Cavitands as Reaction Vessels and Blocking Groups for Selective Reactions in Water

The majority of reactions currently performed in the chemical industry take place in organic solvents, compounds that are generally derived from petrochemicals. To promote chemical processes in water, we examined the use of synthetic, deep water‐soluble cavitands in the Staudinger reduction of long‐...

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Bibliographic Details
Published in:Angewandte Chemie 2016-07, Vol.128 (29), p.8430-8433
Main Authors: Masseroni, Daniele, Mosca, Simone, Mower, Matthew P., Blackmond, Donna G., Rebek Jr, Julius
Format: Article
Language:English
Subjects:
Aliphatic compounds
Amines
Azides (organic)
Cavitanden
Chains
Chemical industry
Chemical reactions
Chemistry
Conformation
Deep water
Diamines
Diazide
Exposure
Organic solvents
Petrochemicals
Phosphine
Phosphines
Reduction
Selektivität
Solvents
Staudinger-Reduktion
Substrates
Supramolekulare Chemie
Terminals
Vessels
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Summary:The majority of reactions currently performed in the chemical industry take place in organic solvents, compounds that are generally derived from petrochemicals. To promote chemical processes in water, we examined the use of synthetic, deep water‐soluble cavitands in the Staudinger reduction of long‐chain aliphatic diazides (C8, C10, and C12). The diazide substrates are taken up by the cavitand in D2O in folded, dynamic conformations. The reduction of one azide group to an amine gives a complex in which the substrate is fixed in an unsymmetrical conformation, with the amine terminal exposed and the azide terminal deep and inaccessible within the cavitand. Accordingly, the reduction of the second azide group is inhibited, even with excess phosphine, and good yields of the monofunctionalized products are obtained. In contrast, the reduction of the free diazides in bulk solution yields diamine products. Halbe Sachen: Ein wasserlöslicher Cavitand mit tiefem Hohlraum bewirkt die selektive partielle Reduktion von Diaziden zu Monoaminen. Dieser ungewöhnliche Prozess kann anhand verschiedener Faltungskonformationen von Ausgangsverbindungen und Produkten im Inneren des Cavitanden erklärt werden.
ISSN:0044-8249
1521-3757
DOI:10.1002/ange.201602355