<i>p</i>-Toluenesulfonyl Azide

Heydt, H.; Regitz, Manfred

doi:10.1002/047084289x.rt141

Cited by 4 publications

(3 citation statements)

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“…A C 2 + N 1 approach to aziridination features an alkene (C 2 ) and a nitrene fragment (N 1 ) combining to make the aziridine . Nitrene fragments most commonly come from protected azides (e.g., TsN 3 , − TcepN 3 , and (SES)N 3 ), , aryl azides, − and, more recently, alkyl azides, all of which are easy to synthesize. ,− While porphyrin and salen complexes are successful catalysts for N -substituted aziridination, ,,,, very few mechanistic studies have been performed for these systems. , This lack of mechanistic studies for group transfer for the nitrene is in direct contrast to the numerous studies that have investigated the mechanisms for epoxidation and the associated group transfer from metal oxos to alkenes. − …”

Section: Introductionmentioning

confidence: 99%

Elucidation of the Reaction Mechanism of C₂ + N₁ Aziridination from Tetracarbene Iron Catalysts

et al. 2019

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A combined computational and experimental study was undertaken to elucidate the mechanism of catalytic C 2 + N 1 aziridination supported by tetracarbene iron complexes. Three specific aspects of the catalytic cycle were addressed. First, how do organic azides react with different iron catalysts and why are alkyl azides ineffective for some catalysts? Computation of the catalytic pathway using density functional theory (DFT) revealed that an alkyl azide needs to overcome a higher activation barrier than an aryl azide to form an iron imide, and the activation barrier with the firstgeneration catalyst is higher than the activation barrier with the second-generation variant. Second, does the aziridination from the imide complex proceed through an open-chain radical intermediate that can change stereochemistry or, instead, via an azametallacyclobutane intermediate that retains stereochemistry? DFT calculations show that the formation of aziridine proceeds via the openchain radical intermediate, which qualitatively explains the formation of both aziridine diastereomers as seen in experiments. Third, how can the formation of the side product, a metallotetrazene, be prevented, which would improve the yield of aziridine at lower alkene loading? DFT and experimental results demonstrate that sterically bulky organic azides prohibit formation of the metallotetrazene and, thus, allow lower alkene loading for effective catalysis. These multiple insights of different aspects of the catalytic cycle are critical for developing improved catalysts for C 2 + N 1 aziridination.

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Section: Introductionmentioning

confidence: 99%

Elucidation of the Reaction Mechanism of C₂ + N₁ Aziridination from Tetracarbene Iron Catalysts

et al. 2019

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“…To test the feasibility of our hypothesis, we commenced our study by evaluating a series of nickel catalysts for the proposed three-component carboamination with 4-methyl- N -(pent-4-en-1-yl)benzenesulfonamide ( 1a ) as the model substrate (Table ). The reaction was attempted using dimethylzinc and 4-methylbenzenesulfonyl azide (TsN 3 ) as an alkyl nucleophile and a nitrene precursor, respectively. In particular, we envisioned that an organic azide would be an attractive nitrene precursor since the amination would then proceed in the absence of external oxidants that could decompose the organozinc coupling partner …”

Section: Resultsmentioning

confidence: 99%

Ligand-Enabled Carboamidation of Unactivated Alkenes through Enhanced Organonickel Electrophilicity

Hwang,

Wisniewski,

Engle

2023

J. Am. Chem. Soc.

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Catalytic carboamination of alkenes is a powerful synthetic tool to access valuable amine scaffolds from abundant and readily available alkenes. Although a number of synthetic approaches have been developed to achieve the rapid buildup of molecular complexity in this realm, the installation of diverse carbon and nitrogen functionalities onto unactivated alkenes remains underdeveloped. Here we present a ligand design approach to enable nickel-catalyzed three-component carboamidation that is applicable to a wide range of alkenyl amine derivatives via a tandem process involving alkyl migratory insertion and inner-sphere metal−nitrenoid transfer. With this method, various nitrogen functionalities can be installed into both internal and terminal unactivated alkenes, leading to differentially substituted diamines that would otherwise be difficult to access. Mechanistic investigations reveal that the tailored Ni(cod)(BQ iPr ) precatalyst modulates the electronic properties of the presumed π-alkene−nickel intermediate via the quinone ligand, leading to enhanced carbonickelation efficiency across the unactivated C�C bond. These findings establish nickel's ability to catalyze multicomponent carboamidation with a high efficiency and exquisite selectivity.

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“…, 2 0 0 3 , 1 0 9 2 -1 0 9 3 DOI: 10.1039/b301335a related complex [Pt(PPh 3 ) 2 (h 2 -t BuC(H)NP(O) t Bu] 9 can be obtained directly by controlled peracid oxidation of 5. 8 Notes and references ‡ NMR data for 6: 31 P{ 1 H} (121.4 MHz, C 6 D 6 ); d 1.5 (dd, P A , 1 J P A P B 260.4, 2 J P A P D 56.6, 1 J P A Pt 368.4 Hz); d 282.6 (dd, P B , 1 J P B P A 260.5, 3 J P B P D 11.0, 2 J P B Pt 68.2 Hz); d 47.3 (d, P C , 2 J P C P D 27.7, 1 J P C Pt 3390 Hz); d 43.1 (ddd, P D , 2 J P D P A 56.7, 2 J P D P C 27.7, 3 J P D P B 11.0, 1 J P D Pt 3166 Hz). 195…”

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confidence: 99%

Synthesis of a η2-2,3-diphosphabutadiene complex of zerovalent platinum from the corresponding η2-phosphaalkyne complex

et al. 2003

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Hydrozirconation of the eta 2-phosphaalkyne complex [Pt(dppe)(eta 2-tBuCP)] with [ZrHCl(eta 5-C5H5)2], followed by treatment with the chlorophosphaalkene ClP=C(SiMe3)2 affords the eta 2-2,3-diphosphabutadiene complex [Pt(dppe)(eta 2-tBuC(H)=PP=C(SiMe3)2]. In the presence of [Pt(PPh3)2] the latter undergoes an addition reaction with water to afford the structurally characterised Pt(II) complex [Pt(dppe)(tBuCH2P(O)HPC(SiMe3)2].

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p-Toluenesulfonyl Azide

Cited by 4 publications

References 50 publications

Elucidation of the Reaction Mechanism of C₂ + N₁ Aziridination from Tetracarbene Iron Catalysts

Elucidation of the Reaction Mechanism of C₂ + N₁ Aziridination from Tetracarbene Iron Catalysts

Ligand-Enabled Carboamidation of Unactivated Alkenes through Enhanced Organonickel Electrophilicity

Synthesis of a η2-2,3-diphosphabutadiene complex of zerovalent platinum from the corresponding η2-phosphaalkyne complex

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p-Toluenesulfonyl Azide

Cited by 4 publications

References 50 publications

Elucidation of the Reaction Mechanism of C2 + N1 Aziridination from Tetracarbene Iron Catalysts

Elucidation of the Reaction Mechanism of C2 + N1 Aziridination from Tetracarbene Iron Catalysts

Ligand-Enabled Carboamidation of Unactivated Alkenes through Enhanced Organonickel Electrophilicity

Synthesis of a η2-2,3-diphosphabutadiene complex of zerovalent platinum from the corresponding η2-phosphaalkyne complex

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Elucidation of the Reaction Mechanism of C₂ + N₁ Aziridination from Tetracarbene Iron Catalysts

Elucidation of the Reaction Mechanism of C₂ + N₁ Aziridination from Tetracarbene Iron Catalysts