Fluorescence screening of tartaric acid-derived azamacrocycles synthesized via sequential hydroformylation/reductive amination as potential ligands for asymmetric catalysis

Azamacrocycles containing a tartaric acid-derived unit and aryl units were synthesized via rhodium-catalyzed hydroformylation while the subsequent reductive amination was carried out in a tandem or stepwise fashion. Upon fluorescence emission experiments, some of the macrocycles showed chelating affinities toward transition metals such as zinc or rhodium.

Figure optionsDownload as PowerPoint slide

(4S,5S)-Benzyl-[5-(benzylamino-methyl)-2,2-dimethyl-[1,3]dioxolan-4-ylmethyl]-amineC21H28N2O2Ee = 100%[α]D20 = −14.6 (c 0.7, CH2Cl2)Source of chirality: (+)-diethyl L-tartrateAbsolute configuration: (4S,5S)

(9S,13S)-7,15-Dibenzyl-11,11-dimethyl-2,10,12,20-tetraoxa-7,15-diaza-tricyclo[19.3.1.09,13]pentacosa-1(24),21(25),22-triene-23-carboxylic acid methyl esterC37H48N2O6Ee = 100%[α]D21 = +13.0 (c 0.2, CH2Cl2)Source of chirality: (+)-diethyl L-tartrateAbsolute configuration: (9S,13S)

(9S,13S)-7,15-Dibenzyl-11,11-dimethyl-2,10,12,20-tetraoxa-7,15-diaza-dinaphtho[a,c]-bicyclo[18.3.0.09,13]-cyclotriacosaneC49H54N2O4Ee = 100%[α]D21 = −78.7 (c 0.8, CH2Cl2)Source of chirality: (+)-diethyl L-tartrateAbsolute configuration: (9S,13S)

(9S,10S)-7,12-Dibenzyl-9,10-dihydroxy-2,17-dioxa-7,12-diaza-bicyclo[16.3.1]docosa-1(21),18(22),19-triene-20-carboxylic acid methyl esterC34H44N2O6Ee = 100%[α]D21 = −24.0 (c 0.06, CH2Cl2)Source of chirality: (+)-diethyl L-tartrateAbsolute configuration: (9S,10S)