Synthesis and Reactivity of Zirconaaziridines

Cummings, Sarah A.; Tunge, Jon A.; Norton, Jack R.

doi:10.1007/b98414

Cited by 16 publications

(27 citation statements)

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“…To date, a comparable coupling of the cyclic imine 7 has only been reported for alkylsamarium complexes. [29] Instead of the C 5 H 5 ligand in 8, Marks et al used the more electron-rich and sterically more demanding C 5 Me 5 ligand in Cp*SmCH(SiMe 3 ) 2 (9). [29] For 9, the deprotonation of the methyl group in 7 is discussed as the key step in the formation of 10 (Scheme 5).…”

Section: Coupling Reactions Of Iminesmentioning

confidence: 98%

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Imines in the Titanium Coordination Sphere: Highly Reactive Titanaaziridines and Larger Titanacycles Formed by Subsequent C–C Coupling Reactions

et al. 2015

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The reductive complexation of aldimines is one of the promising synthetic tools to obtain titanaaziridines by reaction of the corresponding titanium halides and magnesium as a reducing agent. The effects of the substitution pattern of the imine ligand and the nature of the titanium fragment on the degree of activation of the η 2 -coordinated N-C double bond were investigated. With Cp # TiCl 3 (Cp # = cyclopentadienyl or pentamethylcyclopentadienyl) as the precursor for the reductive complexation of the imines N-(4-methylbenzylidene)aniline (2e) and 2-methyl-1-pyrroline (7), the formation of diazatitanacyclopentanes by McMurry-like C-C coupling is found. A six-membered titanacycle 8 is obtained by a Michael-like coupling reaction of 7. By these insights, it is

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Section: Coupling Reactions Of Iminesmentioning

confidence: 98%

“…[8,9,12] Zirconaaziridines undergo insertion reactions into the M-C bond with several substrates containing C-X multiple bonds, [9,15,[32][33][34] whereas the chemistry of titanaaziridines is Scheme 8. Reactivity of the titanoceneaziridines 3a-c.…”

Section: Reactivity Of the Titanoceneaziridinesmentioning

confidence: 99%

Imines in the Titanium Coordination Sphere: Highly Reactive Titanaaziridines and Larger Titanacycles Formed by Subsequent C–C Coupling Reactions

et al. 2015

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“…An alternative catalytic hydroaminoalkylation strategy would feature C–C bond formation between a simple alkyne and the α-carbon of amine starting materials. While stoichiometric variants of this transformation are well established, − the catalytic variant has thus far been unknown. , …”

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confidence: 99%

Zirconium-Catalyzed Hydroaminoalkylation of Alkynes for the Synthesis of Allylic Amines

2020

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A zirconium-catalyzed hydroaminoalkylation of alkynes to access α,β,γ-substituted allylic amines in an atomeconomic fashion is reported. The reaction is compatible with N-(trimethylsilyl)benzylamine and a variety of N-benzylaniline substrates, with the latter giving the allylic amine as the sole organic product. Various internal alkynes with electron-withdrawing and electron-donating substituents were tolerated. Model intermediates of the reaction were synthesized and structurally characterized. Stoichiometric studies on key intermediates revealed that the open coordination sphere at zirconium, imparted by the tethered bis(ureate) ligand, is crucial for the coordination of neutral donors. These complexes may serve as models for the inner-sphere protonolysis reactions required for catalytic turnover.

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“…However, in sharp contrast, analogous reactions of alkynes were faced with tremendous challenges (Fig. 1a), likely owing to difficult alkyne insertion and challenging protonolysis [32][33][34][35][36][37][38][39] . A pioneering investigation was conducted in 1989 by Buchwald and co-workers, who successfully obtained the allylic amine product by aqueous work-up.…”

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confidence: 99%

“…Despite an efficient protonolysis, the regeneration of Zr catalyst cannot be realized in this protocol, leading to stoichiometric Zr-complex needed 32 . Since then, much effort has been devoted to improving the reaction [33][34][35][36][37][38][39] , while the development of a catalytic method has been an elusive challenge. Most recently, during our submission, Schafer group used a tetradentate bis(ureate) ligand and metal Zr to in situ form a bulky Zr catalyst, achieving a catalytic hydroaminoalkylation of alkynes for the first time (Fig.…”

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Ni-catalyzed hydroaminoalkylation of alkynes with amines

Yao

Chen

et al. 2021

Nat Commun

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Allylic amines are versatile building blocks in organic synthesis and exist in bioactive compounds, but their synthesis via hydroaminoalkylation of alkynes with amines has been a formidable challenge. Here, we report a late transition metal Ni-catalyzed hydroaminoalkylation of alkynes with N-sulfonyl amines, providing a series of allylic amines in up to 94% yield. Double ligands of N-heterocyclic carbene (IPr) and tricyclohexylphosphine (PCy3) effectively promote the reaction.

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Synthesis and Reactivity of Zirconaaziridines

Cited by 16 publications

References 0 publications

Imines in the Titanium Coordination Sphere: Highly Reactive Titanaaziridines and Larger Titanacycles Formed by Subsequent C–C Coupling Reactions

Imines in the Titanium Coordination Sphere: Highly Reactive Titanaaziridines and Larger Titanacycles Formed by Subsequent C–C Coupling Reactions

Zirconium-Catalyzed Hydroaminoalkylation of Alkynes for the Synthesis of Allylic Amines

Ni-catalyzed hydroaminoalkylation of alkynes with amines

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