Rhodium‐Catalyzed Stereoselective Amination of Thioethers with N‐Mesyloxycarbamates: DMAP and Bis(DMAP)CH2Cl2 as Key Additives

Lebel, H.; Piras, Henri; Bartholoméüs, Johan

doi:10.1002/anie.201402961

Cited by 86 publications

(44 citation statements)

References 57 publications

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“…These chiral bulky rhodium dimers are also known to adopt various conformers depending of the substituents: C 4 (all-up), C 1 , D 2 and C 2 . [29] The four possible conformations were calculated for Rh 2 [(S)-nttl] 4 ( Figure 13). [28] X-ray crystal structure analysis of N-naphthaloyl chiral dirhodium complexes demonstrated that these catalysts, in the solid state, adopted preferentially the C 4 conformation.…”

Section: Stereoselectivity Of the Aziridination Of Styrene With (R)-pmentioning

confidence: 99%

“…[28] X-ray crystal structure analysis of N-naphthaloyl chiral dirhodium complexes demonstrated that these catalysts, in the solid state, adopted preferentially the C 4 conformation. [29] The four possible conformations were calculated for Rh 2 [(S)-nttl] 4 (Figure 13). The C 4 RhÀ Rh conformation was identified as the lowest in energy with the other conformations higher by 7.8 (C 1 RhÀ Rh ), 9.1 (C 2 RhÀ Rh ) and 10.0 (D 2 RhÀ Rh ) kcal/mol.…”

Section: Full Papermentioning

confidence: 99%

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A Mechanistic Study of the Stereochemical Outcomes of Rhodium‐Catalysed Styrene Aziridinations

et al. 2019

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The stereoselective, rhodium-catalysed aziridination of styrene derivatives with a chiral Nmesyloxycarbamate was found to be highly substrate dependent. A density functional theory (DFT) study is herein reported to elucidate the stereochemical outcome of the aziridination process. Rhodium acetate was initially used as a model catalyst, followed by computational studies conducted with Rh 2 [(S)-nttl] 4 . Both singlet and triplet rhodium nitrene species were identified as intermediates affording concomitant concerted and radical pathways. In the latter case, the radical intermediate appears to undergo a direct ring closure via a minimum energy crossing point (MECP) between the triplet and closed-shell singlet surfaces. Exceptionally for the m-Br-styrene aziridination, an alternative radical pathway with a carbon-carbon bond rotation was observed, accounting for the observed 74:26 mixture of diastereomers. The computational analysis also suggests little control of the metal nitrene conformation with Rh 2 (OAc) 4 with the chiral N-mesyloxycarbamate: two conformers were located affording two diastereomers of the aziridine and correlating our experimental results. On the other hand, only one conformer was found for the nitrene generated from the chiral Nmesyloxycarbamate and Rh 2 [(S)-nttl] 4 . The so-called "all-up" conformer of Rh 2 [(S)-nttl] 4 was not only the most stable metal nitrene species, but also afforded the lowest energy transition state. The calculated dr for p-Br-styrene aziridination agrees with the observed experimental result. The combination of experimental and computational results offers a detailed mechanistic picture, providing insights for further catalyst development to enhance reactivity and selectivity.

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Section: Stereoselectivity Of the Aziridination Of Styrene With (R)-pmentioning

confidence: 99%

Section: Full Papermentioning

confidence: 99%

A Mechanistic Study of the Stereochemical Outcomes of Rhodium‐Catalysed Styrene Aziridinations

et al. 2019

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“…Encouraged by the S-imidation [66][67][68][69][70] isolated yield (81%, entry 15). Lastly, reaction of 1 (1 equiv) with excess amount of 2 (2.5 equiv) under the same conditions gave double imidation product iminophosphonamide (P V ) 3b in excellent yield and selectivity (entry 16).…”

Section: Resultsmentioning

confidence: 99%

Nitrene-Mediated P–N Coupling Under Iron Catalysis

et al. 2022

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P-N and P=N bonds play important roles in the design and synthesis of functional molecules such as bioactive compounds and organic ligands for catalysis. Existing methods for P-N coupling mostly rely on Staudinger condensation or nucleophilic substitution between phosphorus electrophiles and amine nucleophiles. Herein, we report a nitrene-mediated intermolecular P-N coupling reaction between various phosphorus nucleophiles and dioxazolones under simple iron-catalyzed conditions. These reactions offer an efficient, versatile, and broadly applicable method for synthesis of a range of N-P compounds including amidophosphines, iminophosphonamides, phosphinamides, aminophosphines, and iminophosphoranes from readily available precursors under mild conditions.

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“…A chiral N -mesyloxycarbamate caused a stereoselective amination of thioethers in the presence of a chiral dirhodium(II) carboxylate catalyst to yield the corresponding sulfilimines. 290 , 291 The possibility of preparation of sulfoximine through oxidation of sulfilimine with NaIO 4 with RuCl 3 as a catalyst was demonstrated; removal of chiral auxiliary with zinc in acetic acid yielded NH -sulfilimine as a single enantiomer (94%). Lebel and co-workers also applied iron catalyst in a similar preparation.…”

Section: Stereoselective Synthesis Of Sulfoximinesmentioning

confidence: 99%

Modern Stereoselective Synthesis of Chiral Sulfinyl Compounds

2020

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Chiral sulfinyl compounds, sulfoxides, sulfoximines, sulfinamides, and other derivatives, play an important role in asymmetric synthesis as versatile auxiliaries, ligands, and catalysts. They are also recognized as pharmacophores found in already marketed and well-sold drugs (e.g., esomeprazole) and used in drug design. This review is devoted to the modern methods of preparation of sulfinyl derivatives in enantiopure or enantiomerically enriched form. Selected new approaches leading to racemic products for which the asymmetric variant can be developed in the future are mentioned as well.

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Rhodium‐Catalyzed Stereoselective Amination of Thioethers with N‐Mesyloxycarbamates: DMAP and Bis(DMAP)CH₂Cl₂ as Key Additives

Cited by 86 publications

References 57 publications

A Mechanistic Study of the Stereochemical Outcomes of Rhodium‐Catalysed Styrene Aziridinations

A Mechanistic Study of the Stereochemical Outcomes of Rhodium‐Catalysed Styrene Aziridinations

Nitrene-Mediated P–N Coupling Under Iron Catalysis

Modern Stereoselective Synthesis of Chiral Sulfinyl Compounds

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