DFT and AFIR Study on the Mechanism and the Origin of Enantioselectivity in Iron-Catalyzed Cross-Coupling Reactions.
The mechanism of the full catalytic cycle for Fe-chiral-bisphosphine-catalyzed cross-coupling reaction between alkyl halides and Grignard reagents (Nakamura and co-workers, J. Am. Chem. Soc. 2015, 137, 7128) was rationalized by using density functional theory (DFT) and multicomponent artificial forc...
| Publicado en: | Journal of the American Chemical Society Vol. 139; no. 45; pp. 16117 - 16126 |
|---|---|
| Autores principales: | , , , , , , , , |
| Formato: | Artículo |
| Publicado: |
American Chemical Society
11/15/2017
|
| Materias: | |
| Acceso en línea: | Ver este registro en EBSCOhost |
| fields | @attributes: recordID: 1 pdfLink: plink: https://search.ebscohost.com/login.aspx?direct=true&db=hlh&AN=126379969&site=ehost-live header: @attributes: shortDbName: hlh uiTerm: 126379969 longDbName: Humanities International Complete uiTag: AN controlInfo: bkinfo: jinfo: jid: 00027863 ACS jtl: Journal of the American Chemical Society issn: 00027863 maglogo: N pubinfo: dt: 11/15/2017 vid: 139 iid: 45 pid: 997 pub: American Chemical Society artinfo: ui: 126379969 10.1021/jacs.7b05917 ppf: 16117 ppct: 9 formats: tig: atl: DFT and AFIR Study on the Mechanism and the Origin of Enantioselectivity in Iron-Catalyzed Cross-Coupling Reactions. aug: au: Sharma, Akhilesh K. Sameera, W. M. C. Masayoshi Jin Adak, Laksmikanta Chiemi Okuzono Takahiro Iwamoto Masako Kato Masaharu Nakamura Keiji Morokuma affil: Fukui Institute for Fundamental Chemistry, Kyoto University, Kyoto 606-8103, Japan Department of Chemistry, Faculty of Science, Hokkaido University, Kita-Ku, Sapporo 060-0810, Japan International Research Center for Elements Science, Institute for Chemical Research, Kyoto University, Uji, Kyoto 611-0011, Japan Department of Energy and Hydrocarbon Chemistry, Graduate School of Engineering, Kyoto University, Kyoto 615-8510, Japan Process Technology Research Laboratories, Pharmaceutical Technology Division, Daiichi Sankyo Co., Ltd., 1-12-1 Shinomiya, Hiratsuka, Kanagawa 254-0014, Japan su: Enantioselective catalysis Iron catalysts Coupling reactions (Chemistry) Grignard reagents Density functional theory Induced reactions (Chemistry) Haloalkanes sug: subj: Enantioselective catalysis Iron catalysts Coupling reactions (Chemistry) Grignard reagents Density functional theory Induced reactions (Chemistry) Haloalkanes ab: The mechanism of the full catalytic cycle for Fe-chiral-bisphosphine-catalyzed cross-coupling reaction between alkyl halides and Grignard reagents (Nakamura and co-workers, J. Am. Chem. Soc. 2015, 137, 7128) was rationalized by using density functional theory (DFT) and multicomponent artificial force-induced reaction (MC-AFIR) methods. The computed mechanism consists of (a) C-Cl activation, (b) transmetalation, (c) C-Fe bond formation, and (d) C-C bond formation through reductive elimination. Our survey on the prereactant complexes suggested that formation of Fe(BenzP*)Ph and Fe(BenzP*)Ph complexes are thermodynamically feasible. Fe(BenzP*)Cl complex is the active intermediate for C-Cl activation. Fe(BenzP*)Ph complex can be formed if the concentration of Grignard reagent is high. However, it leads to biphenyl (byproduct) instead of the cross-coupling product. This explains why slow addition of Grignard reagent is critical for the cross-coupling reaction. The MC-AFIR method was used for systematic determination of transition states for C-Fe bond formation and C-C bond formation starting from the key intermediate Fe(BenzP*)PhCl. According to our detailed analysis, C-C bond formation is the selectivity-determining step. The computed enantiomeric ratio of 95:5 is in good agreement with the experimental ratio (90:10). Energy decomposition analysis suggested that the origin of the enantioselectivity is the deformation of Ph-ligand in Fe-complex, which is induced by the bulky tert-butyl group of BenzP* ligand. Our study provides important mechanistic insights for the cross-coupling reaction between alkyl halides and Grignard reagents and guides the design of efficient Fe-based catalysts for cross-coupling reactions. pubtype: Academic Journal doctype: Article src: R language: English refInfo: copyright: @attributes: flag: Y dt: @attributes: year: 2017 holdings: @attributes: islocal: N |
|---|