Über Verbindungen mit Urotropin‐Struktur, XXX. Ringschlußreaktionen ausgehend von Bicyclo [3.3.1]nonandion‐(3.7)

Abstract

Die katalytische Hydritrung von Bicyclo[3.3. I]nonandion-(3.7) (1) fiihrte in glatter Reaktion zu 1 -Hydroxy-2-oxa-adamantan (111). das nach Austausch der Hydroxylgruppe gegen Halogen und anschliebnde katalytische Hydrierung das bereits bekannte 2-Oxa-adamantan (VII) liefert. Die Kinetik der Solvolyse des 1 -Brom-2sxa-adamantans wurdeverglichen rnit der des 1-Brom-adamantans. 2) H. STETTER und P. TACKP., Chern. Ber. 96,694 [1963].

Discovery and Exploitation of AZADO: The Highly Active Catalyst for Alcohol Oxidation

“…First, the diketone 12 turned out to be intractable, giving a mixture with the highly polar hydrate form 13, and second, complicated procedures for the NaBH 3 CN-mediated reduction of the in situ-generated half-imine 9 hampered reliable production of the azaadamatanol 15. 35,36) The major product we obtained was the oxaadamantane 14, and the desired azaadamantanol 15 was secured in only a trace amount (Chart 5).…”

“…Treatment of 23 with 5% HCl allowed the deprotection of the ketal and the concomitant aminal formation to give the N-Cbz-1-hydroxy-2-azaadamantane (24). Subsequent deprotection of the Cbz group afforded the known 1-hydroxy-2-azaadamantane, from which 2-azaadamantane (10) was prepared in a straightforward manner, as described by Henkel et al 35,36) (Chart 7). With 1-Me-AZADO (20) and AZADO (11) in hand, we carried out comparative evaluations of their catalytic activities with that of TEMPO (1) under two popular alcohol oxidation conditions, namely, Anelli's conditions using NaOCl as the bulk oxidant (Table 1) and Margarita's conditions using PhI(OAc) 2 as the bulk oxidant (Table 2).…”

Enantioselective Total Syntheses of the Proposed and Revised Structures of Methoxystemofoline: A Stereochemical Revision

“…It is worth mentioning that both the bridgehead radicals and the C–C bond formation based on α-aminoalkyl radicals are well documented . However, very few examples of the generation - reduction of bridgehead N -α-carbon radicals have been reported, , and to our knowledge, the Keck allylation has not been applied to the bridgehead α-aminoalkyl radicals.…”

Thermal and photochemical reactions of sodium salts of .beta.-phosphono tosylhydrazones

“…Results are compared with literature data for the solvolyses of related adamantane substrates (1 and 2), as well as for bicyclo[2.2.2]octyl (3),9 bicyclo[3.3.1]nonyl (4),10 and homoadamantyl (5)11 systems.…”