Prolinamides containing 2-(2-aminocyclohexyl)phenols as highly enantioselective organocatalysts for aldol reactions.

Effective synthesis of prolinamides of 2-(2-aminocyclohexyl)phenols has been accomplished. The novel prolinamides are demonstrated to catalyze the direct aldol reaction between ketones and aldehydes with high stereoselectivity, thus affording up to 99 : 1 anti/syn diastereomeric and 99 : 1 enantiomeric ratio. Experimental results as well as computational investigations have revealed that the electrophile (e.g. aldehyde) is activated by dual hydrogen bonding with the amide NH and phenolic OH group of the catalyst. A rather large spacing between the H-bond donor groups and its conformational flexibility are remarkable structural features of the most enantioselective catalyst.

Catalyst-Tuned Electrophilic Chlorination of Diverse Aromatic Compounds with Sulfuryl Chloride and Regioselective Chlorination of Phenols with Organocatalysts.

In this work, we demonstrate that diverse aromatic compounds can be selectively chlorinated through the fine-tuning of the reactivity of sulfuryl chloride (SO2Cl2) by organocatalysts. Acetonitrile has been identified to activate SO2Cl2 most strongly, thus enabling even chlorination of p-xylene with high yields. 1,4-Dioxane effects chlorination of oxidation-labile aromatic compounds such as p-cresol and 2-naphthol with high yields, 95% and 85%, respectively. An array of potential catalysts has been screened for ortho- and para-selective chlorination of phenols. Thus, we found that acetonitrile, (S)-BINAPO (5 mol %), and diisopropyl ether (4.00 equiv) can catalyze the chlorination of phenols in a para-selective manner (with ≤4:96 o:p ratio), whereas Nagasawa's bis-thiourea (1 mol %), phenyl boronic acid (5 mol %), and (S)-diphenylprolinol (1 mol %) exhibit high ortho selectivity [with ≤99:1 o:p ratio by (S)-diphenylprolinol].

Total Synthesis of Olivacine and Ellipticine via a Lactone Ring-Opening and Aromatization Cascade.

Effective preparation of olivacine and ellipticine via late-stage D-ring cyclization is described. Key features of the synthetic routes include trifluoroacetic acid-mediated formation of a lactone that is fused to a tetrahydrocarbazole derivative and its one-pot two-step ring opening and aromatization mediated by para-toluenesulfonic acid and palladium on carbon, respectively.

Concise total syntheses of (±)-noruleine and (±)-uleine.

The first total synthesis of (±)-noruleine and a concise synthesis of (±)-uleine have been accomplished via the DDQ mediated dehydrogenative cyclization of a tetrahydrocarbazole derivative bearing a non-substituted amide functionality to prepare the key azocino[4,3-b]indole precursor.

An entry to the azocino[4,3-b]indole framework through a dehydrogenative activation of 1,2,3,4-tetrahydrocarbazoles mediated by DDQ: formal synthesis of (±)-uleine.

It is presented that hexahydro-1,5-methano[4,3-b]indoles were efficiently synthesized in high yields (up to 89% yield) through the cyclization reaction of starting tetrahydrocarbazoles bearing a monoalkylaminocarbonylmethyl moiety at the C-2 position mediated by 2,3-dichloro-5,6-dicyanobenzoquinone (DDQ). A mechanistic proposal is also given that mainly includes two cascade reactions: (i) formation of a vinylogous iminium cation via DDQ-mediated dehydrogenation of tetrahydrocarbazole functionality and (ii) intra-molecular and syn-selective addition of the amide functionality as the nucleophile to the vinylogous iminium cation. Furthermore, this cyclization reaction was successfully utilized in the formal total synthesis of (±)-uleine, an Aspidospermatan skeletal type alkaloid.

On the redox states of ruthenium porphyrin oxidation catalysts.

Tetraarylporphyrin ruthenium complexes [Ru(L)(aryl(4)Por)] (L = CO or PF(3); aryl = mesityl or 10-R'-bis-methano-octahydroanthracene-9-yl with R' = H, CF(3), OCH(3) or CH(3)) show a rich electrochemistry with at least five different stable oxidation states (including the parent state). The overall character of the redox behaviour is porphyrin-centred. However detailed spectroelectrochemical investigations using IR, UV/Vis/NIR and EPR spectroscopy (X- and K band) gave clear indication for ruthenium contributions.