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Experiments Towards the Formation of 1,6-Dehydroquadricyclane and Density Functional Calculations on This and Related Molecules

✍ Scribed by Susanne Glück-Walther; Oliver Jarosch; Günter Szeimies

Publisher
John Wiley and Sons
Year
1998
Tongue
English
Weight
507 KB
Volume
1998
Category
Article
ISSN
1434-193X

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✦ Synopsis

quadricyclane (21c), whose NMR spectra could also be recorded. 21c was converted into the corresponding 1,6-disub-1,6-Dibromoquadricyclane (6) was obtained from norbornadiene (11) by hydroboration, oxidation of the diol 12 to the stituted quadricyclanes with D 2 O (87%), chlorotrimethylsilane (92%), dimethyl sulfate (55%), methyl chloroformate diketone 14 and its conversion into 2,6-dibromonorbornadiene (20) using tribromodioxaphosphole 16b followed by (45%), iodine monochloride (62%), and p-toluenesulfonyl chloride (48%). Ϫ Density functional calculations using the treatment of the mixture 17/18 with potassium tert-butoxide in DMSO and photocyclization of 20. Reaction of 6 with tBuLi B3LYP/6-31G* level of theory showed that 1,6-dehydroquadricyclane ( 4) is a local energy minimum in its singlet elec-(2 equiv.) led to the formation of 1-bromo-6-lithioquadricyclane 7, the NMR spectra of which were observed up to 0°C. tronic state. 4 contains a unique structure with 4 condensed cyclopropane units. The parent hydrocarbons 27 and 28, hi-7 did not lose LiBr to give 4, but could be trapped with H 2 O and chlorotrimethylsilane to give 21e (53%) and 21f (64%). therto unknown, are also local energy minima in their singlet electronic states. Reaction of 6 with tBuLi (> 4 equiv.

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