Anion−π Catalysis on Fullerenes

López‐Andarias, Javier; Frontera, Antonio; Matile, Stefan

doi:10.1021/jacs.7b08113

Cited by 74 publications

(85 citation statements)

References 40 publications

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“…The complementary π slides composed of three π ‐acidic naphthalenediimides caused the expected inversion from cation to anion selectivity ( Figure ,c ) . The promise of anion‐ π interactions in synthetic transport systems has since been validated in many variations, also with very small systems, and extended to catalysis …”

Section: Introductionmentioning

confidence: 96%

Mechanosensitive Oligodithienothiophenes: Transmembrane Anion Transport Along Chalcogen‐Bonding Cascades

Macchione

Tsemperouli

Goujon

et al. 2018

Helvetica Chimica Acta

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The design, synthesis, and evaluation of multifunctional dithieno[3,2‐b;2′,3′‐d]thiophene (DTT) trimers is described. Twisted push‐push‐pull or donor‐donor‐acceptor (DDA) trimers composed of one DTT acceptor and two DTT donors show strong mechanochromism in lipid bilayer membranes. Red shifts in excitation rather than emission and fluorescence recovery with increasing membrane order are consistent with planarization of the twisted, extra‐long mechanophores in the ground state. The complementary pull‐pull‐pull or AAA trimers with deep σ holes all along the scaffold are not mechanochromic in membranes but excel with submicromolar anion transport activity. Anion transport along membrane‐spanning strings of chalcogen‐bond donors is unprecedented and completes previous results on transmembrane cascades that operate with equally unorthodox interactions such as halogen bonds and anion‐π interactions.

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Section: Introductionmentioning

confidence: 96%

Mechanosensitive Oligodithienothiophenes: Transmembrane Anion Transport Along Chalcogen‐Bonding Cascades

Macchione

Tsemperouli

Goujon

et al. 2018

Helvetica Chimica Acta

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“…To realize the direct formation of 1,3‐nonadjacent stereocenters on π ‐acidic surfaces, catalysts 4 – 13 were prepared from commercially available starting materials following reported procedures ( Figure ) . Among them, catalysts 4 – 8 were designed to covalently tether tertiary amine bases to the π ‐acidic surface of naphthalenediimides (NDIs) via suitable linkers.…”

Section: Resultsmentioning

confidence: 99%

“…The recently introduced, somehow complementary fullerenes excel in anion‐ π catalysis because of their high polarizability and localized π holes on their surface . Anion‐ π catalysis on fullerenes is particularly attractive because the use of fullerenes in catalysis on the one hand and anion‐ π interactions on fullerenes on the other hand are both underrecognized general topics that deserve scientific attention.…”

Section: Resultsmentioning

confidence: 99%

“…Anion‐ π catalysis on fullerenes is particularly attractive because the use of fullerenes in catalysis on the one hand and anion‐ π interactions on fullerenes on the other hand are both underrecognized general topics that deserve scientific attention. In fullerene anion‐ π catalyst 9 , the preorganization from the chiral cyclohexyldiamine turn was used as in NDI catalysts 4 – 6 to position a tertiary amine base close to the active fullerene surface . This positioning has been shown to be essential to turn on anion‐ π interactions as soon as the negative charge is injected into the substrate by proton transfer to the base .…”

Section: Resultsmentioning

confidence: 99%

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Anion‐π Catalysis: Focus on Nonadjacent Stereocenters

Zhang

Liu

López‐Andarias

et al. 2018

Helvetica Chimica Acta

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In Memory of Gilbert StorkAnion-p interactions have been recently introduced to catalysis with the idea to stabilize anionic intermediates on p-acidic surfaces. Realized examples include enolate, enamine and iminium chemistry, domino processes and DielsAlder reactions. Moving on from the formation of contiguous stereogenic centers on p-acidic surfaces, herein we report the first asymmetric anion-p catalysis of cascade reactions that afford nonadjacent stereocenters. Conjugate addition-protonation of achiral disubstituted enolate donors to 2-chloroacrylonitrile generates 1,3-nonadjacent stereocenters with moderate enantioselectivity and diastereoselectivity. The explored catalysts operate with complementary naphthalenediimide and fullerene surfaces with highly positive quadrupole moments and high polarizability, respectively, and proximal amine bases. We find that anion-p catalysts can increase the diastereoselectivity of the reaction beyond the maximal 1:4.0 dr with conventional catalysts to maximal 5.3:1 dr on the large fullerene surfaces. The enantioselectivity of anion-p catalysts, best on the confined naphthalenediimide surfaces with strong quadrupole moment, exceed the performance of conventional catalysts except for comparable results with a new, most compact, surprisingly powerful bifunctional control catalyst. Simultaneously increased rates and stereoselectivities compared to control catalysts without p-acidic surface support that contributions of anion-p interactions to the catalytic cascade process are significant.

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“…The hydrogen [1,2], halogen [3][4][5][6][7][8][9][10], chalcogen [11][12][13][14][15][16][17][18][19][20][21][22][23][24], pnictogen [25][26][27][28][29][30][31], tetrel [32] bonding, stacking [33][34][35][36][37], cation/anion-π [38][39][40][41][42], and metallophilic interactions [43][44][45] play key roles in many chemical, physical, and biochemical processes, due to their ability to control structures and properties of associates and supramolecular systems.…”

Section: Introductionmentioning

confidence: 99%

Intra-/Intermolecular Bifurcated Chalcogen Bonding in Crystal Structure of Thiazole/Thiadiazole Derived Binuclear (Diaminocarbene)PdII Complexes

et al. 2018

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The coupling of cis-[PdCl2(CNXyl)2] (Xyl = 2,6-Me2C6H3) with 4-phenylthiazol-2-amine in molar ratio 2:3 at RT in CH2Cl2 leads to binuclear (diaminocarbene)PdII complex 3c. The complex was characterized by HRESI+-MS, 1H NMR spectroscopy, and its structure was elucidated by single-crystal XRD. Inspection of the XRD data for 3c and for three relevant earlier obtained thiazole/thiadiazole derived binuclear diaminocarbene complexes (3a EYOVIZ; 3b: EYOWAS; 3d: EYOVOF) suggests that the structures of all these species exhibit intra-/intermolecular bifurcated chalcogen bonding (BCB). The obtained data indicate the presence of intramolecular S•••Cl chalcogen bonds in all of the structures, whereas varying of substituent in the 4th and 5th positions of the thiazaheterocyclic fragment leads to changes of the intermolecular chalcogen bonding type, viz. S•••π in 3a,b, S•••S in 3c, and S•••O in 3d. At the same time, the change of heterocyclic system (from 1,3-thiazole to 1,3,4-thiadiazole) does not affect the pattern of non-covalent interactions. Presence of such intermolecular chalcogen bonding leads to the formation of one-dimensional (1D) polymeric chains (for 3a,b), dimeric associates (for 3c), or the fixation of an acetone molecule in the hollow between two diaminocarbene complexes (for 3d) in the solid state. The Hirshfeld surface analysis for the studied X-ray structures estimated the contributions of intermolecular chalcogen bonds in crystal packing of 3a–d: S•••π (3a: 2.4%; 3b: 2.4%), S•••S (3c: less 1%), S•••O (3d: less 1%). The additionally performed DFT calculations, followed by the topological analysis of the electron density distribution within the framework of Bader’s theory (AIM method), confirm the presence of intra-/intermolecular BCB S•••Cl/S•••S in dimer of 3c taken as a model system (solid state geometry). The AIM analysis demonstrates the presence of appropriate bond critical points for these interactions and defines their strength from 0.9 to 2.8 kcal/mol indicating their attractive nature.

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Anion−π Catalysis on Fullerenes

Cited by 74 publications

References 40 publications

Mechanosensitive Oligodithienothiophenes: Transmembrane Anion Transport Along Chalcogen‐Bonding Cascades

Mechanosensitive Oligodithienothiophenes: Transmembrane Anion Transport Along Chalcogen‐Bonding Cascades

Anion‐π Catalysis: Focus on Nonadjacent Stereocenters

Intra-/Intermolecular Bifurcated Chalcogen Bonding in Crystal Structure of Thiazole/Thiadiazole Derived Binuclear (Diaminocarbene)PdII Complexes

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