74669-79-7Relevant academic research and scientific papers
Enantioselective Conjunctive Cross-Coupling of Bis(alkenyl)borates: A General Synthesis of Chiral Allylboron Reagents
Edelstein, Emma K.,Namirembe, Sheila,Morken, James P.
, p. 5027 - 5030 (2017)
Palladium-catalyzed conjunctive cross-coupling is used for the synthesis of enantioenriched allylboron reagents. This reaction employs nonsymmetric bis(alkenyl)borates as substrates and appears to occur by a mechanism that involves selective activation of the less substituted alkene followed by migration of the more substituted alkene during the course of a Pd-induced metalate rearrangement.
Stereochemistry of Aliphatic Carbocations, 15. Rearrangements in 2-Arylalkyl Systems
Kirmse, Wolfgang,Guenther, Bernd-Rainer,Loosen, Karin
, p. 2140 - 2153 (2007/10/02)
Phenyl shifts from secondary to primary carbon proceed with virtually complete inversion at the migration origin, regardless whether they are induced by solvolysis of the aryl sulfonate 25 or by deamination of the amines 12, 17, 26, and 43.Sequential rearrangements (Ph, CH3 and Ph, H) are likewise stereo- and regiospecific.These results strongly support the intervention of phenonium ions.In contrast, the competitive alkyl shifts (deamination only) from benzylic to primary carbon produce but a small excess of inversion (Me 27percent, Et 13percent, iPr 20percent, tBu 3percent).Obviously, benzyl cations are the predominant intermediates.
