Pillar[5]arene as a co-factor in templating rotaxane formation.
After the manner in which coenzymes often participate in the binding of substrates in the active sites of enzymes, pillar[5]arene, a macrocycle containing five hydroquinone rings linked through their para positions by methylene bridges, modifies the binding properties of cucurbit[6]uril, such that the latter templates azide-alkyne cycloadditions that do not occur in the presence of only the cucurbit[6]uril, a macrocycle composed of six glycoluril residues doubly linked through their nitrogen atoms to each other by methylene groups. Here, we describe how a combination of pillar[5]arene and cucurbit[6]uril interacts cooperatively with bipyridinium dications substituted on their nitrogen atoms with 2-azidoethyl- to 5-azidopentyl moieties to afford, as a result of orthogonal templation, two [4]rotaxanes and one [5]rotaxane in >90% yields inside 2 h at 55 °C in acetonitrile. Since the hydroxyl groups on pillar[5]arene and the carbonyl groups on cucurbit[6]uril form hydrogen bonds readily, these two macrocycles work together in a cooperative fashion to the extent that the four conformational isomers of pillar[5]arene can be trapped on the dumbbell components of the [4]rotaxanes. In the case of the [5]rotaxane, it is possible to isolate a compound containing two pillar[5]arene rings with local C5 symmetries. In addition to fixing the stereochemistries of the pillar[5]arene rings, the regiochemistries associated with the 1,3-dipolar cycloadditions have been extended in their constitutional scope. Under mild conditions, orthogonal recognition motifs have been shown to lead to templation with positive cooperativity that is fast and all but quantitative, as well as being green and efficient.
Department of Chemistry, Northwestern University , 2145 Sheridan Road, Evanston, Illinois 60208, United States.
Chenfeng
C
Ke
Nathan L
NL
Strutt
Hao
H
Li
Xisen
X
Hou
Karel J
KJ
Hartlieb
Paul R
PR
McGonigal
Zhidong
Z
Ma
Julien
J
Iehl
Charlotte L
CL
Stern
Chuyang
C
Cheng
Zhixue
Z
Zhu
Nicolaas A
NA
Vermeulen
Thomas J
TJ
Meade
Youssry Y
YY
Botros
J Fraser
JF
Stoddart
D001952:Bridged-Ring Compounds / Q000138:chemical synthesis / Q000737:chemistry*; D047250:Calixarenes; D006860:Hydrogen Bonding; D007093:Imidazoles / Q000138:chemical synthesis / Q000737:chemistry*; D009682:Magnetic Resonance Spectroscopy; D008958:Models, Molecular; D000644:Quaternary Ammonium Compounds / Q000138:chemical synthesis / Q000737:chemistry*; D043862:Rotaxanes / Q000138:chemical synthesis* / Q000737:chemistry; D047028:Macrocyclic Compounds; D000099246:Cucurbit(n)urils
D001952:Bridged-Ring Compounds; D047250:Calixarenes; D007093:Imidazoles; D000644:Quaternary Ammonium Compounds; D043862:Rotaxanes; C570642:pillar(5)arene; C454805:cucurbit(6)uril; D047028:Macrocyclic Compounds; D000099246:Cucurbit(n)urils