Utilize este identificador para referenciar este registo: http://hdl.handle.net/10400.1/6576
Título: Deep-cavity cavitand octa acid as a hydrogen donor: photofunctionalization with nitrenes generated from
Autor: Choudhury, Rajib
Gupta, Shipra
Silva, José P. da
Ramamurthy, V.
Data: 2013
Editora: American Chemical Society
Resumo: 1-azidoadamantane and 2-azidoadamantane form a 1:1 complex with hosts octa acid (OA) and cucurbit[7]uril (CB7) in water. Isothermal titration calorimetric measurements suggest these complexes to be very stable in aqueous solution. The complexes have been characterized by H-1 NMR in solution and by ESI-MS in gas phase. In both phases, the complexes are stable. Irradiation of these complexes (lambda > 280 nm) results in nitrenes via the loss of nitrogen from the guest azidoadamantanes. The behavior of nitrenes within OA differs from that in solution. Nitrenes included within octa acid attack one of the four tertiary benzylic hydrogens present at the lower interior part of OA. While in solution intramolecular insertion is preferred, within OA intermolecular C-H insertion seems to be the choice. When azidoadainantanes included in CB7 were irradiated (lambda > 280 nm) the same products as in solution resulted but the host held them tightly. Displacement of the product required the use of a higher binding guest. In this case, no intermolecular C-H insertion occurred. Difference in reactivity between OA and CB7 is the result of the location of hydrogens; in OA they are in the interior of the cavity where the nitrene is generated, and in CB7 they are at the exterior. Reactivity of nitrenes within OA is different from that of carbenes that do not react with the host.
Peer review: yes
URI: http://hdl.handle.net/10400.1/6576
DOI: https://dx.doi.org/10.1021/jo301499t
ISSN: 0022-3263
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