The First Synthesis of the Sterically Encumbered Adamantoid Phosphazane P4(NtBu)6: Enabled by Mechanochemistry

Shi, Yao‐Cheng; Xu, Kai; Clegg, Jack K.; Ganguly, Rakesh; Hirao, Hajime; Friščić, Tomislav; Garcı́a, Felipe

doi:10.1002/ange.201605936

Cited by 31 publications

(4 citation statements)

References 79 publications

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“…For example, although 1 i Pr is known, its synthesis via Me 3 SiCl elimination and a thermal rearrangement requires prolonged heating for weeks. Frisčǐcá nd Garcia have reported a rapid mechanochemical route to not only 1 i Pr but also the very bulky derivative 1 t Bu, 84 identifying mechanochemistry as a valuable but underutilized approach to PN cage synthesis. Between the melt-phase dehydrochlorination, salt metathesis, Me 3 SiCl elimination and mechanochemistry, a wide array of adamantoid PN cages are now synthetically accessible starting from inexpensive and commercially available amines and PCl 3 .…”

Section: Syntheses and Stability Of Tetrahedral And Linear Pn Cagesmentioning

confidence: 99%

Three-Dimensional Synthons for Cage-Dense Inorganic Polymers and Materials

Bedard,

Chitnis

2023

Chem. Mater.

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The relationship between the monomer structure and polymer properties is central to materials science. Here we discuss the notion of monomer dimensionality, as it refers to the presence of 1-dimensional chains, 2-dimensional rings, or 3-dimensional cages in inorganic polymers. We first highlight ring-containing systems, followed by classical 3-dimensional inorganic monomers (carboranes and polyhedral oligomeric silsesquioxanes, POSS). We then outline our development of modularly accessible phosphorus− nitrogen (PN) cages into polymerizable synthons to access linear or networked inorganic materials. Finally, we summarize the most important obstacles to advancement in the field and point toward areas where the most impactful discoveries are expected. Throughout the Perspective, an emphasis is placed on the properties that emerge when three-dimensional inorganic cages are present in the main chain, particularly as they contrast with materials containing monomers of lower dimensionality.

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Section: Syntheses and Stability Of Tetrahedral And Linear Pn Cagesmentioning

confidence: 99%

Three-Dimensional Synthons for Cage-Dense Inorganic Polymers and Materials

Bedard,

Chitnis

2023

Chem. Mater.

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“…These advantages can be attributed to efficient surface contact, high local concentration, and temperature. Intriguingly, in some cases, the chemical structures of the products formed under mechanochemical conditions are substantially different from these under classical solution conditions and forbidden transformations take place . It should be noticed that there is a fundamental difference between mechanochemical processes involving small molecules and macromolecules.…”

Section: Introductionmentioning

confidence: 99%

Porous Molecular Capsules as Non‐Polymeric Transducers of Mechanical Forces to Mechanophores

Jędrzejewska

Wielgus

Kaźmierski

et al. 2020

Chemistry A European J

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Mechanicalg rinding/milling can be regarded as historically the first technology for changing the properties of matter.M echanicallya ctivated molecular units (mechanophores) can be present in various structures:p olymers,m acromolecules, or smallm olecules. However,o nly polymers have been reported to effectively transduce energy to mechanophores,w hich induces breakage of covalentb onds. In this paper,asecond possibility is presented-molecular capsules as stress-sensitiveu nits. Mechanochemical encapsulation of fullerenes in cystine-based covalent capsules indi-cates that complexation takes place in the solid state, despite the fact that the capsules do not possess large enough entrance portals. By using as et of solvent-free MALDI (sf-MALDI) and solid-state NMR (ss-NMR) experiments,i th as been provent hat encapsulation proceedsduring milling and in this process hydrazones and disulfides get activated for breakage, exchange, and re-forming. The capsules are porousa nd therefore prone to collapse under solvent-free conditions and their conformational rigidity promotes the collapse by the breaking of covalent bonds.[a] Dr.

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“… [6b] . This enabling technology provides advantages such as prevent the use of excessive solvent, [6h] short reaction time, [6r–s] high efficiency [6t–u] and unique reactivity, [6f] and unlocks a new route toward numerous compounds not attainable by other synthetic techniques [6v] . Recent significant advances of “medicinal mechanochemistry” [8] promise to revolutionize the pharmaceutical industry, providing synthetic routes devoid of environmentally harmful solvents with diversified reactivity but excellent selectivity.…”

Section: Introductionmentioning

confidence: 99%

Mechanochemical C−X/C−H Functionalization: An Alternative Strategic Access to Pharmaceuticals

Yang

et al. 2022

Eur J Org Chem

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In the pursuit of clean pharmaceutical production, chemists in medicinal industry require access to new sustainable methodologies to reduce and even eliminate pollution, which is mainly produced by the overuse of organic solvents during chemical synthesis of active pharmaceutical ingredients (APIs). In this context, the solvent-free/less mechanochemical functionalization of small molecules has gradually emerged as a powerful strategy for the green synthesis and modification of APIs, bioactive compounds, and functional materials. In this review, we present an overview of mechanochemical CÀ X/CÀ H functionalization applications to medicinal chemistry, involving cross-coupling, cross-dehydrogenative coupling, oxidative coupling (via CÀ H activation pathway), and direct coupling (via radical pathway) as key steps for the preparation of APIs and bioactive compounds.

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The First Synthesis of the Sterically Encumbered Adamantoid Phosphazane P₄(N^tBu)₆: Enabled by Mechanochemistry

Cited by 31 publications

References 79 publications

Three-Dimensional Synthons for Cage-Dense Inorganic Polymers and Materials

Three-Dimensional Synthons for Cage-Dense Inorganic Polymers and Materials

Porous Molecular Capsules as Non‐Polymeric Transducers of Mechanical Forces to Mechanophores

Mechanochemical C−X/C−H Functionalization: An Alternative Strategic Access to Pharmaceuticals

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