The synthesis and conformation of oxygenated trianglimine macrocycles

Abstract

The synthesis of series of D(2h) and C(2v) symmetric oxygenated aromatic dicarboxaldehydes, using dilithiation methodology, is described along with their reactivity in the [3+3] cyclocondensation reaction with (1R,2R)-diaminocyclohexane to give oxygenated trianglimine macrocycles. Macrocycles derived from C(2v) symmetric dialdehydes give macrocycles with a stereogenic aromatic plane with complete diastereocontrol, as a mixture of rotamers.

4,2’:6’,4”- and 3,2’:6’,3”-Terpyridines: The Conflict between Well-Defined Vectorial Properties and Serendipity in the Assembly of 1D-, 2D- and 3D-Architectures

“…1 H NMR (500 MHz, CDCl 3 ) δ/ppm 10.52 (s, 2H, H CHO ), 7.43 (s, 2H, H C3 ), 4.05 (t, J = 6.5 Hz, 4H, H a ), 1.93–1.74 (m, 4H, H b ), 1.06 (m, J = 7.4 Hz, 6H, H c ). This matches the literature data [26]. …”

“…Compound 8a (Scheme 3) was prepared from the commercially available 2,5-dibromohydroquinone and then reacted with n BuLi followed by DMF to yield the dialdehyde 8b . The 1 H NMR spectrum of 8b was consistent with previously reported data [26]. The one-pot method of Hanan [9] (Scheme 3) was then used to transform 8b into compound 8 .…”

Functionalized Paddle Wheel Complexes from BODIPY Carboxylic Acids

“…Attempts to purify the compound led to decomposition. Benzyloxycarbonylphenyl)-1,3,5,7,8-pentamethyl-BODIPY (11): 2-IodoBODIPY 8 [24] (141 mg, 0.41 mmol), stannylbenzoic acid benzylester 10 [25] (250 mg, 0.50 mmol), and Pd(PPh 3 ) 4 (10 mg, 8 μmol) in dry toluene were heated to 100°C for 24 h. After removal of the solvent the mixture was subjected to silica chromatography with dichloromethane/pentane 1:1 to yield the title compound (140 mg, 0.30 mmol, 72 %). , 1 H, β-H Benzyloxycarbonylphenyl)-1,3,5,7-tetramethyl-8-mesityl-BODIPY (12): 2-IodoBODIPY 9 [ 2 6 ] (200 mg, 0.41 mmol), 4-stannylbenzoic acid benzylester 10 [25] (250 mg, 0.50 mmol) and Pd(PPh 3 ) 4 (10 mg, 8 μmol) in dry toluene were heated to 100°C for 24 h. After removal of the solvent the mixture was subjected to silica chromatography with dichloromethane/pentane 1:1 to yield the title compound (216 mg, 0.38 mmol, 93 %).…”

“…Benzyloxycarbonylphenyl)-1,3,5,7,8-pentamethyl-BODIPY (11): 2-IodoBODIPY 8 [24] (141 mg, 0.41 mmol), stannylbenzoic acid benzylester 10 [25] (250 mg, 0.50 mmol), and Pd(PPh 3 ) 4 (10 mg, 8 μmol) in dry toluene were heated to 100°C for 24 h. After removal of the solvent the mixture was subjected to silica chromatography with dichloromethane/pentane 1:1 to yield the title compound (140 mg, 0.30 mmol, 72 %). , 1 H, β-H Benzyloxycarbonylphenyl)-1,3,5,7-tetramethyl-8-mesityl-BODIPY (12): 2-IodoBODIPY 9 [ 2 6 ] (200 mg, 0.41 mmol), 4-stannylbenzoic acid benzylester 10 [25] (250 mg, 0.50 mmol) and Pd(PPh 3 ) 4 (10 mg, 8 μmol) in dry toluene were heated to 100°C for 24 h. After removal of the solvent the mixture was subjected to silica chromatography with dichloromethane/pentane 1:1 to yield the title compound (216 mg, 0.38 mmol, 93 %). [26] (168 mg, 0.34 mmol), 4-ethinylbenzoic acid 16 [27] (50 mg, 0.34 mmol), Pd(PPh 3 ) 4 (15 mg, 13 μmol), and copper(I)iodide (10 mg, 52 μmol) in dry THF (8 mL) and Hünig base (2 mL) were stirred at 55°C for 24 h. After cooling the solvent was removed in vacuo and the residue was subjected to silica chromatography with ethyl ether/n-hexane 2:1 + 1 % acetic acid.…”

Probing the mechanism and dynamic reversibility of trianglimine formation using real‐time electrospray ionization time‐of‐flight mass spectrometry

“…Trianglamines are readily synthesized in quantitative yields by reducing trianglimines with sodium borohydride . We have shown that trianglimines can be obtained from almost any synthetically accessible aromatic dialdehyde with complete control of the size of the macrocycle and functionalities incorporated into the aromatic moiety . More importantly, we have demonstrated that trianglimines can be incorporated into more sophisticated structures such as catenanes and shown their promise in chiral recognition .…”