Deep-cavity cavitand octa acid as a hydrogen donor: Photofunctionalization with nitrenes generated from azidoadamantanes

Rajib Choudhury, Shipra Gupta, José P. Da Silva, V. Ramamurthy

Research output: Contribution to journalArticlepeer-review

20 Scopus citations

Abstract

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 1H NMR in solution and by ESI-MS in gas phase. In both phases, the complexes are stable. Irradiation of these complexes (λ > 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 azidoadamantanes included in CB7 were irradiated (λ > 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.

Original languageEnglish (US)
Pages (from-to)1824-1832
Number of pages9
JournalJournal of Organic Chemistry
Volume78
Issue number5
DOIs
StatePublished - Mar 11 2013

ASJC Scopus subject areas

  • Organic Chemistry

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