Supramolecular approaches to mediate chemical reactivity
The aim of this thematic issue is to outline the most innovative researches regarding supramolecular catalysis using macrocyclic and acyclic hosts, as well as intriguing architectures such as self-assembled capsules, metallocages, and MOFs. A particular attention will be devoted to the most innovative trends in supramolecular catalysis, concerning the biomimetic catalysis in confined space and the design of efficient supramolecular systems able to perform stereoselective catalysis.
- Letter
- Published 10 Feb 2022
-
PDF -
Album-
![]()
Graphical Abstract
-
![]()
Figure 1: Selected examples of: a) calix[4]arene-; b) resorcin[4]arene-; c) calix[6]arene-gold(I) macrocyclic...
-
![]()
Scheme 1: i) NH2NH2∙H2O, Pd/C in EtOH, 80 °C (quant.); ii) diphenylphosphinobenzoic acid, EDC∙HCl, DMAP (cat....
-
![]()
Figure 2: Stacked-plot, mid-field expanded region of the 1H NMR spectrum (400 MHz, 298 K) of A(AuCl)2, B(AuCl)...
-
![]()
Figure 3: Stacked plot 1H NMR (tetrachloroethane-d2) of A(AuCl)2 at variable temperature.
-
![]()
Scheme 2: Synthesis of the monomeric gold catalyst analogues A’,B’,C’(AuCl). Conditions: i) diphenylphosphino...
-
-
Supp. Info
- Review
- Published 14 Mar 2022
-
PDF -
Album-
![]()
Graphical Abstract
-
![]()
Figure 1: Site-selective Diels–Alder reaction of anthracene and phthalimide mediated by aqueous organopalladi...
-
![]()
Figure 2: Site-selective Diels–Alder and [2 + 2]-photoaddition reactions between naphthalene and phthalimide ...
-
![]()
Figure 3: Cage host A-mediated selective 1,4-radical addition of o-quinone 10.
-
![]()
Figure 4: Cyclodextrin-mediated site-selective reductions.
-
![]()
Figure 5: Selective reduction of an α,ω-diazide compound mediated by water-soluble cavitand D.
-
![]()
Figure 6: Selective radical reduction of α,ω-dihalides mediated by water-soluble cavitands E and F.
-
![]()
Figure 7: Site-selective hydrogenation of polyenols mediated by supramolecular encapsulated rhodium catalyst.
-
![]()
Figure 8: Site-selective oxidation of steroids using cyclodextrin as the anchoring template.
-
![]()
Figure 9: Site-selective oxidations of linear diterpenoids with the help of cage host A.
-
![]()
Figure 10: Site-selective monoepoxidation of α,ω-dienes mediated by the water-soluble cavitand host E.
-
![]()
Figure 11: Site-selective ring-opening reaction of epoxides mediated by cavitand I with an inwardly directed c...
-
![]()
Figure 12: Site-selective nucleophilic substitution reaction of allylic chlorides mediated by cage host J.
-
![]()
Figure 13: Site-selective monohydrolysis of α,ω-difunctional compounds using deep water-soluble cavitands.
-
- Letter
- Published 18 Mar 2022
-
PDF -
Album-
![]()
Graphical Abstract
-
![]()
Scheme 1: Proposal of a Se···O bonding catalysis approach.
-
![]()
Scheme 2: Se···O bonding catalysis approach to the synthesis of calix[4]pyrrole 2a.
-
![]()
Scheme 3: Reaction scope.
-
![]()
Scheme 4: Proposed activation mode.
-
-
Supp. Info
- Letter
- Published 28 Mar 2022
-
PDF -
Album-
![]()
Graphical Abstract
-
![]()
Scheme 1: Resorcin[4]arene 1 forming the corresponding hexameric capsule 16 and the species used for control ...
-
![]()
Scheme 2: Carbonyl–ene intramolecular cyclization of (S)-citronellal to the corresponding diastereoisomeric c...
-
![]()
Figure 1: 1H NMR spectra in water-saturated CDCl3 except for G. A: [16] (7.5 mM); B: citronellal; C: citronel...
-
![]()
Scheme 3: Dehydration reaction of 1,1-diphenylethanol to 1,1-diphenylethylene.
-
![]()
Figure 2: 1H NMR spectra in water-saturated CDCl3 except for G. A: [16] (7.5 mM); B: 1,1-diphenylethanol; C: ...
-
![]()
Scheme 4: Possible isomerization products from β-pinene and α-pinene.
-
![]()
Figure 3: 1H NMR spectra in water-saturated CDCl3 except for G. A: [16] (7.5 mM); B: α-pinene; C: α-pinene (7...
-
![]()
Figure 4: 1H NMR spectra in water-saturated CDCl3 except for G. A: [16] (7.5 mM); B: β-pinene; C: β-pinene (7...
-
![]()
Figure 5: 1H NMR spectra in water-saturated CDCl3, except for E. A: [16] (7.5 mM); B: β-pinene; C: β-pinene (...
-
-
Supp. Info
- Full Research Paper
- Published 13 Apr 2022
-
PDF -
Album-
![]()
Graphical Abstract
-
![]()
Scheme 1: Graphical representation of the fabrication of supramolecular m-TPEWP5
![[Graphic 5]](/bjoc/content/inline/1860-5397-18-45-i7.svg?max-width=637&scale=1.18182)
G-EsY self-assembled photocat...
-
![]()
Figure 1: 1H NMR (400 MHz, D2O, 298 K) spectra of m-TPEWP5 (1.0 mM), m-TPEWP5 (1.0 mM) + G (1.0 mM), and G (1...
-
![]()
Figure 2: (a) Fluorescence spectra of m-TPEWP5 (1 × 10−5 M) with different concentrations of G (0 to 1.2 equi...
-
![]()
Figure 3: TEM images of (a) m-TPEWP5
![[Graphic 15]](/bjoc/content/inline/1860-5397-18-45-i17.svg?max-width=637&scale=1.18182)
G; (b) m-TPEWP5![[Graphic 16]](/bjoc/content/inline/1860-5397-18-45-i18.svg?max-width=637&scale=1.18182)
G-EsY. [m-TPEWP5] = 1 × 10−4 M, [G] = 1 × 10−4 M, [EsY] = ...
-
![]()
Figure 4: (a) Normalized absorption and emission spectra of the EsY acceptor and the m-TPEWP5
![[Graphic 25]](/bjoc/content/inline/1860-5397-18-45-i27.svg?max-width=637&scale=1.18182)
G donor assembly...
-
![]()
Scheme 2: Products from 2-bromo-1-phenylethanone dehalogenation reactions in the presence of m-TPEWP5
![[Graphic 43]](/bjoc/content/inline/1860-5397-18-45-i45.svg?max-width=637&scale=1.18182)
G-EsY na...
-
![]()
Figure 5: Proposed mechanism for the 2-bromo-1-phenylethanone dehalogenation reaction mediated by m-TPEWP5
![[Graphic 48]](/bjoc/content/inline/1860-5397-18-45-i50.svg?max-width=637&scale=1.18182)
G-E...
-
-
Supp. Info
- Full Research Paper
- Published 02 May 2022
-
PDF -
Album-
![]()
Graphical Abstract
-
![]()
Figure 1: Design of PKS-inspired multifunctional amino-thiourea macrocycle catalysts.
-
![]()
Scheme 1: Synthesis of tetraamino-bisthiourea chiral macrocycles M1–M12. The synthesis of M1, M5, M7, and M8 ...
-
![]()
Scheme 2: Substrate scope of isatin imines. Reaction conditions: 6 (0.2 mmol), 7a (0.3 mmol), and 5 mol % M3 ...
-
![]()
Scheme 3: Substrate scope of MAHTs. Reaction conditions: 6a (0.2 mmol), 7 (0.3 mmol), and 5 mol % M3 in 2 mL ...
-
![]()
Figure 2: Proposed catalytic mechanism.
-
-
Supp. Info
- Review
- Published 06 May 2022
-
PDF -
Album-
![]()
Graphical Abstract
-
![]()
Figure 1: Molecular structures of (R)-BINOL (left) and (S)-BINOL (right).
-
![]()
Figure 2: Synthesis of Sauvage´s [2]catenanes (S,S)-5 and (S,S)-6 containing two BINOL units by the passive m...
-
![]()
Figure 3: Synthesis of Saito´s [2]rotaxane (R)-10 from a BINOL-based macrocycle by the active metal template ...
-
![]()
Figure 4: Synthesis of Stoddart´s [2]rotaxane (rac)-14 by an ammonium crown ether template.
-
![]()
Figure 5: Synthesis of Stoddart´s BINOL-containing [2]catenanes 18/20/22/24 by π–π recognition.
-
![]()
Figure 6: Synthesis of Takata´s rotaxanes featuring chiral centers on the axle: a) rotaxane (R,R,R/S)-27 obta...
-
![]()
Figure 7: Takata´s chiral polyacetylenes 32/33 featuring BINOL-based [2]rotaxane side chains.
-
![]()
Figure 8: Synthesis of Takata´s chiral thiazolium [2]rotaxanes (R)-35a/b and (R)-38.
-
![]()
Figure 9: Results for the asymmetric benzoin condensation of benzaldehyde (39) with catalysts (R)-35a/b and (R...
-
![]()
Figure 10: Synthesis of Takata´s pyridine-based [2]rotaxane (R)-42.
-
![]()
Figure 11: The asymmetric desymmetrization reaction of meso-1,2-diols with rotaxane (R)-42.
-
![]()
Figure 12: Synthesis of Niemeyer´s axially chiral [2]catenane (S,S)-47.
-
![]()
Figure 13: Results for the enantioselective transfer hydrogenation of 2-phenylquinoline with catalysts (S,S)-47...
-
![]()
Figure 14: Synthesis of Niemeyer´s chiral [2]rotaxanes (S)-56/57.
-
![]()
Figure 15: Results for the enantioselective Michael addition with different rotaxane catalysts (S)-56a/56b/57a/...
-
![]()
Figure 16: Synthesis of Beer´s [2]rotaxanes 64a/b for anion recognition.
-
![]()
Figure 17: Association constants of different anions (used as the Bu4N+ salts) to the [2]rotaxanes (S)-64a/b a...
-
![]()
Figure 18: Synthesis of Beer´s [3]rotaxane (S)-68.
-
![]()
Figure 19: Association constants of different anions (used as the Bu4N+-salts) to the [2]rotaxane (S)-68 and a...
-
- Review
- Published 27 May 2022
-
PDF -
Album-
![]()
Graphical Abstract
-
![]()
Figure 1: Butterfly 1 (Figure was reprinted with permission from [45]. Copyright 2012 American Chemical Society. ...
-
![]()
Figure 2: Synthesis of the three-component heteroleptic molecular boat 8 and its use as a catalyst for the Kn...
-
![]()
Figure 3: Synthesis of the two-component triangle 14 and three-component heteroleptic prism 15 [59]. Figure was a...
-
![]()
Figure 4: Catalytic Michael addition reaction using the urea-decorated molecular prism 15 [59].
-
![]()
Figure 5: Self-assembly of two-component tetragonal prismatic architectures with different cavity size. Figur...
-
![]()
Figure 6: Construction of artificial LHS using rhodamine B as an acceptor and 24b as donor generating a photo...
-
![]()
Figure 7: Synthesis of supramolecular spheres with varying [AuCl] concentration inside the cavity. Figure was...
-
![]()
Figure 8: Hydroalkoxylation reaction of γ-allenol 34 in the presence of [AuCl]-encapsulated molecular spheres ...
-
![]()
Figure 9: Two-component heteroleptic triangles of different size containing a BINOL functionality. Figure was...
-
![]()
Figure 10: Asymmetric conjugate addition of chalcone 42 with trans-styrylboronic acid (43) catalyzed by BINOL-...
-
![]()
Figure 11: Encapsulation of monophosphoramidite-Rh(I) catalyst into a heteroleptic tetragonal prismatic cage 47...
-
![]()
Figure 12: (a) Representations of the basic HETPYP, HETPHEN, and HETTAP complex motifs. (b) The three-componen...
-
![]()
Figure 13: Two representative four-component rotors, with a (top) two-arm stator and (bottom) a four-arm stato...
-
![]()
Figure 14: Four-component rotors with a monohead rotator. Figure was adapted with permission from [94]. Copyright ...
-
![]()
Figure 15: (left) Click reaction catalyzed by rotors [Cu2(55)(60)(X)]2+. (right) Yield as a function of the ro...
-
![]()
Figure 16: A supramolecular AND gate. a) In truth table state (0,0) two nanoswitches serve as the receptor ens...
-
![]()
Figure 17: Two supramolecular double rotors (each has two rotational axes) and reference complex [Cu(78)]+ for...
-
![]()
Figure 18: The slider-on-deck system (82•X) (X = 83, 84, or 85). Figure is from [98] and was reprinted from the jo...
-
![]()
Figure 19: Catalysis of a conjugated addition reaction in the presence of the slider-on-deck system (82•X) (X ...
-
![]()
Figure 20: A rotating catalyst builds a catalytic machinery. For catalysis of the catalytic machinery, see Figure 21. F...
-
![]()
Figure 21: Catalytic machinery. Figure was adapted from [100] (“Evolution of catalytic machinery: three-component n...
-
![]()
Figure 22: An information system based on (re)shuffling components between supramolecular structures [99]. Figure ...
-
![]()
Figure 23: Switching between dimeric heteroleptic and homoleptic complex for OFF/ON catalytic formation of rot...
-
![]()
Figure 24: A chemically fueled catalytic system [112]. Figure was adapted from [112]. Copyright 2021 American Chemical S...
-
![]()
Figure 25: (Top) Operation of a fuel acid. (Bottom) Knoevenagel addition [112].
-
![]()
Figure 26: Development of the yield of Knoevenagel product 118 in a fueled system [112]. Figure was reprinted with ...
-
![]()
Figure 27: Weak-link strategy to increased catalytic activity in epoxide opening [119]. Figure was adapted from [24]. C...
-
![]()
Figure 28: A ON/OFF polymerization switch based on the weak-link approach [118]. Figure was reprinted with permissi...
-
![]()
Figure 29: A weak-link switch turning ON/OFF a Diels–Alder reaction [132]. Figure was reprinted with permission fro...
-
![]()
Figure 30: A catalyst duo allowing selective activation of one of two catalytic acylation reactions [133] upon subs...
-
![]()
Figure 31: A four-state switchable nanoswitch (redrawn from [134]).
-
![]()
Figure 32: Sequential catalysis as regulated by nanoswitch 138 and catalyst 139 in the presence of metal ions ...
-
![]()
Figure 33: Remote control of ON/OFF catalysis administrated by two nanoswitches through ion signaling (redrawn...
-
