Catalyst control over pentavalent stereocentres
Abstract A monumental diversity of catalytic methods imparts the ability to select one of two configurations of tetravalent stereocentres. Conversely, catalyst control over pentavalent stereocentres, where a fifth moiety bound to the central atom encodes an expanded stereochemical space, remained a...
| Main Authors: | , , , |
|---|---|
| Format: | Article |
| Language: | English |
| Published: |
Nature Portfolio
2023-12-01
|
| Series: | Nature Communications |
| Online Access: | https://doi.org/10.1038/s41467-023-43750-w |
| _version_ | 1797397894397952000 |
|---|---|
| author | Anton Budeev Jianyang Dong Daniel Häussinger Christof Sparr |
| author_facet | Anton Budeev Jianyang Dong Daniel Häussinger Christof Sparr |
| author_sort | Anton Budeev |
| collection | DOAJ |
| description | Abstract A monumental diversity of catalytic methods imparts the ability to select one of two configurations of tetravalent stereocentres. Conversely, catalyst control over pentavalent stereocentres, where a fifth moiety bound to the central atom encodes an expanded stereochemical space, remained a challenge to be accomplished. Herein, we report the feasibility of the catalytic tractability of pentavalent stereocentres. A bifunctional iminophosphorane thiourea catalyst enables enantio- and diastereocontrol over pentavalent phosphoranes to differentiate configurationally stable enantiomers and ensembles of diastereomers which emerge together from a single stereocentre. The desired dioxophosphorane stereoisomers are obtained with excellent yield and selectivity (up to 99% yield, 96:4 e.r. and 99:1 d.r.), while stereodivergent catalysis reroutes the reaction for selective access to each of the viable stereoisomeric states of pentavalent phosphoranes. Considering the diversity of high-valent main group species, it is expected that catalyst control over pentavalent stereocentres significantly increases the synthetically addressable stereochemical space. |
| first_indexed | 2024-03-09T01:17:50Z |
| format | Article |
| id | doaj.art-a90c889dcfad45208c0d3f7831de771e |
| institution | Directory Open Access Journal |
| issn | 2041-1723 |
| language | English |
| last_indexed | 2024-03-09T01:17:50Z |
| publishDate | 2023-12-01 |
| publisher | Nature Portfolio |
| record_format | Article |
| series | Nature Communications |
| spelling | doaj.art-a90c889dcfad45208c0d3f7831de771e2023-12-10T12:23:34ZengNature PortfolioNature Communications2041-17232023-12-011411610.1038/s41467-023-43750-wCatalyst control over pentavalent stereocentresAnton Budeev0Jianyang Dong1Daniel Häussinger2Christof Sparr3Department of Chemistry, University of BaselDepartment of Chemistry, University of BaselDepartment of Chemistry, University of BaselDepartment of Chemistry, University of BaselAbstract A monumental diversity of catalytic methods imparts the ability to select one of two configurations of tetravalent stereocentres. Conversely, catalyst control over pentavalent stereocentres, where a fifth moiety bound to the central atom encodes an expanded stereochemical space, remained a challenge to be accomplished. Herein, we report the feasibility of the catalytic tractability of pentavalent stereocentres. A bifunctional iminophosphorane thiourea catalyst enables enantio- and diastereocontrol over pentavalent phosphoranes to differentiate configurationally stable enantiomers and ensembles of diastereomers which emerge together from a single stereocentre. The desired dioxophosphorane stereoisomers are obtained with excellent yield and selectivity (up to 99% yield, 96:4 e.r. and 99:1 d.r.), while stereodivergent catalysis reroutes the reaction for selective access to each of the viable stereoisomeric states of pentavalent phosphoranes. Considering the diversity of high-valent main group species, it is expected that catalyst control over pentavalent stereocentres significantly increases the synthetically addressable stereochemical space.https://doi.org/10.1038/s41467-023-43750-w |
| spellingShingle | Anton Budeev Jianyang Dong Daniel Häussinger Christof Sparr Catalyst control over pentavalent stereocentres Nature Communications |
| title | Catalyst control over pentavalent stereocentres |
| title_full | Catalyst control over pentavalent stereocentres |
| title_fullStr | Catalyst control over pentavalent stereocentres |
| title_full_unstemmed | Catalyst control over pentavalent stereocentres |
| title_short | Catalyst control over pentavalent stereocentres |
| title_sort | catalyst control over pentavalent stereocentres |
| url | https://doi.org/10.1038/s41467-023-43750-w |
| work_keys_str_mv | AT antonbudeev catalystcontroloverpentavalentstereocentres AT jianyangdong catalystcontroloverpentavalentstereocentres AT danielhaussinger catalystcontroloverpentavalentstereocentres AT christofsparr catalystcontroloverpentavalentstereocentres |