Effect of copper(I) on the conformation of the thiacalixarene platform in azide-alkyne cycloaddition

Thiacalix[4]arene’s Lower Rim Derivatives: Synthesis and Supramolecular Properties

“…[72][73][74] The aromatic rings form a cup-shaped structure with C 2v symmetry (so called, pinched cone PC conformer) where each free phenolic group interacts only with one of the adjacent oxygen atom of substituted aryl moieties (Figure 4c,d). There are many examples of similar structures in the Cambridge Structural Database: distally disubstituted p-tert-butylthiacalix [4]arenes containing substituents with different electronic and steric characteristics, such as methyl, [75] propyl, [71] butyl, [68] allyl, [76] phenacyl, [71] diethers CH 2 COEt with-and without tert-butyl grous on the upper rim, [77] cyanomethxy [78] as well as monocrown, [79] bisporphyrin, [80] biscalixarene [81] and disubsituted with different substituents macrocycle 86. [71] The differences in the spatial structure of disubstituted methylene and sulfur bridged macrocycle are also observed in the solution ( Figure 5).…”

“…So, the original approach was developed for the design of new type of amphiphilic compound based on bifunctional thiacalixarenes in 1,3-alternate stereoisomeric form. [68,70,87,88] Selective functionalization of the macrocycle lower rim creates two molecular domains with quite different properties located on opposite sides of the macrocycles central plane. One of them has lipophilic properties due to the introduction of long chain alkyl substituents.…”

“…[93] Second, such thin thiacalix [4]arene films are stable in aqueous solution in the presence of biological active compounds such as dihydroquercetin up to pH 5.0, but cytochrome c is extracted by ascorbic acid from TCA films very intensively. 100: R'=(CH 2 ) 3 Br, Alk=C 14 H 29 ; [87] 101: R'=(CH 2 ) 2 Br, Alk=C 14 H 29 ; [87] 102: R'=(CH 2 ) 3 N 3 , Alk=C 14 H 29 ; [87] 103: R'=(CH 2 ) 2 N 3 , Alk=C 14 H 29 ; [87] 104: R'=(CH 2 ) 3 N 3 , Alk=C 4 H 9 , C 8 H 17 , C 14 H 29 ; [88] 105: R'=(CH 2 ) 3 N 3 , Diynyl=CH 2 C≡C-C≡C-C 6 H 5 ; [70] B: 106: n=3; Y=COOH, Z=COOH, Alk=C 4 H 9 ,C 8 H 17 , C 14 H 29 ; [87] 107: n=3; Y=CH 2 NH 2 , Z=H, Alk=C 14 H 29 ; [87] 108: n=3; Y=CH 2 OH, Z=H, Alk=C 14 H 29 ; [87] 109: n=3; Y=CH 2 N + (Et) 3 Br -, Z=H, Alk=C 4 H 9 , C 8 H 17 , C 14 H 29 ; [88] 110: n=3; Y=CH 2 С 6 H 5 , Z=H, Diynyl=CH 2 C≡C-C≡C-C 6 H 5 ; [70] 111: n=3; Y=CH 2 NH 2 , Z=H, Diynyl=CH 2 C≡C-C≡C-C 6 H 5 ; [70] 112: n=3; Y=COOH, Z=COOH, Diynyl=CH 2 C≡C-C≡C-C 6 H 5 ; [70] 113: n=3; Y=phtalimide, Z=H, Diynyl=CH 2 C≡C-C≡C-C 6 H 5 ; [70] [92] 99: Alkynyl=-CH 2 C≡CH, Alk=C 4 H 9 , C 8 H 17 , C 14 H 29 ; [68] A: 117: n=1; X=Bn, Alk=C 4 H 9 , C 8 H 17 , C 14 H 29 ; [68] 118: n=1; X=p-NO 2 C 6 H 4 , Alk=C 4 H 9 , C 8 H 17 , C 14 H 29 ; [68] 119: n=1; X=Bn, Alk=C 4 H 9 , C 8 H 17 , C 14 H 29 ; [68] 120: n=1; X=2,4,6-trichlorophenyl, Alk=C 4 H 9 ; [68] 121: n=1; X=p-MeOC 6 H 4 , Alk=C 4 H 9 ; [68] 122: n=1; X=CH 2 C(O)O-t-Bu, Alk=C 4 H 9 ; [68] Scheme 10. New type of ligands on the basis of thiacalix [4]arene platform in 1,3-alternate conformation was designed for gold surface functionalization.…”

“…[60] Scheme 3. 72: R=CH 3 ; [62] 73: R=CH 2 COOEt; [63] 74: R=CH 2 COOH; [63] 75: R=CH 2 C 6 H 5 ; [64] 76: R=CH 2 CN; [65] 77: R=CH 2 CONHC 6 H 4 NO 2 ; [66] 78: R=(CH 2 ) n Y; [67] 79: R=(CH 2 ) n СH 3 (n=3, 7, 13); [68] 80: R=(CH 2 ) 2 SMe; [69] 81: R=(CH 2 ) 2 SBz; [69] 82: R=(CH 2 ) 3 Set; [69] 83: R=diynyl=CH 2 C≡C-C≡C-C 6 H 5 ; [70] 84: R=CH 2 COC 6 H 5 ; [71] 85: R=C 3 H 7 .…”

Azide–Akyne Click Approach to the Preparation of Dendrimer–Type Multi(thia)calix[4]arenes with Triazole Linkers

“…Thermal isomerization is also possible in the case of tetrapropoxythiacalix [4]arene. [18] However, Burilov et al [19] showed that the partial cone-to-1,3alternate transition occurs upon azide-alkyne coupling with copper catalyst and exclusively 1,3-alternate atropoisomer of triazole product is formed.…”