By-design molecular architectures<i>via</i>alkyne metathesis

Huang, Shaofeng; Lei, Zepeng; Zhang, Wei

doi:10.1039/d1sc01881g

Cited by 51 publications

(35 citation statements)

References 74 publications

(97 reference statements)

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“… All it took was to react diyne 42 at 60 °C with a catalyst generated in situ from 17 upon exchange of the original amide ligands for triphenylsilanolates. Together with other similarly intricate applications in the literature, − this example suggests that alkyne metathesis has a bright future in the context of material science in general and DCC in particular. ,, …”

Section: Shape-persistent Objectssupporting

confidence: 66%

“…For this reason, it qualifies for applications to dynamic covalent chemistry (DCC) which mandates that a system is able to correct initial “mistakes” by scrambling of the mixture until the most stable product (distribution) has been reached. In so doing, DCC provides access to molecular objects beyond reach of more conventional approaches …”

Section: Shape-persistent Objectsmentioning

confidence: 99%

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The Ascent of Alkyne Metathesis to Strategy-Level Status

Fürstner

2021

J. Am. Chem. Soc.

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For numerous enabling features and strategic virtues, contemporary alkyne metathesis is increasingly recognized as a formidable synthetic tool. Central to this development was the remarkable evolution of the catalysts during the past decades. Molybdenum alkylidynes carrying (tripodal) silanolate ligands currently set the standards; their functional group compatibility is exceptional, even though they comprise an early transition metal in its highest oxidation state. Their performance is manifested in case studies in the realm of dynamic covalent chemistry, advanced applications to solid-phase synthesis, a revival of transannular reactions, and the assembly of complex target molecules at sites, which one may not intuitively trace back to an acetylenic ancestor. In parallel with these innovations in material science and organic synthesis, new insights into the mode of action of the most advanced catalysts were gained by computational means and the use of unconventional analytical tools such as 95Mo and 183W NMR spectroscopy. The remaining shortcomings, gaps, and desiderata in the field are also critically assessed.

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Section: Shape-persistent Objectssupporting

confidence: 66%

Section: Shape-persistent Objectsmentioning

confidence: 99%

The Ascent of Alkyne Metathesis to Strategy-Level Status

Fürstner

2021

J. Am. Chem. Soc.

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“…The discovery that silanolate ligands synergize remarkably well with molybdenum alkylidynes marks an important step in the development of alkyne metathesis. [ 1 , 2 , 3 , 4 , 5 , 6 ] Even the parent complexes of type 2 combine high activity with a previously unknown tolerance towards functional groups (Scheme 1 );[ 7 , 8 , 9 , 10 , 11 ] therefore, these catalysts opened new vistas for material science[ 12 , 13 ] and stood the test of natural product total synthesis in numerous demanding cases. [ 14 , 15 ] Moreover, the derived phenanthroline adducts [ 2 ⋅ (phen)] are bench‐stable and hence easy to handle, yet can be re‐converted into the catalytically active species on treatment with ZnCl 2 or MnCl 2 .…”

Section: Introductionmentioning

confidence: 99%

Canopy Catalysts for Alkyne Metathesis: Investigations into a Bimolecular Decomposition Pathway and the Stability of the Podand Cap

Hillenbrand

Korber

Leutzsch

et al. 2021

Chemistry A European J

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Molybdenum alkylidyne complexes with a trisilanolate podand ligand framework ("canopy catalysts") are the arguably most selective catalysts for alkyne metathesis known to date. Among them, complex 1 a endowed with a fence of lateral methyl substituents on the silicon linkers is the most reactive, although fairly high loadings are required in certain applications. It is now shown that this catalyst decomposes readily via a bimolecular pathway that engages the Mo�CR entities in a stoichiometric triple-bond metathesis event to furnish RC�CR and the corresponding dinuclear complex, 8, with a Mo�Mo core. In addition to the regular analytical techniques, 95 Mo NMR was used to confirm this unusual outcome. This rapid degradation mechanism is largely avoided by increasing the size of the peripheral substituents on silicon, without unduly compromising the activity of the resulting complexes. When chemically challenged, however, canopy catalysts can open the apparently somewhat strained tripodal ligand cages; this reorganization leads to the formation of cyclo-tetrameric arrays composed of four metal alkylidyne units linked together via one silanol arm of the ligand backbone. The analogous tungsten alkylidyne complex 6, endowed with a tripodal tris-alkoxide (rather than siloxide) ligand framework, is even more susceptible to such a controlled and reversible cyclo-oligomerization. The structures of the resulting giant macrocyclic ensembles were established by single-crystal X-ray diffraction.

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“…Covalent organic cages have attracted considerable attention for the recent decade. [1][2][3][4][5][6][7][8] Their most important characteristic is the intrinsic porosity, 7 and this feature has been applied to selective recognition/separation, [2][3]9 sensing, 10 catalysis, [11][12] etc. The other characteristic of cages is the geometric diversity, 6,13 which provides a panoply of polyhedra including tetrahedron, [14][15] octahedron, cuboctahedron, 16 cube, 14,17 prism, [18][19][20] as well as catenated structures.…”

Section: Introductionmentioning

confidence: 99%

Guest-Mediated Hierarchical Self-Assembly of Dissymmetric Organic Cages to Form Supramolecular Ferroelectrics

Liu

Zhu

et al. 2022

CCS Chem

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We herein report on the guest-responsive hierarchical self-assembly of dissymmetric cage DC-1 with intrinsic dipole along its C 3 -symmetric axis. DC-1 molecules self-assemble into supramolecular columns with the molecular dipoles aligned along the columnar axis. Mediated by different host-guest interactions of ethyl acetate (EtOAc) and chloroform (CHCl 3 ), the columns are arranged in an anti-parallel and parallel fashion, respectively, leading to a switch of centrosymmetric and non-centrosymmetric superstructures. The symmetry of the molecular packing of DC-1 molecules of the non-centrosymmetric crystalline phase is therefore broken, producing a supramolecular ferroelectric with second-harmonic generation and piezoelectric responses. We demonstrate that cages could serve as promising building blocks for the discovery of supramolecular materials with emergent functions and properties, including but not limited to, organic ferroelectrics and non-linear optics.

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By-design molecular architecturesviaalkyne metathesis

Abstract: The recent synthesis of novel shape-persistent 2D and 3D molecular architectures via alkyne metathesis is reviewed and the critical role of catalysts is also highlighted.

Cited by 51 publications

References 74 publications

The Ascent of Alkyne Metathesis to Strategy-Level Status

The Ascent of Alkyne Metathesis to Strategy-Level Status

Canopy Catalysts for Alkyne Metathesis: Investigations into a Bimolecular Decomposition Pathway and the Stability of the Podand Cap

Guest-Mediated Hierarchical Self-Assembly of Dissymmetric Organic Cages to Form Supramolecular Ferroelectrics

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