91142-22-2Relevant academic research and scientific papers
Dynamic Kinetic Resolution of Alkenyl Cyanohydrins Derived from α,β-Unsaturated Aldehydes: Stereoselective Synthesis of E-Tetrasubstituted Olefins
Majhi, Jadab,Turnbull, Ben W. H.,Ryu, Ho,Park, Jiyong,Baik, Mu-Hyun,Evans, P. Andrew
, p. 11770 - 11774 (2019/08/16)
A novel dynamic kinetic resolution (DKR) of tetrasubstituted alkenyl cyanohydrins prepared from the corresponding α,β-unsaturated aldehydes is described. The deprotonation of a geometrical mixture of tetrasubstituted alkenyl cyanohydrins with sodium diiso
Contiguous Quaternary Centers from a AuI-Catalyzed Nazarov Cyclization
Congmon, Jonathan,Tius, Marcus A.
supporting information, p. 2926 - 2930 (2018/06/27)
The cationic AuI-catalyzed cyclization of highly substituted enynes has been shown to provide cyclopentenones with up to two contiguous, all-carbon atom quaternary centers in a diastereospecific process. In the more challenging examples in whic
Stereochemistry of Carbenic 1,2-Vinyl Shifts
Kirmse, Wolfgang,Kopannia, Siegfried
, p. 1178 - 1184 (2007/10/03)
Various 1-phenylbut-3-enylidenes, (Ph)CCR2CH=CHR', were generated thermally and photolytically from tosylhydrazone (diazo) precursors. 1,2-Vinyl shifts, leading to 1,3-dienes, R′CH=CHC(Ph)=CR2, were found to predominate over γ-C-H insertion (R = Me) and to compete with 1,2-H shifts (R = H). Intramolecular addition to the double bond was detected in the case of R = R′ = Me. The resulting bicyclobutane is thermally stable and does not mediate the vinyl shift. Stereospecific migration of 1-propenyl groups (R′ = Me), with retention of configuration, was observed on thermolysis and direct photolysis of appropriate substrates. These data exclude the intervention of a triplet diradical and point to vinyl migration in the singlet manifold. Benzophenone-sensitized generation of the carbenes led to partial stereomutation but did not provide conclusive evidence for a triplet rearrangement (isomerization of the diene products could not be avoided under these conditions).
