Tuning the size of macrocyclic cavities in trianglimine macrocycles

Abstract

The synthesis of aromatic dicarboxaldehydes is described along with their reactivity in the [3 + 3] cyclocondensation reaction with (1R,2R)-diaminocyclohexane to give trianglimine macrocycles. In particular, the scope and limitation of the reaction with regard to complete control of the cavity size of the macrocycles is discussed producing a total of 11 macrocycles with different cavity sizes ranging from 9 to 23 angstroms.

Synthesis, Structure, and Electronic Properties of Extended π‐Conjugated Group 6 Fischer Alkoxy–Bis(carbene) Complexes

“…NMR spectra were recorded at 25 8C in CDCl 3 on a Bruker Avance 300 (300 MHz for 1 H and 75 MHz for 13 All commercially available products were used without further purification. The following dialdehydes were prepared according to literature: 9,10-diformylanthracene, [30] b,b'-p-phenylen-di-acrolein, [31] 2,6-naphthalenedicarbaldehyde, [32] 5-bromoisophthalaldehyde, [33] 4,4'-diformyl-1,1'-biphenyl, [34] 4,4'-diformylphenyl ether, [35] 2,5-diformylfuran, [36] 2,5-difor- Table 2. Electrochemical data [a] and HOMO energies [b] of complexes 1, 2 and 5. mylthiophene, [37] 5,5'-diformyl-2,2'bithiophene [38] and 1,1'-ferrocene dicarbaldehyde, [39] The following metal carbenes were prepared according to previously described methods:…”

“…All commercially available products were used without further purification. The following dialdehydes were prepared according to literature: 9,10‐diformylanthracene,30 b,b′‐ p ‐phenylen‐di‐acrolein,31 2,6‐naphthalenedicarbaldehyde,32 5‐bromoisophthalaldehyde,33 4,4′‐diformyl‐1,1′‐biphenyl,34 4,4′‐diformylphenyl ether,35 2,5‐diformylfuran,36 2,5‐diformylthiophene,37 5,5′‐diformyl‐2,2′bithiophene38 and 1,1′‐ferrocene dicarbaldehyde,39 The following metal carbenes were prepared according to previously described methods: pentacarbonyl[(ethoxy)(methyl)carbene]chromium(0) ( 3 a ),40 pentacarbonyl[(ethoxy)(methyl)carbene]tungsten(0) ( 3 b ),41 decacarbonyl‐μ‐[1,4‐phenylenbis(1‐ethoxy‐2‐propen‐3‐yl‐1‐yliden)]dichromium ( 2 aa )13 and decacarbonyl‐μ‐[1,3‐phenylenbis(1‐ethoxy‐2‐propen‐3‐yl‐1‐yliden)]dichromium ( 2 ab ) 13…”

One‐Step Construction of the Shape Persistent, Chiral But Symmetrical Polyimine Macrocycles

“…Macrocyclic polyimines of this shape, based on ( R,R )‐ DACH therefore force the construction of the symmetrical dialdehyde linkers to adapt the angle between formyl groups close to 120°. Hence, the definition of rhombimine does not include all products of [2+2] cycloadditions of dialdehydes to ( R,R )‐ DACH , however, the group that directs aldehydes to the angle of 120° can be both a single atom or a group of atoms ,,…”

“…In the simple dialdehydes A7a ‐ A7f p ‐substituted aromatic rings are separated by one atom. Due to the electronic and steric factors the 120° angle, which is defined by the Ar‐X−Ar bonds, is not always strictly preserved,,, and vary between 110° and 120°. In all known rhombimines this does not influence the product type and its yield.…”

Samarium(III) nitrate-catalyzed one-pot synthesis of 42-membered N,S,O-containing cyclophanes

“…[1][2][3][4][5][6][7] A considerable drawback of this method is the formation of by-products arising from linear polycondensation or simultaneous [n+n]-cyclocondensation of the initial α,ω-bifunctional compounds. [8][9][10][11][12][13][14] The formation of by-products is minimised, as a rule, by using high dilution, 11,15,16 templates, [17][18][19][20][21][22] and catalytic reactions. [23][24][25][26][27] Cyclophanes containing benzene rings in the molecule have rigid cyclic skeletons, which is important for their complexation of metal ions 5 and organic molecules.…”