Lithiation-electrophilic trapping of N-sulfonyl-activated ethylene aziridines

Huang, Jianhui; Moore, Stephen P.; O’Brien, Peter; Whitwood, Adrian C.; Gilday, John

doi:10.1039/b815957b

Cited by 18 publications

(18 citation statements)

References 27 publications

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“…The knowledge of the exact structure of the deprotonation substrate is usefull for further discussions of metalleted or substituted derivatives. The succesful deprotonation of such aziridines similar to the title compound were already reported by Huang et al, 2009. The synthesis of the title compound via sulfonium ylide transfer was most recently reportet by Kavanagh et al, 2013. π-π-Interactions between parallel phenyl groups of adjacent molecules are indicated by a plane-to-plane distance of 3.76 (1) Å, whereas the distance between the isopropyl substituted benzene rings is far longer with 6.30 (1) Å (distance of the centroids).…”

Section: Methodssupporting

confidence: 59%

“…For structures containing the triisopropylbenzenesulfonyl group with detailed discussion of the geometry, see: Sandrock et al (2004); Laba et al (2009). For the lithiation of activated aziridines, see: Huang et al (2009) and for a general review on aziridinylanions, see: Florio & Luisi (2010). For the most recent synthesis of the title compound, see: Kavanagh et al (2013).…”

Section: Related Literaturementioning

confidence: 99%

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rac-2-Phenyl-1-[(2,4,6-triisopropylbenzene)sulfonyl]aziridine

2014

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In the title compound, C23H31NO2S, the geometry of the triisopropylphenyl group is slightly distorted, with elongated C—C bonds at the ipso-C atom, and an S atom which deviates from the benzene ring plane by 0.228 (2) Å. This distortion is caused by the bulky substituents and, in comparison, an unbent geometry is observed in N-toluenesulfonylaziridine [Zhu et al. (2006 ▶). Acta Cryst. E62, o1507–o1508]. π–π interactions between adjacent benzene rings [centroid–centroid distance = 3.7928 (11) Å] and are observed.

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Section: Methodssupporting

confidence: 59%

Section: Related Literaturementioning

confidence: 99%

rac-2-Phenyl-1-[(2,4,6-triisopropylbenzene)sulfonyl]aziridine

2014

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“…On one hand, most of O3‐Na x MO 2 compounds are very hygroscopic against moist atmosphere, leading to the formation of electrochemically inactive NaOH, NaHCO 3 , or Na 2 CO 3 by partial Na extraction. These alkaline species would accelerate the defluorination of polyvinylidene fluoride binder and corrosion of current collector due to their dissolution into N ‐methyl‐2‐pyrrolidone solvent, drastically impeding their practical viability . On the other hand, extraction and insertion of Na ions from layered compounds inevitably leads to several first‐order phase transformations sequences accompanied by multiple voltage plateaus and steps in the electrochemical curves, incurring low diffusion coefficients and complicated cation diffusion mechanisms as additional energy barrier is needed in moving the Na ions from neighboring phase boundaries.…”

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confidence: 99%

An Ordered Ni₆‐Ring Superstructure Enables a Highly Stable Sodium Oxide Cathode

et al. 2019

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The ORCID identification number(s) for the author(s) of this article can be found under https://doi.org/10.1002/adma.201903483. Sodium-based layered oxides are among the leading cathode candidates for sodium-ion batteries, toward potential grid energy storage, having large specific capacity, good ionic conductivity, and feasible synthesis. Despite their excellent prospects, the performance of layered intercalation materials is affected by both a phase transition induced by the gliding of the transition metal slabs and air-exposure degradation within the Na layers. Here, this problem is significantly mitigated by selecting two ions with very different MO bond energies to construct a highly ordered Ni 6 -ring superstructure within the transition metal layers in a model compound (NaNi 2/3 Sb 1/3 O 2 ). By virtue of substitution of 1/3 nickel with antimony in NaNiO 2 , the existence of these ordered Ni 6 -rings with super-exchange interaction to form a symmetric atomic configuration and degenerate electronic orbital in layered oxides can not only largely enhance their air stability and thermal stability, but also increase the redox potential and simplify the phase-transition process during battery cycling. The findings reveal that the ordered Ni 6 -ring superstructure is beneficial for constructing highly stable layered cathodes and calls for new paradigms for better design of layered materials. Sodium-Ion Batteries

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“…The lithiation is accomplished with s-BuLi (3 equiv) and pentamethyldiethylenetriamine (PMDTA) at −78 • C in tetrahydrofuran (THF). The trapping with aldehydes provides a stereoselective route to syn-hydroxyalkyl aziridines (Scheme 7.9, condition B) [9].…”

Section: Three-membered Rings: Lithiated Aziridinesmentioning

confidence: 99%

Nitrogen‐Bearing Lithium Compounds in Modern Synthesis

Degennaro¹,

Musio²,

Luisi³

2014

Lithium Compounds in Organic Synthesis

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IntroductionNitrogen-containing compounds are ubiquitous and are extremely important in synthesis. This chapter reports some general aspects of the generation, structure, and reactivity of nitrogen-bearing organolithiums showing the progress made over the last decade. The chapter does not cover comprehensively the field but the aim is to provide the reader with useful information on the generation, reactivity, and potential in synthesis of this kind of lithiated intermediates.Throughout the chapter, the name amino-organolithiums is used to describe reactive intermediates lithiated at sp 3 -hybridized carbon atoms adjacent (α) to a nitrogen atom that could be included also in a ring. Amino-organolithiums can be generated mainly in three different ways: (i) deprotonation of a parent amine or its derivative; (ii) transmetallation by using an alkyllithium; and (iii) reductive cleavage of C-heteroatom bond (e.g., C-S). Each way has advantages and disadvantages and in some cases they complement each other (Scheme 7.1).Direct deprotonation is a widely used strategy to generate amino-organolithiums even in chiral form, while tin-lithium exchange reactions are preferred when direct deprotonations are difficult (high kinetic barrier) or regiochemical issues apply. Concerning the direct deprotonation of amines, this is not a simple task because the corresponding lithiated intermediates suffer from destabilizing interactions that make this reaction very difficult unless a ''stabilizing group'' (SG) is introduced either on the nitrogen atom or on the lithium-bearing carbon (Scheme 7.2).The SG (Scheme 7.2) has a pivotal role, either reducing the kinetic barrier in the hydrogen/lithium permutation or stabilizing the organolithium mesomerically or by coordination. For these reasons, often, amino-organolithiums are classified as stabilized or unstabilized. The chemistry of unstabilized amino-organolithiums has been so far less developed however, lithiation of simple tertiary amines could be accomplished by two main strategies: (i) by tin/lithium exchange reaction and (ii) by deprotonation of quaternary ammonium complexes (Scheme 7.3).

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Lithiation-electrophilic trapping of N-sulfonyl-activated ethylene aziridines

Cited by 18 publications

References 27 publications

rac-2-Phenyl-1-[(2,4,6-triisopropylbenzene)sulfonyl]aziridine

rac-2-Phenyl-1-[(2,4,6-triisopropylbenzene)sulfonyl]aziridine

An Ordered Ni₆‐Ring Superstructure Enables a Highly Stable Sodium Oxide Cathode

Nitrogen‐Bearing Lithium Compounds in Modern Synthesis

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Lithiation-electrophilic trapping of N-sulfonyl-activated ethylene aziridines

Cited by 18 publications

References 27 publications

rac-2-Phenyl-1-[(2,4,6-triisopropylbenzene)sulfonyl]aziridine

rac-2-Phenyl-1-[(2,4,6-triisopropylbenzene)sulfonyl]aziridine

An Ordered Ni6‐Ring Superstructure Enables a Highly Stable Sodium Oxide Cathode

Nitrogen‐Bearing Lithium Compounds in Modern Synthesis

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An Ordered Ni₆‐Ring Superstructure Enables a Highly Stable Sodium Oxide Cathode