title: Cavitands as Reaction Vessels and Blocking Groups for Selective Reactions in Water.
abstract: 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 D2 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.
authors.affiliation: Department of Chemistry, Fudan University, 220 Handan Road, Shanghai, 200433, China.
authors.forename: Daniele
authors.identifier: 0000-0002-4526-3838
authors.initials: D
authors.lastname: Masseroni
authors.affiliation: Department of Biotechnology and Biosciences, University of Milano-Bicocca, 20126, Milano, Italy.|Department of Chemistry and The Skaggs Institute for Chemical Biology, The Scripps Research Institute, 10550 North Torrey Pines Road, La Jolla, CA, 92037, USA.
authors.forename: Simone
authors.initials: S
authors.lastname: Mosca
authors.affiliation: Department of Chemistry and The Skaggs Institute for Chemical Biology, The Scripps Research Institute, 10550 North Torrey Pines Road, La Jolla, CA, 92037, USA.
authors.forename: Matthew P
authors.initials: MP
authors.lastname: Mower
authors.affiliation: Department of Chemistry and The Skaggs Institute for Chemical Biology, The Scripps Research Institute, 10550 North Torrey Pines Road, La Jolla, CA, 92037, USA. blackmond@scripps.edu.
authors.forename: Donna G
authors.initials: DG
authors.lastname: Blackmond
authors.affiliation: Department of Chemistry, Fudan University, 220 Handan Road, Shanghai, 200433, China. jrebek@scripps.edu.|Department of Chemistry and The Skaggs Institute for Chemical Biology, The Scripps Research Institute, 10550 North Torrey Pines Road, La Jolla, CA, 92037, USA. jrebek@scripps.edu.
authors.forename: Julius
authors.initials: J
authors.lastname: Rebek
keywords: Staudinger reduction; cavitands; diazides; selectivity; supramolecular chemistry