Stereoinversion in Pd-catalyzed allylic substitution induced by modification of olefinic moiety in chiral phosphine-acrylamide ligands
We synthesized a series of phosphine-acrylamide chiral compounds 4 from chiral aminophosphine (<i>S</i>)-5 with various acyl chlorides and demonstrated that they can be used as chiral ligands in the Pd-catalyzed asymmetric allylic substitution reactions of allylic acetate with malonates or indoles. Although the ligands shared the same axial chirality, we found that the substitution pattern of the acrylamide led to an inversion in the stereoselectivity of the product and then investigated the underlying mechanism based on DFT calculations.
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)
- Yasumitsu Toba
- Shinya Mita
- Manami Kumada
- Yusuke Kanda (ORCID: https://orcid.org/0000-0003-3992-799X)
- Masami Sakamoto (ORCID: https://orcid.org/0000-0001-9489-2641)
- Tomoko Yagi
- Kento Kanauchi
Institutions
- University of Shizuoka (JP)
- Chiba University (JP)
- Chiba Institute of Technology (JP)
Publication Details
- Journal
- Organic & Biomolecular Chemistry
- Published
- 2025-01-01
- DOI
- https://doi.org/10.1039/d5ob01034a
- Primary Topic
- Axial and Atropisomeric Chirality Synthesis
- Type
- article
- Field-Weighted Citation Impact
- 0.00
Funders
- Japan Society for the Promotion of Science