Synthesis of rotacatenanes by the combination of Cu-mediated threading reaction and the template method: the dual role of one ligand

Abstract

Rotacatenanes were synthesized by the catalytic reaction using a macrocyclic phenanthroline-CuI complex followed by the installation of another ring by the template method. In this approach, the size of the ring component of the rotaxane turns out to be a very important factor for the synthesis of rotacatenanes.

Synthesis of [3]Rotaxanes by the Combination of Copper-Mediated Coupling Reaction and Metal-Template Approach

“…[2]Rotaxane (6). 7m A mixture of macrocyclic phenanthroline 1a (9.0 mg, 0.013 mmol) and [Cu(CH 3 CN) 4 ]PF 6 (2) (4.8 mg, 0.013 mmol) in dry CH 2 Cl 2 (1.0 mL) was stirred at room temperature for 20 min (mixture A).…”

“…On the other hand, the attempted synthesis of the rotacatenane from 7d and 16 failed: the low stability of the corresponding tetrahedral Cu I complex was assumed to be the reason for the unsuccessful result. 6 As we expected, the [3]rotaxane was synthesized by the reaction of 7b, 16, and 12 in 56% yield. Unexpectedly, the reaction of 7d, 16, and 12 also proceeded, and the corresponding [3]rotaxane was synthesized in lower yield (23%).…”

Construction of a hetero pseudo[2]rota[2]catenane

“…17 Accordingly, the design and construction of mechanically 18 interlocked molecules with multiple topology units has become 19 one of the most important projects. For example, rotaxane may 20 fuse catenane to compose the corresponding rotacatenane 21 integration [21][22][23][24]. In recent years, rotacatenanes have also 22 attracted increasing interests owing to the fact that it can lead to 23 different chemical structures with interesting functionalities 24 [21][22][23][24].…”

“…For example, rotaxane may 20 fuse catenane to compose the corresponding rotacatenane 21 integration [21][22][23][24]. In recent years, rotacatenanes have also 22 attracted increasing interests owing to the fact that it can lead to 23 different chemical structures with interesting functionalities 24 [21][22][23][24]. Motivated by the advancements of our previous works 25 [25][26][27][28][29][30][31][32][33][34][35], we recently reported a type of novel rotacatenane 26 topological structures, as shown in Scheme 1(A) [36].…”

Construction of rotacatenanes using rotaxane and catenane frameworks

“…9 Saito's group also recently reported a series of [2]rota[2]catenanes which were synthesized by a catalytic reaction using a macrocyclic phenanthroline-CuI complex followed by the installation of another ring under the template effect. 10 In view of the structural character described above and based on the novel building blocks of heterorotaxane integration, herein we have designed a series of novel ammonium blocks (B) which incorporate an ammonium on the linear component of the backbone and another ammonium on the macrocyclic component of the backbone (in Scheme 1). The ammonium on the linear component of the backbone was designed to have the ability to construct the rotaxane while another ammonium on the macrocyclic component of the backbone played a role in the construction of the catenane.…”