Adamantane diazirine

In another experiment tritiated adamantane diazirine fixed to the hydrocarbon core of a membrane gave rise to carbene insertion into the catalytic subunit of ATP-ase. After protolytic degradation adjacent areas of the original structure became evident (80JBC(255)860). 

Unsubstituted alkyl diazirines are ruled out because carbenes from them rearrange to olefins (Fig. 3.14). The constraints of the caged ring system do not allow this possibility with the useful adamantane diazirine, although here a fraction of the carbene is lost by intramolecular insertion (Fig. 3.15). 

In contrast to 3-H-3-aryldiazirines, adamantane diazirine may be prepared in high yield by a method (Isaev et al., 1973 Bayley and Knowles, 1980) based on a general procedure for dialkyl diazirines devised by Schmitz and Ohme (1961) (Fig. 3.23). Such a convenient synthesis is most attractive but as yet adamantane diazirines further functionalized to allow their attachment to molecules of biological interest, have not been prepared, although this should not be a difficult task. 

Adamantane diazirine 372 nm/245 1,750 Carbene and diazoada-mantane Bayley and Knowles (1978a,b, 1980), Goldman et al. (1979), Farley et al. (1980)... 

It should be pointed out that despite their high reactivity carbenes are selective, and while they will react with hydrocarbons in the absence of nucleophiles, a nucleophilic group exposed within the bilayer will preferentially be attacked. Some properties of the three most thoroughly tested reagents iodonaphthyl azide, adamantane diazirine, and 3-trifluoromethyl-3-(m-iodophenyl)diazirine are summarized in Table 6.1. There follows a brief description of a typical experimental procedure, a discussion of control experiments, and several caveats, followed by some examples of the applications of hydrophobic reagents. 

Kupfer, R., Poliks, M.D. and Brinker, U.H. (1994). Carbenes in constrained systems. 2. First carbene reactions within zeolites-solid state photolysis of adamantane-2-spiro-3 -diazirine. J. Am. Chem. Soc. 116, 7393-7398... 

C6o reacts with diazomethane to yield fulleroids [97,99,100,234], Carbene generated from the thermolysis of precursors such as diazirines, sodium trichloroac-etate, cyclopropene, oxadiazole, and tosylhydrazone [60,235] adds onto C6o leading to methanofullerenes [12,15,236], Recently, Akasaka et al. described the photochemical reaction of diazirine with C6o [237], Irradiation of a benzene solution of 2-adamantane-2,3 -[3H]-diazirine 58 and C6o with a high pressure mercury lamp (cutoff <300 nm) at 15°C in a Pyrex tube resulted in the formation of mixture of the isomers 59a and 59b in a ratio of 51/49 (Scheme 24). 

This chapter focuses on publications since 1995 and builds on the corresponding chapter in the previous editions <1984CHEC(7)195, 1996GHEC-II(1A)347>. In this chapter, the discussion of diazirine 1 systems is followed by diaziridine 2 systems. The nomenclature of both saturated and unsaturated systems follows the Hantszch-Widman convention and is exemplified here by structures 3-5. The presence of the diaziridine group has often been indicated by the prefix azi (e.g., azi-adamantane <2001TL9161, 1998JA11627>), and this nomenclature has been employed when used in source reference. 

D. Krois, U. H. Brinker, Induced circular dichroism and UV-vis absorption spectroscopy of cyclodextrin inclusion complexes structural elucidation of supramolecular aziadamantane (spiro[adamantane-2,3 -diazirine]), /. Am. Chem. Soc., 1998, 120, 11627-11632. 

Adamantylidenes, when generated by photolysis of the corresponding diazirines incarcerated within an organic container, were found to behave differently from free carbenes and the chemistry ensuing was determined by the structure of the host-guest complexes. Thus, the substituent pattern on the adamantane skeleton affected the orientation of the carbene within the host cavity. ... 

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