Chemical transformations of tetracyclo[3.3.1.1.3,7.0.1,3]decane (1,3-dehydroadamantane): I. Reaction of 1,3-dehydroadamantane with carboxylic acids esters

Synthesis and Properties of 1,3-Disubstituted Ureas Containing (Adamantan-1-yl)(phenyl)methyl Fragment Based on One-Pot Direct Adamantane Moiety Inclusion

“…Then they were involved in the reaction with phenylacetic acid ethyl ester. The adamantylation reaction of phenylacetic acid ethyl ester proceeded into the α-position to the carbonyl group, with the obtaining of ethyl esters of (±)-(adamantane-1-yl)phenylacetic acid 3a and (±)-3,5-dimethyl-(adamantane-1-yl)phenylacetic acid 3b acids, yielding 91% and 85%, respectively (Scheme 1) [13]. (3,5-dimethyladamantyl) and phenyl in the structure of 1,3-disubstituted urea molecules will allow us to clarify the limiting dimensions of structures that can be used as sEH inhibitors, since the catalytical center of the enzyme is a "tunnel" of limited dimensions, with the following geometrical parameters: d(O2-H2) = 0.89 (2) Å, d(H2•••O1') = 1.78(2) Å, d(O2•••O1') = 2.6631 (11) Å, (O2-H2•••O1') = 171 (2)°, symmetry operation 1-x, 2-y, 1-z [8].…”

“…Then they were involved in the reaction with phenylacetic acid ethyl ester. The adamantylation reaction of phenylacetic acid ethyl ester proceeded into the α-position to the carbonyl group, with the obtaining of ethyl esters of (±)-(adamantane-1-yl)phenylacetic acid 3a and (±)-3,5-dimethyl-(adamantane-1-yl)phenylacetic acid 3b acids, yielding 91% and 85%, respectively (Scheme 1) [13]. Obtained adamantyl containing derivatives of phenylacetic acid ethyl ester 3a and 3b were hydrolyzed in ethylene glycol in the presence of KOH at the temperature of 190 °C [10], to produce (±)-(adamantane-1-yl)phenylacetic acid 4a and (±)-3,5-dimethyl-(adamantane-1-yl)phenylacetic acid 4b, with yields of 67% and 73%, respectively.…”

“…The structure of the obtained compounds was confirmed by 1 H, 13 C, and 19 F NMR spectroscopy, chromatography-mass spectrometry, and elemental analysis. Mass spectra were recorded on an Agilent GC 7820A/MSD 5975 chromatography-mass spectrometer (Agilent Technologies, Santa Clara, CA, USA) in fullscan (EI) mode.…”

“…%): 241 (1% [M] + ), 135 (12% [Ad] + ), 106 (100% [Ph-CH 2 -NH 2 ] + ) (Figures S7 and S8). Procedure for synthesis series of 1,3-disubstituted ureas 8a-j and 10a-c. Atom labels for 13 C NMR presented on Figure 2. Procedure for synthesis series of 1,3-disubstituted ureas 8a-j and 10a-c. Atom labels for 13 C NMR presented on Figure 2.…”

“…Procedure for synthesis series of 1,3-disubstituted ureas 8a-j and 10a-c. Atom labels for 13 C NMR presented on Figure 2. Procedure for synthesis series of 1,3-disubstituted ureas 8a-j and 10a-c. Atom labels for 13 C NMR presented on Figure 2. (±)-1-((Adamantyl)(phenyl)methyl)-3-phenyl urea (8a).…”