The synthesis of trianglimines: on the scope and limitations of the [3 + 3] cyclocondensation reaction between (1R,2R)-diaminocyclohexane and aromatic dicarboxaldehydes

Abstract

The synthesis of aromatic dicarboxaldehydes, using dilithiation methodology is described along with their reactivity, in the [3 + 3] cyclocondensation reaction, with (1R,2R)-diaminocyclohexane to give trianglimine macrocycles. The scope and limitations of the cyclocondensation reaction are studied and some comments on the properties of the novel macrocycles are made such as their conformation in solution and temperature dependent dynamic NMR behaviour.

Efficient Phenanthrene, Helicene, and Azahelicene Syntheses

“…The method was next extended to [7]helicenes by conjoining bis(aldehyde) 16 [23] with 2 equivalents of phosphonium salt 2. The resulting 3:1 mixture of Z,Z and E,Z bis-(stilbene)s 19 was separated by column chromatography, and (Z,Z)-19 was treated with 5 equivalents of tributyltin hydride and 0.4 equivalents of VAZO in toluene at 90 8C to give 9,10-dimethoxy [7]helicene (20) as large yellow needles in 75 % yield (Scheme 5).…”

Synthesis and capsule formation of upper rim substituted tetra-acrylamido calix[4]arenes

“…Within our research programme aimed at the synthesis of macrocyclic libraries 14, 15 we have recently reported on the palladium catalysed Heck reaction of tetra-iodo calix [4]arenes to produce tri-and tetra-olefinic calix [4]arenes. 14 In order to expand the scope of the C-C bond formation process, we became interested in coupling acrylamides to the broader rim of the calix [4]arene.…”

Facile Synthesis of New Polyazamacrocycles by the Pd-Catalyzed Amination of 3,3'-Dibromobiphenyl

“…A two-neck flask equipped with a magnetic stirrer and a condenser, flushed with dry argon, was charged with 3,3'-dibromobiphenyl (1) (0.5 mmol, 156 mg), absolute dioxane (25 ml), Pd(dba) 2 (24 mg, 8 mol%) and BINAP (28 mg, 9 mol%). The mixture was stirred for 2 min, then appropriate polyamine 2 (0.5 mmol) and t BuONa (1.5 mmol) were added, and the reaction mixture was refluxed for 24 h. After cooling to the ambient temperature and filtration of the precipitate dioxane was evaporated in vacuo and the residue was chromatographed on silica gel using a sequence of eluents: CH 2 7,10,13,24,27,.1 2,6 .1 14,18 .1 19,23 ] octatriaconta-1(35),2(38), 3,5,14(37), 15,17,19(36), 20,22,31, 7,10,13,16,3.1.1 2,6 ]pentacosa-1 (24) ,2(25),3,5,20,22- h e x a c o n t a -1 ( 6 1 ) , 2 ( 6 6 ) , 3 , 5 , 1 7 ( 6 5 ) , 1 8 , 2 0 , 2 2 ( 6 4 ) , 23,25,37(63) …”

“…[9] More sophisticated macrocycles like peptide-biphenyl hybrid [10] and hemispherand macrocycle [11] with bi-and quaterphenyl moieites have been recently reported. Cyclic triamides [12] as well as cyclic Schiff bases (trianglimines) [13,14] comprise three 3,3'-disubstituted biphenyls, the latter can be aslo built on the basis of 4,4'-disubstituted biphenyls. In some cases biphenyl fragment was built using Pd-catalyzed coupling of two benzene moieties at the step of macrocyclization, as it was in the case of the compound with diazacrown, dipeptide and biphenyl fragments.…”