Pd-Сatalyzed Amination for the Synthesis of Macropolycycles Comprising Cyclen, Cyclam and Naphthalene Moieties

Abstract

Pd-catalyzed amination reactions were employed for the synthesis of macrobicyclic compounds possessing cyclen or cyclam moieties, naphthylmethyl spacers and polyamine linkers. The results of the macrocyclization reactions involving 1,7-bis(4-bromonaphthyl-1-methyl)cyclen and 1,8-bis(4-bromonaphthyl-1-methyl)Ключевые слова: Pd-Катализируемое аминирование, макрополициклические соединения, циклен, циклам.

Chiral Cryptands Possessing Tetraazamacrocyclic and BINAM Moieties: Synthesis and Evaluation as Fluorescent Detectors

“…They were successfully employed by us earlier to obtain various macrobicyclic and macrotricyclic derivatives of cyclen (1,4,7,10-tetraazacyclododecane) and cyclam (1,4,8,11-tetraazacyclotetradecane). [24][25][26][27][28][29][30][31] The starting compounds, N,N'-di(bromobenzyl) substituted cyclens 1, 2 and cyclams 3, 4 were synthesized in high yields from free tetraazamacrocycles by three-step procedures described previously. [24,25] The reactions of these compounds with (S)-BINAM (5) were carried out in the presence of the catalytic system Pd(dba) 2 /BINAP (8/9 mol%) in boiling dioxane at the concentration of the starting compounds 0.02 M using sodium tert-butoxide as a base (Scheme 1).…”

Synthesis of Macrocycles Containing Endocyclic Chiral BINAM Moieties

“…7, 13,14,15,16,18,19,20,21,23,24,25,26,12:31, [1,26,5,11,16,22] dioxatetraazacyclotriacontine (3b). Obtained from compound 4 (0.17 mmol, 100 mg), dioxadiamine 2b (0.17 mmol, 34 mg), in the presence of Pd(dba) 2 -Bis (7-…”

“…The reaction mixture is refluxed for 24 h, after cooling it down to ambient temperature the solvent is filtered, the precipitate is washed with CH 2 Cl 2 (5 ml), combined organic fractions are evaporated in vacuo, and the residue is chromatographed on silica gel using a sequence of eluents: CH 2 Cl 2 , CH 2 Cl 2 /MeOH (200:1 -3:1). 7,8,15,16,18,19,22,23,29,13:28, [1,2-q:2',1'-o] [1,4,7,14,19,26] Macrocycles Containing Endocyclic Chiral BINAM Moieties from 22 to 27 %, thus only the diamine with the shortest chain provided two times higher yield, probably due to a better adjustment of its two amino groups to two bromine atoms in the compound 4.…”

“…[18][19][20][21] On the other hand, catalytic macrocyclization of di(bromobenzyl) derivatives afforded enough high yields. [22][23][24][25] We attempted the synthesis of N,N'-di (3-bromobenzyl) substituted BINAM by the reaction with 2 equiv. of 3-bromobenzyl bromide in boiling MeCN in the presence of potassium carbonate and isolated the target compound 7 in 32 % yield (Scheme 4).…”