000204058 001__ 204058
000204058 005__ 20181203023718.0
000204058 0247_ $$2doi$$a10.1002/chem.201403662
000204058 022__ $$a0947-6539
000204058 02470 $$2ISI$$a000344358900031
000204058 037__ $$aARTICLE
000204058 245__ $$aBase-Catalyzed Intramolecular Hydroamination of Cyclohexa-2,5-dienes: Insights into the Mechanism through DFT Calculations and Application to the Total Synthesis of epi-Elwesine
000204058 260__ $$bWiley-V C H Verlag Gmbh$$c2014$$aWeinheim
000204058 269__ $$a2014
000204058 300__ $$a12
000204058 336__ $$aJournal Articles
000204058 520__ $$aThe base-catalyzed intramolecular hydroamination of 1-ethylaminocyclohexa-2,5-dienes is described. The transformation proceeds through isomerization of the cyclohexa-1,4-dienyl fragment into the corresponding conjugated 1,3-diene prior to the hydroamination step. Attaching a chiral glycinol ether auxiliary on the amino group allows the protonation to occur with complete diastereocontrol. The resulting lithium amide then adds onto the 1,3-dienyl moiety, affording the desired fused pyrrolidine ring along with the corresponding lithium allylic anion. Protonation of the latter then proceeds with high regiocontrol to favor the resulting allylic amines. In contrast, when the reaction was performed on primary amines, fused pyrrolidines bearing a homoallylic amino group were obtained. The stereochemical course of the process and determination of the reaction pathways were established based on calculations performed at the DFT level. Finally, application of the methodology to the enantioselective synthesis of (+)-epi-elwesine, a crinane alkaloid, is described.
000204058 6531_ $$aalkaloids
000204058 6531_ $$ahydroamination
000204058 6531_ $$aisomerization
000204058 6531_ $$areaction mechanisms
000204058 6531_ $$arearrangements
000204058 700__ $$uUniv Bordeaux, ISM, UMR 5255, F-33400 Talence, France$$aRousseau, Geraldine
000204058 700__ $$uUniv Bordeaux, ISM, UMR 5255, F-33400 Talence, France$$aLebeuf, Raphael
000204058 700__ $$0241567$$g153052$$aSchenk, Kurt
000204058 700__ $$uUniv Bordeaux, ISM, UMR 5255, F-33400 Talence, France$$aCastet, Frederic
000204058 700__ $$uUniv Bordeaux, ISM, UMR 5255, F-33400 Talence, France$$aRobert, Frederic
000204058 700__ $$aLandais, Yannick$$uUniv Bordeaux, ISM, UMR 5255, F-33400 Talence, France
000204058 773__ $$j20$$tChemistry-A European Journal$$k45$$q14771-14782
000204058 909C0 $$0252442$$pIPSB$$xU11993
000204058 909CO $$particle$$ooai:infoscience.tind.io:204058
000204058 937__ $$aEPFL-ARTICLE-204058
000204058 973__ $$rREVIEWED$$sPUBLISHED$$aEPFL
000204058 980__ $$aARTICLE