Intermolecular Hydroamination of 1,3-Dienes Catalyzed by Bis(phosphine)carbodicarbene–Rhodium Complexes

Goldfogel, Matthew J.; Roberts, Courtney C.; Meek, Simon J.

doi:10.1021/ja502275w

Cited by 144 publications

(65 citation statements)

References 49 publications

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“…At this juncture, attempts to isolate the free pincer CDC 45 were unsuccessful. The salt 44 could be converted to the square‐planar complex 46 via cyclometalation with [Rh(cod)Cl] 2 in the presence of NaOMe base . The Rh I complex 46 was crystallized as an orange/yellow solid, with the 13 C NMR signal of the CDC carbon(0) appearing as a doublet of triplets at ≈73 ppm.…”

Section: Development and Structural Diversity Of Carbodicarbenesmentioning

confidence: 99%

“…The teams of Meek and Ong are considered pioneers in employing CDCs as supporting ligands in catalysis. Meek and coworkers demonstrated that the pincer CDC Rh I complex 46 efficiently catalyzed intermolecular hydroamination of 1,3‐diene substrates with various aryl and alkyl amines (Scheme ) . For example, complex 46 in the presence of a catalytic amount of AgBF 4 catalyzed the hydroamination of phenyl 1,3‐butadiene ( O1‐a ) with p ‐CF 3 or p ‐methoxy‐substituted anilines ( O2 ) to afford allylic amines ( O4 ) with >98 % γ‐selectivity in excellent yield.…”

Section: Carbodicarbenes In Catalysismentioning

confidence: 99%

“…The salt 44 could be converted to the square-planar complex 46 via cyclometalation with [Rh(cod)Cl] 2 in the presence of NaOMe base. [21] The Rh I complex 46 was crystallized as an orange/yellow solid, with the 13 CNMR signal of the CDC carbon(0) appearing as a doublet of tripletsa t% 73 ppm. Thisv alue is consistentw ith previously reportedR hc omplexes bearing monodentate CDCs and the up-fields hift emphasized the electron-rich nature of the divalent carbon (0).…”

Section: Pincer Carbodicarbenesmentioning

confidence: 99%

“…Meek and coworkers demonstrated that the pincer CDC Rh I complex 46 efficientlyc atalyzed intermolecular hydroamination of 1,3-dienes ubstrates with various aryl and alkyl amines (Scheme 16). [21] For example, complex 46 in the presence of ac atalytic amount of AgBF 4 catalyzed the hydroamination of phenyl 1,3-butadiene (O1-a)w ith p-CF 3 or p-methoxy-substituted anilines( O2)t oa fford allylic amines (O4)w ith > 98 % g-selectivity in excellent yield. For alkyl amine cases (O3), the (CDC)-Rh-catalyzed hydroamination requires highert emperatures (80 8C) to proceed compared to aryl amines (50-60 8C).…”

Section: Carbodicarbenes In Catalysismentioning

confidence: 99%

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Carbodicarbenes and their Captodative Behavior in Catalysis

et al. 2018

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That of carbones is a new family member in the class of low‐valent carbon compounds. Unlike its cousin, the conventional carbene, the carbone possesses two free electron lone pairs. In combination with their unique allene‐type structure, they possess stronger σ‐donating ability than conventional carbenes such as NHCs or CAACs. Because of this property, they have a huge potential to become a new class of ligands in organometallic chemistry and catalysis. Although carbodiphosphoranes (CDP) were initially discovered in 1961, nearly 50 years were needed to attract the attention of the chemical community with the synthesis of the carbodicarbene (CDC). This Concept paper summarizes developments over the last 10 years and future outlooks for this new class of σ‐donors, particularly carbodicarbenes.

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Section: Development and Structural Diversity Of Carbodicarbenesmentioning

confidence: 99%

Section: Carbodicarbenes In Catalysismentioning

confidence: 99%

Section: Pincer Carbodicarbenesmentioning

confidence: 99%

Section: Carbodicarbenes In Catalysismentioning

confidence: 99%

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Carbodicarbenes and their Captodative Behavior in Catalysis

et al. 2018

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“…2,3 Other alkenes that have been activated for hydroamination include those possessing substituents that enable a stepwise pathway. Examples of such alkenes include Michael acceptors, alkenes bearing directing groups, 12–14 and alkenes that react to form allyl or benzyl complexes, such as dienes, 15–17 allenes, and vinylarenes. 18–26 Likewise, strained bicyclic alkenes 27,28 undergo migratory insertion steps more quickly than unstrained alkenes and form alkyl intermediates that do not undergo β-hydrogen elimination to form oxidized products.…”

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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