55086-02-7Relevant academic research and scientific papers
Deep-cavity cavitand octa acid as a hydrogen donor: Photofunctionalization with nitrenes generated from azidoadamantanes
Choudhury, Rajib,Gupta, Shipra,Da Silva, José P.,Ramamurthy
, p. 1824 - 1832 (2013)
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.
Study of the structure and photochemical decomposition of azidoadamantanes entrapped in α- And β-cyclodextrin
Brinker, Udo H.,Walla, Peter,Krois, Daniel,Arion, Vladimir B.
, p. 1249 - 1255 (2011)
Photolysis of 1-azidoadamantane (1), either in its neat state or in alkane solution, yields the dimeric product 4. In contrast, amino alcohol 3 is formed as the sole product in high yield when 1 is confined within cyclodextrins (CyDs). To understand the discrepancy in product distribution caused by supramolecular encapsulation, CyD inclusion complexes (ICs) of azidoadamantanes were fully characterized. Indeed, intermolecular selectivity was influenced by reactant orientation and mobility. Both, 1- (1) and 2-azidoadamantane (5) yield 1:1 ICs with β-CyD and 1:2 ICs with α-CyD. As inferred from 2-D ROESY spectra in D2O, 1 is accommodated at the wider rim of β-CyD with the azido group pointing into the cavity. However, two principal orientations of 5 inside the cavity of β-CyD were found. Single crystal X-ray analysis of solid 5 also demonstrates a bimodal orientation within β-CyD. In addition, the first induced circular dichroism (ICD) study of an alkyl azide entrapped within CyD cavities is reported. From these data, it was concluded that azide 1 is bound more strongly within β-CyD in H 2O/EtOH = 8:2 at 293 K (Ka = 20240 ± 1000 M -1) than is 2-azidoadamantane (5) (Ka = 7450 ± 400 M-1).
Rearrangement of 1-Azidoadamantane to 3-Aryl-4-azahomoadamantane in the Presence of Aluminum Chloride and Aromatic Substrates
Margosian, Daniel,Kovacic, Peter
, p. 877 - 880 (2007/10/02)
Reaction of 1-azidoadamantane (1) with aromatic substrates in the presence of aluminum chloride at 80 deg C for 1.25 h gave the corresponding 3-aryl-4-azahomoadamantane (2) in >90 percent yield.The reaction of 1 to 2 represents the first report of intermolecular aminoalkylation of aromatics in the benzene series, presumably from an imine intermediate.At 18 deg C, only 3-hydroxy-4-azahomoadamantane is obtained.Addition of water to the reaction system at 80 deg C yielded 1-phenyladamantane (4) as the major product.Mechanistic features are treated.
Synthesis of Adamantane Derivatives. 54. Synthesis of Novel 4-Azahomoadamantano-Fused Heterocycles via Hydrocyanation of 4-Azahomoadamant-3-ene
Sasaki, Tadashi,Eguchi, Shoji,Okano, Takashi
, p. 4474 - 4477 (2007/10/02)
Photolysis of 1-azidoadamantane (1) in an aqueous NaCN-n-hexane two-phase system with Adogen 464 as a phase-transfer catalyst gave 3-cyano-4-azahomoadamantane (3), a hydrocyanation product of 4-azahomoadamant-3-ene (2).AlCl3-catalyzed decomposition of 1 in the presence of trimethylsilyl cyanide also afforded 3. 3 gave the corresponding amino acid 6 and its ester 7. 4-Azahomoadamantano-fused hydantoin, iminohydantoin, iminothiohydantoin, and thiohydantoin, 12-17, were readily prepared by the reactions of 3 with appropriate isocyanates and isothiocyanates.The reactions of 3 with dimethyl acetylenedicarboxylate, methyl vinyl ketone, and diketene afforded the corresponding iminopyrroline (20), aminopyrroline (23), and aminopyrrolinone (26).Acetylation of 3 gave N-acetylamino derivative 27, which was converted to Δ2-oxazolinium perchlorate 30 via N-acetylamino acid 29.
