Mechanism-based enantiodivergence in manganese reduction catalysis: a chiral pincer complex for the highly enantioselective hydroboration of ketones
A manganese alkyl complex containing a chiral bis(oxazolinyl-methylidene)isoindoline pincer ligand is a precatalyst for a catalytic system of unprecedented activity and selectivity in the enantioselective hydroboration of ketones, thus producing preparatively useful chiral alcohols in excellent yiel...
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| Main Authors: | , , , |
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| Format: | Article (Journal) |
| Language: | English |
| Published: |
24 May 2017
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| In: |
Angewandte Chemie
Year: 2017, Volume: 129, Issue: 29, Pages: 8513-8517 |
| ISSN: | 1521-3757 |
| DOI: | 10.1002/ange.201704184 |
| Online Access: | Verlag, lizenzpflichtig, Volltext: https://doi.org/10.1002/ange.201704184 Verlag, lizenzpflichtig, Volltext: https://onlinelibrary.wiley.com/doi/abs/10.1002/ange.201704184 
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| Author Notes: | Vladislav Vasilenko, Clemens K. Blasius, Hubert Wadepohl, and Lutz H. Gade |
| Summary: | A manganese alkyl complex containing a chiral bis(oxazolinyl-methylidene)isoindoline pincer ligand is a precatalyst for a catalytic system of unprecedented activity and selectivity in the enantioselective hydroboration of ketones, thus producing preparatively useful chiral alcohols in excellent yields with up to greater than 99 % ee. It is applicable for both aryl alkyl and dialkyl ketone reduction under mild reaction conditions (TOF >450 h−1 at −40 °C). The earth-abundant base-metal catalyst operates at very low catalyst loadings (as low as 0.1 mol %) and with a high level of functional-group tolerance. There is evidence for the existence of two distinct mechanistic pathways for manganese-catalyzed hydride transfer and their role for enantiocontrol in the selectivity-determining step is presented. |
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| Item Description: | Gesehen am 15.12.2022 |
| Physical Description: | Online Resource |
| ISSN: | 1521-3757 |
| DOI: | 10.1002/ange.201704184 |