52776-45-1Relevant articles and documents
Observation of a stable carbocation in a consecutive Criegee rearrangement with trifluoroperacetic acid
Krasutsky,Kolomitsyn,Kiprof,Carlson,Fokin
, p. 3926 - 3933 (2000)
Selective oxidative cleavage - cyclization of adamantane through the bridge carbon was developed in trifluoroperacetic acid (TFPAA). The methyl group in the bridge position was found to be the substituent that directs consecutive oxygen insertion into the cage structure during the course of a Criegee rearrangement. The formation of stable 5-methyl-4,6-dioxabishomoadamant-5-yl cation at -25°C was observed. Stable carboxonium ion formation allows control of the selectivity of further transformations. Hydrolysis leads to the stereospecific formation of endo, endo-3-hydroxy-7-acetoxybicyclo[3.3.1]nonane. Its single-crystal X-ray structure was obtained. An increase in temperature results in deprotonation of the 5-methyl-4,6-dioxabishomoadamant-5-yl cation to endo-3-trifluoroacetoxybicyclo[3.3.1]non-6-ene, which undergoes further epoxidation with TFPAA and acidic transannular cyclization in trifluoroacetic acid (TFAA). The described reactions can be used as a convenient method for the synthesis of bicyclo[3.3.1]nonane and oxaadamantane derivatives. The proposed mechanism for each transformation, as well as supporting ab initio theoretical calculations of the strain energy and the stabilization energy of the relevant oxacage structures, are discussed.
Synthesis of 4-(aminoalkyl) substituted 1,3-dioxanes as potent NMDA and σ receptor antagonists
Utech, Tina,K?hler, Jens,Wünsch, Bernhard
experimental part, p. 2157 - 2169 (2011/06/24)
Elongation of the distance between the oxygen heterocycle and the basic amino moiety or ring expansion of the oxygen heterocycle of the NMDA receptor antagonists dexoxadrol and etoxadrol led to compounds with promising NMDA receptor affinity. Herein the c
Acid-base reactions of adamantanethione S-methylide and its spiro-1,3,4-thiadiazoline precursor
Mloston, Grzegorz,Huisgen, Rolf
, p. 145 - 151 (2007/10/03)
The spiro-1,3,4-thiadiazoline 1 loses N2 at 45°C, and, as recently reported, the short-lived adamantanethione S-methylide (2) is an active 1,3-dipole. Interception of 2 by acids HX consists of CH2-protonation and ion recombination. Even 1 acts as HX vs 2 and - after electrocyclic ring opening of the anion (13 →15) - affords the dithioacetal C22H32N2S2 (14). The Δ3-thiadiazoline 1 is converted by base or acid catalysis to the Δ2-tautomer 21. Amidrazones (25, 26) are formed from 1 and sec-amines. The mechanisms are discussed and the structures elucidated.