Asymmetric Transfer Hydrogenation Catalyzed by Chiral Ruthenium Complexes

Claisen rearrangement over the past nine decades.

α,α-Diaryl(dialkyl)prolinol ethers constitute a potent organocatalyst family which has been shown to be very general for a broad range of reactions involving enamine and iminium ion activation or a combination of both. The reactions are characterized by an efficient steric control approach and can lead to a variety of α-, β-, γ-, and α,β-functionalized carbonyl compounds with excellent stereocontrol. As a full expression of their catalytic activity, these compounds are also excellent promoters of elegant cascade processes and valuable catalysts in water-compatible systems.



Los trimetilsilil eteres derivados del prolinol han emergido como potentes organocatalizadores que permiten la funcionalizacion de compuestos carbonilicos tanto via enamina como ion iminio. Actualmente se han descrito diferentes procedimientos para la alfa, beta, gamma y alfa-beta funcionalizacion, asi como procesos en cascada y multicomponentes de gran interes para la comunidad cientifica. En esta revision se presentan los ultimos avances en este contexto.

α,α-Diarylprolinol Ethers: New Tools for Functionalization of Carbonyl Compounds

http://www.chtf.stuba.sk/~szolcsanyi/education/files/Organicka%20chemia%20II/Prednaska%201_Aminy_Vlastnosti%20a%20priprava/Doplnkove%20studijne%20materialy/Structure%20and%20Properties/Quaternary%20centres%20bearing%20nitrogen%20(a-tertiary%20amines)%20as%20products%20of%20molecules%20rearrangements.pdf

Quaternary centres bearing nitrogen (α-tertiary amines) as products of molecular rearrangements

The nature and the size of the benzylic substituent are shown to be the key to controlling receptor selectivity (CCR5 vs M1, M2) and potency in the title compounds. Optimization of the lead benzylic methyl compound 3 led to the methoxymethyl analogue 30, which had excellent receptor selectivity and oral bioavailability in rats and monkeys. Compound 30 (Sch-417690/Sch-D), a potent inhibitor of HIV-1 entry into target cells, is currently in clinical trials.

Piperazine-based CCR5 antagonists as HIV-1 inhibitors. IV. Discovery of 1-[(4,6-dimethyl-5-pyrimidinyl)carbonyl]- 4-[4-[2-methoxy-1(R)-4-(trifluoromethyl)phenyl]ethyl-3(S)-methyl-1-piperazinyl]- 4-methylpiperidine (Sch-417690/Sch-D), a potent, highly selective, and orally bioavailable CCR5 antagonist.

Synthese d'amines allyliques N-tosylees, N-t-butoxycarbonylees et N-benzyloxycarbonylees, d'(alcene-2yl alkyl) amines et d'α-aminoacides. Mecanismes de la transposition des seleniures allyliques

Allylic selenides in organic synthesis: new methods for the synthesis of allylic amines

Treatment of the ketone (Ia) with sodium methylate yields the enol (II) instead of the expected epimeric ketone (Ib).

Daniel V. Pratt

Papers

Allylic selenides in organic synthesis: new methods for the synthesis of allylic amines

Isolation and characterization of a stable simple enol

Synthesis of protected racemic β,γ-unsaturated-α-amino acids via γ-phenylseleno-α,β-unsaturated esters

Practical large-scale oxidation of 1,4-hydroquinones to 1,4-benzoquinones using hydrogen peroxide/catalytic diphenyl diselenide

Diastereocontrol of the Claisen rearrangement by substituents external to the pericyclic array: synthetic studies on betaenone B and stemphyloxin I