Annulated carbamates are precursors for the ring contraction of the adamantane framework

Abstract

We report a protocol for the one-pot two-step synthesis of noradamantane methylene amines.

Spatial arrangements of cyclodextrin host–guest complexes in solution studied by 13C NMR and molecular modelling

“…Compounds 1 – 8 (as hydrochloride salts or free bases), were attempted to co-crystallize with α-, β- and γ-cyclodextrins. Compounds 1 , 6 and 8 are commercial, compounds 2 – 5 [ 21 ] and 7 [ 22 ] were prepared according to published procedures. Compound 2 (as a free amine) crystallized in the supramolecular capsule of two α-cyclodextrins, and the mono-crystal was subjected to X-ray analysis.…”

The Versatile and Strategic O-Carbamate Directed Metalation Group in the Synthesis of Aromatic Molecules: An Update

“…Another area of interest involves the extension of the metalation chemistry of ArOAms to alkenyl and alkyl O -carbamates, e.g., (hetero)­benzylic compounds. , Since this has not yet been reported, it is implicit that these systems are too unreactive. Nevertheless, the ready access to linear, cyclic, and annulated (e.g., adamantyl) aliphatic O -carbamates − beckons a foray into this potentially rich field.…”

Synthesis of 1,2-Disubstituted Adamantane Derivatives by Construction of the Adamantane Framework

“…Adamantane represents the bottom of a thermodynamic stability well of C 10 H 16 hydrocarbon constitutional isomers, where all others tend to fall to under thermodynamic conditions, already apparent from its method of industrial synthesis [4,74]. Close ringcontracted derivatives, such as protoadamantane (Figure 1) [75,76] and noradamantane (Figure 2) [77,78], have a certain degree of strain and have been used as 'spring-loaded' compounds that rearrange to more stable adamantane, revealing carbocations during the process. These reactions have been exploited in the synthesis of 1,2-disubstituted adamantane derivatives.…”