71720-43-9Relevant articles and documents
Friedel-Crafts acylation of 2-trimethylsilylnorbornene. Effect of acyl group on the position of attack
Nagendrappa, Gopalpur,Begum, Noor Shahina
, p. 7923 - 7934 (2007/10/03)
The acylation of 2-trimethylsilylnorbornene 1 in the presence of aluminium chloride gives minor quantities of the expected 2-norbornenyl ketones 4. The formation of 3 and 5 as major products indicates that either α- or β-attack takes place predominantly depending on the nature of the acyl group, and the β-silicon effect is not a decisive factor. The β-silyl cation intermediate 2 mainly leads to nortricyclyl ketones 3 through 1,3- deprotonation, and the α-silyl cation 8 undergoes rearrangement to give novel bridge-head silylated products 5.
Simple Synthesis of 3-Acetyl-2-norbornanone via Diels-Alder Reaction and Reactivity of its Derivatives
Gottschalk, Franz-Josef,Weyerstahl, Peter
, p. 555 - 565 (2007/10/02)
Cyclopentadiene reacts SnCl4-catalyzed with the readily accessible benzyl ether 1b to give norbornene 2.Benzyl cleavage leads to the diol 3, on the other hand hydrogenation yields the 3-acetonorbornanol 13 which is oxidized and methylated via 6 to 7.The acetyl group of diketone 7 reacts selectively with ylen (-> 8) and orthoformate (-> 9).With methyl lithium however the diol 12 is formed.Selective reaction of the 2-ketogroup of 2 is only possible after protecting the acetyl function in 2 (-> 5 -> 14 -> 10 -> 19).The Grignard reaction of 2 is sterically hindered and leads with methyl or ethyl magnesium halide to 4a or b.The α,β-unsaturated ketones 16 resp. 17a and b are obtained from 4a resp. b via hydrogenation (->15a, b), oxidation (-> 11a, b) and dehydration.
