Rhodium Catalyzed Asymmetric Hydroamination of Internal Alkynes with Indoline: Mechanism, Origin of Enantioselectivity, and Role of Additives.
| Autor: | Athira C; Department of Chemistry, Indian Institute of Technology Bombay , Powai, Mumbai 400076, India., Changotra A; Department of Chemistry, Indian Institute of Technology Bombay , Powai, Mumbai 400076, India., Sunoj RB; Department of Chemistry, Indian Institute of Technology Bombay , Powai, Mumbai 400076, India. |
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| Jazyk: | angličtina |
| Zdroj: | The Journal of organic chemistry [J Org Chem] 2018 Mar 02; Vol. 83 (5), pp. 2627-2639. Date of Electronic Publication: 2018 Feb 16. |
| DOI: | 10.1021/acs.joc.7b03047 |
| Abstrakt: | A comprehensive mechanistic study on the title reaction by using DFT(B3LYP-D3) computational method is reported. Explicit consideration of mono- (m-xylylic) and dicarboxylic acid (phthalic) in the key transition states reveals active participation of the carboxylic acid, beginning with the generation of a monomeric Rh(I) active catalyst and in the ensuing catalytic steps. In the early catalytic event, uptake of alkyne is predicted to take place only after the oxidative addition of the Rh(I) active catalyst to the carboxylic acid. The hydrometalation of the alkyne bound to the Rh(III)-H intermediate then generates a Rh(III)-vinyl intermediate, which in turn converts to a Rh(III)-allyl species. The inclusion of m-xylylic acid results in a two-step pathway to Rh(III)-allyl species via Rh-allene intermediate. A number of weak noncovalent interactions (hydrogen bonding and C-H···π) between the catalyst and the substrates and that involving m-xylylic acid are found to have a direct impact on the regiochemical preference toward the branched product and the enantiocontrolling hydroamination step involving C-N bond formation leading to the major enantiomer (S-allylic amine). The chiral induction is enabled by cumulative effect of noncovalent interactions, which is an insight that could aid future developments of chiral ligands for asymmetric hydroamination. |
| Databáze: | MEDLINE |
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