-22641.

PMID: 39083568 PMC: 11328136. DOI: 10.1021/jacs.4c07117.

Application of sSPhos as a Chiral Ligand for Palladium-Catalyzed Asymmetric Allylic Alkylation.

Docherty P, Kadarauch M, Mistry N, Phipps R Org Lett. 2023; 26(14):2862-2866.

PMID: 38147571 PMC: 11020163. DOI: 10.1021/acs.orglett.3c04025.

Organocatalytic Michael Addition of Unactivated α-Branched Nitroalkanes to Afford Optically Active Tertiary Nitrocompounds.

Lorea B, Garcia-Urricelqui A, Odriozola J, Razkin J, Espinal-Viguri M, Oiarbide M Org Lett. 2023; 25(48):8590-8595.

PMID: 38009850 PMC: 10714440. DOI: 10.1021/acs.orglett.3c03340.

Interrogating the Crucial Interactions at Play in the Chiral Cation-Directed Enantioselective Borylation of Arenes.

Ermanis K, Gibson D, Genov G, Phipps R ACS Catal. 2023; 13(19):13043-13055.

PMID: 37822864 PMC: 10563137. DOI: 10.1021/acscatal.3c03384.

Enantioselective Allylation of Stereogenic Nitrogen Centers.

Zaitseva S, Prescimone A, Kohler V Org Lett. 2023; 25(10):1649-1654.

PMID: 36881477 PMC: 10028698. DOI: 10.1021/acs.orglett.3c00195.

References

Chisholm D, McIndoe J . Charged ligands for catalyst immobilisation and analysis. Dalton Trans. 2008; (30):3933-45. DOI: 10.1039/b800371h. View

Trost B, Crawley M . Asymmetric transition-metal-catalyzed allylic alkylations: applications in total synthesis. Chem Rev. 2003; 103(8):2921-44. DOI: 10.1021/cr020027w. View

Lu Z, Ma S . Metal-catalyzed enantioselective allylation in asymmetric synthesis. Angew Chem Int Ed Engl. 2007; 47(2):258-97. DOI: 10.1002/anie.200605113. View

Mohr J, Stoltz B . Enantioselective Tsuji allylations. Chem Asian J. 2007; 2(12):1476-91. PMC: 2967289. DOI: 10.1002/asia.200700183. View

Meeuwissen J, Reek J . Supramolecular catalysis beyond enzyme mimics. Nat Chem. 2010; 2(8):615-21. DOI: 10.1038/nchem.744. View

Hamilton G, Joo Kang E, Mba M, Toste F . A powerful chiral counterion strategy for asymmetric transition metal catalysis. Science. 2007; 317(5837):496-9. DOI: 10.1126/science.1145229. View

Jiang G, List B . Direct asymmetric α-allylation of aldehydes with simple allylic alcohols enabled by the concerted action of three different catalysts. Angew Chem Int Ed Engl. 2011; 50(40):9471-4. DOI: 10.1002/anie.201103263. View

Trost B, Van Vranken D . Asymmetric Transition Metal-Catalyzed Allylic Alkylations. Chem Rev. 1996; 96(1):395-422. DOI: 10.1021/cr9409804. View

van Leeuwen P, Rivillo D, Raynal M, Freixa Z . Enantioselective supramolecular catalysis induced by remote chiral diols. J Am Chem Soc. 2011; 133(46):18562-5. DOI: 10.1021/ja207912d. View

10.

Liao S, List B . Asymmetric counteranion-directed transition-metal catalysis: enantioselective epoxidation of alkenes with manganese(III) salen phosphate complexes. Angew Chem Int Ed Engl. 2009; 49(3):628-31. DOI: 10.1002/anie.200905332. View

11.

Nakoji M, Kanayama T, Okino T, Takemoto Y . Chiral phosphine-free Pd-mediated asymmetric allylation of prochiral enolate with a chiral phase-transfer catalyst. Org Lett. 2001; 3(21):3329-31. DOI: 10.1021/ol016567h. View

12.

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

13.

Mukherjee S, List B . Chiral counteranions in asymmetric transition-metal catalysis: highly enantioselective Pd/Brønsted acid-catalyzed direct alpha-allylation of aldehydes. J Am Chem Soc. 2007; 129(37):11336-7. DOI: 10.1021/ja074678r. View

14.

Jiang G, Halder R, Fang Y, List B . A highly enantioselective Overman rearrangement through asymmetric counteranion-directed palladium catalysis. Angew Chem Int Ed Engl. 2011; 50(41):9752-5. DOI: 10.1002/anie.201103843. View

15.

Dydio P, Rubay C, Gadzikwa T, Lutz M, Reek J . "Cofactor"-controlled enantioselective catalysis. J Am Chem Soc. 2011; 133(43):17176-9. DOI: 10.1021/ja208589c. View

16.

Wiester M, Ulmann P, Mirkin C . Enzyme mimics based upon supramolecular coordination chemistry. Angew Chem Int Ed Engl. 2010; 50(1):114-37. DOI: 10.1002/anie.201000380. View