Rhodium Phosphine−π-Arene Intermediates in the Hydroamination of Alkenes

Liu, Zhijian; Yamamichi, Hideaki; Madrahimov, Sherzod T.; Hartwig, John F.

doi:10.1021/ja1057949

Cited by 93 publications

(88 citation statements)

References 61 publications

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“…13 Similar  1 interactions have been found with Au I , 14 Rh I , 15 V V , 16 and Pd 0 centers. 17 Anchored arenes coordinated in an  2 mode to Rh I , 18 Ir I , 19 and Ru II 20 have also been described. Finally, low hapticity coordination of biaryl groups is also common in the quintuply bonded Ar'CrCrAr' complexes reported by…”

Section: Introductionmentioning

confidence: 99%

Electronic and Structural Effects of Low-Hapticity Coordination of Arene Rings to Transition Metals

2014

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A DFT computational study and a structural analysis of the coordination of arenes to transition metals in low hapticity ( 1 and  2 ) modes have been developed, including a pseudosymmetry analysis of the molecular orbitals and the introduction of a hapticity map that makes evident the different degrees of intermediate hapticities.Calculations on [Pt II L 3 (C 6 H 6 )] model complexes reveal a preference for the  2 mode, while the  1 coordination is found to be a low energy transition state for a haptotropic shift. The attachment of the arene to a side group that is coordinated to the metal introduces geometrical constraints which result in hapticities intermediate between one and two. Comparison of the  1 arene complexes with benzonium cations shows that in the former case the bonding to the metal involves essentially the  system of the arene, affecting only slightly the delocalized nature of the carbon-carbon bonds. This behavior is in sharp contrast with the frequently found  1 coordination of Cp that involves  bonding and full dearomatization of the ring.2

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Section: Introductionmentioning

confidence: 99%

Electronic and Structural Effects of Low-Hapticity Coordination of Arene Rings to Transition Metals

2014

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“…However, data imply that these reactions occur with a turnover-limiting step that is different from that of reactions catalyzed by late transition metal complexes of Rh [48], Pd [6], Pt [33], and Ir [49]. This change in the turnover-limiting step and resulting high catalyst activity stem from favorable rates for protonolysis of the Rh-C bond.…”

Section: Rhodium-catalyzed Reactionsmentioning

confidence: 92%

“…Notably, this was the first late transition metal catalyst to cyclize primary aminoalkenes (53; R 0 ¼ H); however, higher temperatures and gem-disubstitution (R ¼ Ph) on the alkyl chain were required to facilitate cyclization. Detailed mechanistic studies revealed the active catalyst to be an η 6 , κ 1 complex that readily binds olefin to allow for intramolecular nucleophilic attack of the pendant amine [48]. Protonolysis of the Rh-C bond was found to be the rate-limiting step in the catalytic cycle.…”

Section: Rhodium-catalyzed Reactionsmentioning

confidence: 99%

Synthesis of Saturated Heterocycles via Metal-Catalyzed Alkene Hydroamination or Hydroalkoxylation Reactions

Julian

2013

Topics in Heterocyclic Chemistry

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The intramolecular hydrofunctionalization of carbon-carbon multiple bonds has emerged as a powerful way to form cyclic structures. A particularly important class of reactions involves the use of amine or alcohol nucleophiles, and alkenes or allenes as electrophiles, to form pyrrolidine, piperidine, tetrahydrofuran, and tetrahydropyran heterocycles in a highly efficient manner using late transition metal catalysts. Asymmetric methods for hydroamination and hydroalkoxylation reactions have recently emerged, allowing for the enantioselective synthesis of such saturated heterocycles. This review covers recent developments (over the last 5-10 years) in late transition metal-catalyzed hydroamination and hydroalkoxylation reactions that generate saturated heterocycles.

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“…Upon establishing steric and electronic requirements for catalyst activity in the computational study, we prepared catalysts for the hydroamination reactions of aminoalkenes that react to form product in yields that are higher than those of reactions catalyzed by the previously reported rhodium catalyst ligated by a biarylphosphine in an η 6 ,κ 1 fashion. 34,37 …”

Section: Introductionmentioning

confidence: 99%

Synthetic and Computational Studies on the Rhodium-Catalyzed Hydroamination of Aminoalkenes

2016

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The influence of ligand structure on rhodium-catalyzed hydroamination has been evaluated for a series of phosphinoarene ligands. These catalysts have been evaluated in a set of catalytic intramolecular Markovnikov hydroamination reactions. The mechanism of hydroamination catalyzed by the rhodium(I) complexes in this study was examined computationally, and the turnover-limiting step was elucidated. These computational studies were extended to a series of theoretical hydroamination catalysts to compare the electronic effects of the ancillary ligand substituents. The relative energies of intermediates and transition states were compared to those of intermediates in the reaction catalyzed by the unsubstituted catalyst. The experimental difference in the reactivities of electron-rich and electron-poor catalysts was compared to the computational results, and it was found that the activity for the electron-poor catalysts predicted from the reaction barriers was overestimated. Thus, the analysis of the catalysts in this study was expanded to include the binding preference of each ligand, in comparison to that of the unsubstituted ligand. This information accounts for the disparity between observed reactivity and the calculated overall reaction barrier for electron-poor ligands. The ligand-binding preferences for new ligand structures were calculated, and ligands that were predicted to bind strongly to rhodium generated catalysts for the experimental catalytic reactions that were more reactive than those predicted to bind more weakly.

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Rhodium Phosphine−π-Arene Intermediates in the Hydroamination of Alkenes

Cited by 93 publications

References 61 publications

Electronic and Structural Effects of Low-Hapticity Coordination of Arene Rings to Transition Metals

Electronic and Structural Effects of Low-Hapticity Coordination of Arene Rings to Transition Metals

Synthesis of Saturated Heterocycles via Metal-Catalyzed Alkene Hydroamination or Hydroalkoxylation Reactions

Synthetic and Computational Studies on the Rhodium-Catalyzed Hydroamination of Aminoalkenes

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