5457-27-2Relevant articles and documents
Catalytic Kinetic Resolution of Disubstituted Piperidines by Enantioselective Acylation: Synthetic Utility and Mechanistic Insights
Wanner, Benedikt,Kreituss, Imants,Gutierrez, Osvaldo,Kozlowski, Marisa C.,Bode, Jeffrey W.
supporting information, p. 11491 - 11497 (2015/09/21)
The catalytic kinetic resolution of cyclic amines with achiral N-heterocyclic carbenes and chiral hydroxamic acids has emerged as a promising method to obtain enantio-enriched amines with high selectivity factors. In this report, we describe the catalytic kinetic resolution of disubstituted piperdines with practical selectivity factors (s, up to 52) in which we uncovered an unexpected and pronounced conformational effect resulting in disparate reactivity and selectivity between the cis- and trans-substituted piperidine isomers. Detailed experimental and computational studies of the kinetic resolution of various disubstituted piperidines revealed a strong preference for the acylation of conformers in which the α-substituent occupies the axial position. This work provides further experimental and computational support for the concerted 7-member transition state model for acyl transfer reagents and expands the scope and functional group tolerance of the secondary amine kinetic resolution.
A Novel Route to 6-Substituted Piperidin-3-ols via Domino Cyclization of 2-Hydroxy-6-phosphinyl-5-hexenyl Tosylates with Primary Amines: Synthesis of (±)-Pseudoconhydrine and (±)- epi -Pseudoconhydrine
Scherner, Cathrin,Ergüden, Jens-Kerim,Adiwidjaja, Gunadi,Schaumann, Ernst
, p. 2506 - 2514 (2015/12/26)
2-Hydroxy-6-phosphinyl-5-hexenyl tosylates, oxirane ring-opening products derived from glycidyl tosylates and phosphinyl-substituted allyl anions, undergo domino SN2-Michael reactions with primary amines to give 6-phosphinylmethylpiperidin-3-ols. The phosphinyl unit can be used in Horner olefination reactions. This approach is applied to the synthesis of racemic pseudoconhydrine and its epimer.
Hydroboration of Enecarbamates and the Synthesis of β-Hydroxypiperidine Alkaloids
Plehiers, Mark,Hootele, Claude
, p. 7569 - 7570 (2007/10/02)
The β-hydroxypiperidine alkaloids 5, 6 and 8 were diastereoselectively synthesized using hydroboration of enecarbamates 2b-c as a key step.