A New and Versatile Access to Polyazamacroheterocycles and Cryptands Through Ring-Closing Bis(hydroaminomethylation)

Abstract

The RhI‐catalyzed hydroformylation of dienes in the presence of primary amines or secondary α,ω‐diamines has been applied to macroheterocyclic ring synthesis. Starting from (hetero)diallylic systems, 12‐ to 36‐membered polyheterocycles have been readily obtained in up to 56% yield. In addition, we show that the macrocyclic systems thus obtained can be debenzylated and that the resulting macrocyclic diamines undergo a second ring‐closing bis(hydroaminomethylation) to give cryptand systems.

Methylformate as replacement of syngas in one-pot catalytic synthesis of amines from olefins

“…At high temperature the selectivity decreases due to the partial involvement of isomeric alkenes in the reaction. Neither aldehyde nor enamine was observed in the final products while using Ru 3 (CO) 12 . The reaction occurred much more slowly than that with rhodium because of the lower activity of ruthenium phosphine complexes in hydroformylation.…”

“…The hydroaminomethylation has continued to draw the attention of researchers since the time of its discovery by Reppe at BASF. 1 This is evident from the large number of publications, both reviews and articles [2][3][4][5][6] dedicated to the syntheses of amines from olefins with terminal and internal double bonds, 7,8 complicated N-containing organic compounds, e.g., heterocycles, 9,10 N-containing macrocycles, [11][12][13] and dendrimers. [14][15][16] Reductive aminomethylation of olefins while using Rh complexes with bidentate phosphine ligands that are highly active in hydroformylation have been used for the regioselective preparation of amines.…”

Metal‐Assisted Multicomponent Reactions Involving Carbon Monoxide—Towards Heterocycle Synthesis

“…This strategy of repeated sequential hydroformylation and reductive amination of terminal dialkenes and a diamine also enabled rapid access to the cryptand system 14 (Scheme ) 12b…”

Metallvermittelte Mehrkomponentenreaktionen mit Kohlenmonoxid – eine modulare Heterocyclensynthese

“…Über die vorgestellte Strategie wiederholter Hydroformylierungen und reduktiver Aminierungen mit terminalen Dialkenen und Diaminen wurde auch ein rascher Zugang zu den Cryptanden 14 erschlossen (Schema ) 12b…”