Hydrogen bonding-directed multicomponent dynamic covalent assembly of mono- and bimacrocycles. Self-sorting and macrocycle exchange.
This paper describes the multicomponent dynamic covalent assembly of macrocyclic structures by utilizing hydrogen bonding-driven zigzag anthranilamides as "leading" components. Two or three amino groups have been introduced to one side of hydrogen bonded anthranilamide oligomers. The preorganization of the frameworks enabled the amino groups to condense with structurally matched aldehydes to form mono- and bimacrocycles in good to quantitative yields. Reactions from up to five components have been investigated, which involved one-step formation of up to six imine bonds. The preorganization of the templates highly enhanced the stability of the macrocyclic structures. As a result, all the macrocycles could be purified by simply recrystallizing the crude products from suitable solvents. Coexisting experiments of three series of three to five components were also performed, which all revealed that the preorganized precursors possessed high self-sorting capacity. On the basis of the same approach, a hydrazone-based macrocycle was also prepared quantitatively, while an intermacrocycle hydrazone-imine exchange was revealed to facilitate the formation of the hydrazone-based macrocycle from an imine-based macrocycle.
Lin
Jian-Bin
JB
State Key Laboratory of Bio-Organic and Natural Products Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai 200032, China.
Xu
Xiao-Na
XN
Jiang
Xi-Kui
XK
Li
Zhan-Ting
ZT
D000588:Amines / Q000737:chemistry; D002625:Chemistry, Organic / Q000379:methods*; D006835:Hydrazones / Q000737:chemistry; D006860:Hydrogen Bonding; D007094:Imides / Q000737:chemistry; D007097:Imines / Q000737:chemistry; D009682:Magnetic Resonance Spectroscopy; D008958:Models, Molecular; D008968:Molecular Conformation; D015394:Molecular Structure; D013816:Thermodynamics
D000588:Amines; D006835:Hydrazones; D007094:Imides; D007097:Imines