Asymmetric Introduction of Nucleophiles to the 2-Position of Pyrrolidine Ring through N-Acylpyrrolidinium Ion

Asymmetric carbon-carbon bond-forming reaction at the 2-position of a pyrrolidine ring was achieved. The reaction involved a chiral Ti(IV) catalyzed coupling between 1-methoxycarboyl-2-methoxypyrrolidine and silyl enol ethers to afford 2-substituted pyrrolidines with up to 53 % ee

Memory of Chirality in the Electrochemical Oxidation of N-o-Phenylbenzoylated Prolinols

Memory of chirality in electrochemical carbon-carbon bond cleavage of N-o-phenylbenzoylated (S)-prolinol derivatives was observed. Substituents of the α-position affected the ee of the products. The reaction of α,α-diarylated (S)-prolinol derivatives proceeded smoothly to afford optically active α-methoxylated pyrrolidine with up to 73% ee

Nonenzymatic kinetic resolution of racemic β-hydroxyalkanephosphonates with a chiral copper catalyst

Kinetic resolution of β-hydroxyalkanephosphonates was efficiently performed by 2-fluorobenzoylation in the presence of copper(II) triflate and (R,R)-Ph-BOX as a catalyst with good s value of up to 21

New organic activators for the enantioselective reduction of aromatic imines with trichlorosilane

N-Picolinoyl-(2S)-(diphenylhydroxymethyl)pyrrolidine was found to work as an organic activator in the reduction of aromatic imines to the corresponding amines by Cl3SiH. The highest selectivity was 80% ee. These are the first data showing that N-formyl group is not always essential as N-protecting group of pyrrolidine derivatives for the reduction of imines by Cl3SiH

Asymmetric oxidation of 1,2-diols using N-bromosuccinimide in the presence of chiral copper catalyst

Asymmetric oxidation of 1,2-diols using N-bromosuccinimide (NBS) in the presence of copper(II) triflate and (R,R)-Ph-BOX has been exploited. This oxidation was applicable to asymmetric desymmetrization of meso-hydrobenzoin and kinetic resolution of dl-hydrobenzoin and racemic-cycloalkane-cis-1,2-diols to afford optically active ﾎｱ-ketoalcohols with good to high enantiomeric excess

Copper complex catalyzed asymmetric monosulfonylation of meso-vic-diols

Asymmetric desymmetrization of meso-vic-diols was performed by tosylation in the presence of copper(II) triflate and (R,R)-Ph-BOX as a catalyst. The method was successfully applied to asymmetric desymmetrization of cyclic and acyclic meso-vic-diols in high enantioselectivity with up to >99% ee

Stereoselective synthesis of 3-deoxy-piperidine iminosugars from l-lysine

A new method using electrochemical oxidation and/or OsO4 oxidation has been used for the stereoselective synthesis of 2,3,6-trihydroxylated (5S)-piperidine derivatives. The electrochemical method was successively used for the conversion of N-protected piperidines to N-protected 1-methoxypiperidines and for the conversion of 2,3-didehydro-1-methoxypiperidine derivatives to 2,3-trans-1,2,3-triacetoxypiperidine derivatives. These triacetates were easily transformed into (2S,3S)-6-triacetoxy-(5S)-methylpiperidine and (2R,3R)-6-triacetoxy-(5S)-methylpiperidine. In addition, the 2,3-cis-dihydroxylation of 2,3-didehydro-1-methoxypiperidine derivatives with OsO4 afforded (2R,3S)-6-triacetoxy-(5S)-methylpiperidine and (2S,3R)-6-triacetoxy-(5S)-methylpiperidine

Catalytic monoalkylation of 1,2-diols

A catalytic monoalkylation of 1,2-diols by using a weak base has been developed. Copper(II) dichloride and boronic acids are effective catalysts for activating 1,2-diols in the presence of potassium carbonate as a base. Various 1,2-diols were selectively monoalkylated with allyl-, benzyl- and alkyl- halides in DMF by choosing a suitable catalyst for each 1,2-diols

Memory of Chirality in the Electrochemical Oxidation of Thiazolidine-4-carboxylic Acid Derivatives

Memory of chirality in the electrochemical oxidation of thiazolidine-4-carboxylic acid derivatives was observed. The relatively larger size of sulphur atom than the oxygen atom for oxazolidine-4-carboxylic acid derivative may slightly improved the enantioselectivities of the oxidized products. The bulkier penicillamine derivative 1c furnished 2c with much better enantioselectivity (91% ee) than that of the cysteine derivative 2b (85% ee). The presence of two extra dimethyl groups, for the penicillamine derivative improved the enantioselectivities of the thiazolidine derivatives from 85% ee to 91 % ee

Ring Contraction of α,β-Unsaturated Cyclic Amines with cis-Dihydroxylation at the α,β-Position

α,β-Unsaturated cyclic amines are oxidized by OsO4 to afford α,β-cis-dihydroxylated compounds which are thermodynamically transformed into ring-opened keto-alcohols. The keto-alcohols are then cyclized to form synthetically useful ring-contracted cyclic amines