Fluxional Axially Chiral P,Pyridine Ligands for Pd-Catalyzed Asymmetric Allylic Alkylation
We synthesized chiral P,pyridine-type ligands (<i>S</i>)-<b>L1-4</b> with fluxional chirality and demonstrated Pd-catalyzed asymmetric allylic alkylation with malonates achieving high enantioselectivities (up to 91% ee). DFT calculations suggest that the chiral phenylethyl moiety plays a crucial role in attaining enantioselectivity by regulating not only the fluxional axial chirality of the ligand but also the orientation of the π-allyl group through CH-π interactions.
Authors
- Yoshio Kasashima (ORCID: https://orcid.org/0000-0002-6224-4495)
- Yasushi Yoshida (ORCID: https://orcid.org/0000-0002-3498-3696)
- Takashi Mino (ORCID: https://orcid.org/0000-0003-1588-1202)
- Kohei Watanabe (ORCID: https://orcid.org/0000-0002-3146-5439)
- Ryo Takita (ORCID: https://orcid.org/0000-0003-4104-9890)
- Atsuhito SUZUKI
- Masami Sakamoto (ORCID: https://orcid.org/0000-0001-9489-2641)
- Nana Oguri
Institutions
- University of Shizuoka (JP)
- Chiba University (JP)
- Chiba Institute of Technology (JP)
Publication Details
- Journal
- The Journal of Organic Chemistry
- Published
- 2026-01-05
- DOI
- https://doi.org/10.1021/acs.joc.5c02806
- Primary Topic
- Axial and Atropisomeric Chirality Synthesis
- Type
- article
- Field-Weighted Citation Impact
- 0.00