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Cavitands as Reaction Vessels and Blocking Groups for Selective Reactions in Water
Author(s) -
Masseroni Daniele,
Mosca Simone,
Mower Matthew P.,
Blackmond Donna G.,
Rebek Julius
Publication year - 2016
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201602355
Subject(s) - chemistry , azide , cavitand , amine gas treating , phosphine , diamine , selective reduction , organic chemistry , combinatorial chemistry , polymer chemistry , supramolecular chemistry , molecule , catalysis
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 (C 8 , C 10 , and C 12 ). The diazide substrates are taken up by the cavitand in D 2 O 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.