Synthesis of [2]Catenanes by Oxidative Intramolecular Diyne Coupling Mediated by Macrocyclic Copper(I) Complexes

Sato, Yuta; Yamasaki, Ryu; Saito, Shinichi

doi:10.1002/anie.200804864

Cited by 92 publications

(36 citation statements)

References 31 publications

Supporting

Mentioning

Contrasting

Unclassified

Order By: Relevance

“…This has been demonstrated initially for the synthesis of rotaxanes obtained by assembling the dumbbell component from its stoppered precursors directly inside the ring component (Figure 6(a)), using the Cu(I)-catalyzed azide-alkyne 1,3-cycloaddition [28][29][30]. Since then many other metalpromoted C-X or C-C bond forming reactions have been used efficiently, including the Pd-catalyzed Heck [31] and Sonogashira [32], the Cu-catalyzed Glaser-Hay [33,34] and Cadiot-Chodkiewicz [29,35] coupling reactions. Remarkably, the search for novel active metal templates led to the discovery of new catalytic reactions, such as the Ni-promoted sp 3 -sp 3 homocoupling of unactivated alkylbromides [36].…”

mentioning

confidence: 99%

Transition metal-templated synthesis of catenanes and rotaxanes

Chambron

Sauvage

2011

Sci. China Chem.

View full text Add to dashboard Cite

Catenanes are molecules made of two or more interlocked rings, and rotaxanes are composed of rings threaded onto axles that look like dumbbells because they are terminated by stoppers large enough to prevent unthreading ( Figure 1) [1]. [n]Catenanes are constituted by n interlocked rings, whereas [n]rotaxanes are made of n-m rings and m dumbbell components. Both constitute the prototypical molecular objects featuring the so-called "mechanical bond". Whereas the first syntheses of catenanes and rotaxanes date back to the late sixties [2], the real burst of these exotic-at-that-time classes of compounds really started a decade later, after the very first template methods (metal coordination [3], and - donor-acceptor interactions [4]) were discovered and developed [5,6]. Since then catenanes and rotaxanes, from the status of molecular curiosities (in terms of topology and synthetic access), attained the rank of useful synthetic molecules that could be endowed with functions. Indeed, the last two decades have seen the development of molecular machines that rely heavily on catenanes and rotaxanes, taking advantage of the mechanical bonds for the generation and observation of net molecular motions [7,8]. This contribution will account for the metal template technology, as among all the methods developed for making interlocked molecules, it is certainly the one that proved itself to be the most versatile and productive. Figure 1 The simplest [2]catenane and [2]rotaxane, made of two interlocked components.The exceptional power of metal templates, and especially transition metal templates, stems from their richness and variety in terms of coordination geometries, oxidation states, bond strength and lability, and reactivity. Metal templates were early recognized as being either kinetic and/or thermodynamic, depending on the property used [9]. A kinetic template preorganizes the reactants in order to drive the formation of a geometrically-or topologically-selective reaction, that is for instance a macrocycle vs. a polymer, or a catenane vs a macrocycle. A thermodynamic template works essentially the same, except that the intermediates are in equilibrium, which allows for the selection of the most stable one and the product thereof. The earliest metal templates that were used for making catenanes and rotaxanes were based on the Cu(dpp) 2 + complex fragment in which the Cu(I) cation in tetrahedral geometry intertwines two dpp (2,9-diphenyl-1,10-phenanthroline) chelates orthogonally to each other and this was followed by many other Cu(I) bis-diimine complex systems [10]. Other coordination geometries were demonstrated to work equally well (Figure 2), providing that the adequate metal/ligand combination is chosen, for example linear (two-coordinate) Au(I)/pyridyl (py) [11] and octahedral (six-coordinate) Ru(II)/2,2′;6′, 2″-terpyridyl (terpy) [12]. The use of less straightforward four-coordinate square planar (sp) Pd(II), and five-coordinate square-based pyramidal (sqp) and trigonal bipyramidal (tbp) Zn(II) and Cu(II) involved...

show abstract

mentioning

confidence: 99%

Transition metal-templated synthesis of catenanes and rotaxanes

Chambron

Sauvage

2011

Sci. China Chem.

View full text Add to dashboard Cite

show abstract

“…The residue was dissolved in CH 2 Cl 2 and water. The aqueous layer was extracted with CH 2 Cl 2 , and combined organic extracts were washed with water, dried over Na 2 SO 4 1, 143.8, 131.9, 124.5, 119.3, 117.2, 115.9, 113.4, 101.0, 96.8, 69.8, 47.3, 39.4, 39.3, 39.02, 39.00, 38.9, 38.74, 38.73, 36.3;IR (ATR): 2920, 2850, 1594, 1583, 1487, 1468, 1419, 1281, 1254, 1177, 1158, 1140, 1110, 1083, 1054, 1019, 1000 Macrocyclic PhenanthrolineCopper(I) Complex (9). To a solution of 8 (85 mg, 0.15 mmol) in CH 2 Cl 2 (7 mL) was added the solution of CuI (29 mg, 0.15 mmol) in CH 3 CN (3 mL) with stirring at rt.…”

Section: Generalmentioning

confidence: 99%

“…This approach was initially reported independently by Leigh's group 7 and our group. 8 In our approach, macrocyclic 2,9-diaryl-1,10-phenanthrolineCu complexes were used as the substrates for the synthesis of [2]rotaxanes, 8 [2]catenanes, 9 and more complex interlocked compounds. 10,11 Some coupling reactions such as Glaser coupling 8a,8b,911 and Sonogashira-type reaction 8c could be mediated by the macrocyclic 2,9-diaryl-1,10-phenanthrolineCu complexes such as 1 (Scheme 2).…”

mentioning

confidence: 99%

See 1 more Smart Citation

A Macrocyclic Phenanthroline–Copper Complex with Less Steric Hindrance: Synthesis, Structure, and Application to the Synthesis of a [2]Rotaxane

Saito

Ohkubo

Yamazaki

et al. 2015

Bulletin of the Chemical Society of Japan

Self Cite

View full text Add to dashboard Cite

We synthesized a macrocyclic 2,9-dialkyl-1,10-phenanthrolineCu complex (9) from 1,10-phenanthroline. Compound 9 existed as a dinuclear complex in solid state. In solution, however, the compound existed as a mononuclear complex. Compound 9 mediated the Glaser reaction of an alkyne with a bulky blocking group and the formation of a [2]rotaxane was observed. The reactivity of the 2,9-dialkyl-1,10-phenanthrolineCu complex (9) was lower than that of a diaryl analogue.2,9-Diaryl-1,10-phenanthroline derivatives have been known as useful bidentate ligands, 1 and they have been employed as building blocks for the metal-templated synthesis of interlocked compounds.2 These compounds form stable tetrahedral complexes with Cu I ion, and the introduction of this structural motif by Sauvage and Dietrich-Buchecker provided a new and efficient method for the synthesis of catenanes, 3 rotaxanes, 4 and related interlocked compounds. 5 In contrast, 2,9-dialkyl-1,10-phenanthroline derivatives, which are less sterically hindered compared to the corresponding arylated phenanthrolines, have been much less employed as substrates. 6 We have been interested in the synthesis of interlocked compounds by utilizing the catalytic activity of the macrocyclic metal complex. The macrocyclic metal complex could promote the bond-forming reaction inside the ring, and a rotaxane could be synthesized efficiently if the substrate was properly designed and the dissociation of the axle component was inhibited by the presence of large blocking groups (Scheme 1). This approach was initially reported independently by Leigh's group 7 and our group. 8 In our approach, macrocyclic 2,9-diaryl-1,10-phenanthrolineCu complexes were used as the substrates for the synthesis of [2]rotaxanes, 8 [2]catenanes, 9 and more complex interlocked compounds.10,11 Some coupling reactions such as Glaser coupling 8a,8b,911 and Sonogashira-type reaction 8c could be mediated by the macrocyclic 2,9-diaryl-1,10-phenanthrolineCu complexes such as 1 (Scheme 2).We suspect that the presence of the bulky aryl groups in close proximity to the Cu atom could reduce the catalytic activity of the macrocyclic 2,9-diaryl-1,10-phenanthrolineCu complex. Accordingly, a macrocyclic 2,9-dialkyl-1,10-phenanthrolineCu complex could be a better substrate for the synthesis of [2]rotaxanes. 12 In this paper we report the synthesis and structure of a macrocyclic 2,9-dialkyl-1,10-phenanthrolineCu complex. The application of this complex to the synthesis of [2]rotaxanes was also studied. Results and DiscussionSynthesis and Structure of a Macrocyclic 2,9-Dialkyl-1,10-phenanthrolineCu Complex.On the basis of our previous studies of arylated phenanthrolines, we designed a new macrocyclic 2,9-dialkyl-1,10-phenanthroline 8 (Scheme 3). The size of the macrocycle was adjusted so that the threading reaction (the coupling reaction inside the ring) would proceed and the [2]rotaxane would not dissociate under experimental conditions. The synthesis of 8 is summarized in Scheme 3.The MOM-protected bromodecanol 4 13...

show abstract

“…The KCN workup was designed to detach the copper from the phenanthroline moiety of the rotaxane, but does not always appear to be necessary (vide infra). Leigh has termed such protocols “active metal template” syntheses, and many variants have been developed, including extensions to catenane syntheses …”

Section: Introductionmentioning

confidence: 99%

Syntheses, Structures, and Spectroscopic Properties of 1,10‐Phenanthroline‐Based Macrocycles Threaded by PtC₈Pt, PtC₁₂Pt, and PtC₁₆Pt Axles: Metal‐Capped Rotaxanes as Insulated Molecular Wires

Amini

Baranová

Weisbach

et al. 2019

Chemistry A European J

View full text Add to dashboard Cite

The platinum polyynyl complexes trans‐(C6F5)(p‐tol3P)2Pt(C≡C)n/2H undergo oxidative homocoupling (O2, CuCl/TMEDA) to diplatinum polyynediyl complexes trans, trans‐(C6F5)(p‐tol3P)2Pt(C≡C)nPt(Pp‐tol3)2(C6F5) (n=4, 2; 6, 5; 8, 8; 92–97 %) as reported previously. When related reactions are conducted in the presence of CuI adducts of the 1,10‐phenanthroline‐based macrocycles 2,9‐(1,10‐phenanthrolinediyl)(p‐C6H4O(CH2)6O)2(1,3‐C6H4) (10, 33‐membered) or 2,9‐(1,10‐phenanthrolinediyl)(p‐C6H4O(CH2)6O)2(2,7‐naphthalenediyl) (11, 35‐membered), excess K2CO3, and I2 (oxidant), rotaxanes are isolated that feature a Pt(C≡C)nPt axle that has been threaded through the macrocycle (2⋅10, 9 %; 5⋅10, 41 %; 5⋅11, 28 %; 8⋅10, 12 %; 8⋅11, 9 %). Their crystal structures are determined and analyzed in detail, particularly with respect to geometric perturbations and the degree of steric sp carbon chain insulation. NMR spectra show a number of shielding effects. UV/Vis spectra do not indicate significant electronic interactions between the Pt(C≡C)nPt axles and macrocycles, although cyclic voltammetry data suggest rapid reactions following oxidation.

show abstract

Synthesis of [2]Catenanes by Oxidative Intramolecular Diyne Coupling Mediated by Macrocyclic Copper(I) Complexes

Cited by 92 publications

References 31 publications

Transition metal-templated synthesis of catenanes and rotaxanes

Transition metal-templated synthesis of catenanes and rotaxanes

A Macrocyclic Phenanthroline–Copper Complex with Less Steric Hindrance: Synthesis, Structure, and Application to the Synthesis of a [2]Rotaxane

Syntheses, Structures, and Spectroscopic Properties of 1,10‐Phenanthroline‐Based Macrocycles Threaded by PtC₈Pt, PtC₁₂Pt, and PtC₁₆Pt Axles: Metal‐Capped Rotaxanes as Insulated Molecular Wires

Contact Info

Product

Resources

About

Synthesis of [2]Catenanes by Oxidative Intramolecular Diyne Coupling Mediated by Macrocyclic Copper(I) Complexes

Cited by 92 publications

References 31 publications

Transition metal-templated synthesis of catenanes and rotaxanes

Transition metal-templated synthesis of catenanes and rotaxanes

A Macrocyclic Phenanthroline–Copper Complex with Less Steric Hindrance: Synthesis, Structure, and Application to the Synthesis of a [2]Rotaxane

Syntheses, Structures, and Spectroscopic Properties of 1,10‐Phenanthroline‐Based Macrocycles Threaded by PtC8Pt, PtC12Pt, and PtC16Pt Axles: Metal‐Capped Rotaxanes as Insulated Molecular Wires

Contact Info

Product

Resources

About

Syntheses, Structures, and Spectroscopic Properties of 1,10‐Phenanthroline‐Based Macrocycles Threaded by PtC₈Pt, PtC₁₂Pt, and PtC₁₆Pt Axles: Metal‐Capped Rotaxanes as Insulated Molecular Wires