35242-17-2Relevant academic research and scientific papers
Polycyclo Dyes and Use Thereof
-
, (2013/06/05)
The invention relates to a family of fluorescent compounds that comprise a bridged polycyclo moiety. The compounds can be chemically linked to biomolecules, such as proteins, nucleic acids, and therapeutic small molecules. The compounds can be used for imaging in a variety of medical, biological and diagnostic applications, and are particularly useful for the in vivo imaging of regions of interest within a mammal.
Asymmetric allylic oxidation of bridged-bicyclic alkenes using a copper-catalysed symmetrising-desymmetrising Kharasch-Sosnovsky reaction
Clark, J. Stephen,Clarke, Melanie-Rose,Clough, John,Blake, Alexander J.,Wilson, Claire
, p. 9447 - 9450 (2007/10/03)
Enantioselective symmetrising-desymmetrising allylic oxidation of racemic bridged bicyclic alkenes using an asymmetric copper-catalysed Kharasch-Sosnovsky reaction has been explored. Good yields and reasonable levels of induction (up to 70% ee) have been
3-Trimethylsilylbicyclo[3.2.1]oct-2-ene in the synthesis of functionalized bicyclo[3.2.1]octane systems
Patil, Govindagouda S.,Nagendrappa, Gopalpur
, p. 1019 - 1024 (2007/10/03)
3-Trimethylsilylbicyclo[3.2.1]oct-2-ene 5 is shown to be useful in the synthesis of functionalized bicyclo[3.2.1]octanes. It undergoes acylation to give 3-bicyclo[3.2.1]oct-2-enyl ketones 6-10 without undergoing skeletal rearrangement, in contrast to the acylation of 2-trimethylsilylbicyclo[2.2.1]hept-2-ene 23. It can be epoxidized and the epoxysilane 21 hydrolyzes to the silyldiol 22 in normal way as against the resistance of 2-trimethylsilylbicyclo[2.2.1]hept-2-ene epoxide 24 towards hydrolysis.
DEAMINATION OF ENDO - AND EXO-BICYCLOOCTAN-3-YLAMINES AND THEIR DERIVATIVES
Maskill, H.,Wilson, Alan A.
, p. 1369 - 1376 (2007/10/02)
Bicyclooctan-3-ylamines have been deaminated in acetic acid by nitrous acid and via their N-phenyltriazines; their ethyl N-nitrosocarbabamates have also been solvolysed in ethanol.The exo-isomers give mainly unrearranged substitution, some elimination, and very little rearrangement.The unrearranged substitution is derived from both the solvent (the external nucleophile, either acetic acid or ethanol) and internal nucleophile liberated in the deaminative fragmentation step (water from the nitrous acid reaction, aniline from the triazene, and ethyl carbonate from the nitrosocarbamate).It is of predominantly retained configuration i n all three reactions with the solvents, and, as demonstrated in the solvolysis, with the internal nucleophile.The endo-isomers give mainly elimination, some unrearranged substitution, and appereciable rearrangement.The solvent-derived unrearranged substitution is with predominant inversion of configuration in all three reactions whereas that from the internal nucleophile, established by the nitrosocarbamate solvolysis, is predominantly with retention.Rearangement from both endo- and exo-compounds is best explained in terms of hydride shift from the first formed carbonium ions (in nitrogen-separated complex ion-pairs with hydrogen-bonded anions) produced in the deaminative fragmentation.This gives rearranged classical bicyclooctan-2-yl carbonium ions which, in competition with nucleophilic capture and proton loss, undergo further stepwise rearrangement to a common unsymmetrical non-classical carbonium ion.The non-classical cation and its classical precursors (which, from exo-and endo-substrates, differ in the location of the counter-anion) give rise to substitution products derived from solvent and the internal nucleophile.The non-classical carbonium ion also gives some tricyclo2,7>octane.The high yields of internal substitution products from both endo- and exo-compounds rule out long lived intermediates such as diazonium ions.
