Enantioselective α-amination enabled by a BINAM-derived phase-transfer catalyst

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Enantioselective α-amination enabled by a BINAM-derived phase-transfer catalyst† †Electronic supplementary information (ESI) available: Procedures and characterization data. CCDC 1025135. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c4sc02494j Click here for additional data file. Click here for additional data file.

Chiral anion phase-transfer of aryldiazonium cations was utilized to achieve highly enantioselective α-amination of carbonyl compounds. A broad scope of indanone- and benzosuberone-derived substrates was amenable to this strategy. Critical to obtaining high levels of enantioselectivity was the use of BINAM-derived phosphoric acids. The utility of this transformation was demonstrated through fac...

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Enantioselective synthesis of α-halo-α-alkylmalonates via phase-transfer catalytic α-alkylation.

A new enantioselective synthetic method for α-halo-α-alkylmalonates is reported. α-Alkylation of diphenylmethyl tert-butyl α-halomalonates under phase-transfer catalytic conditions (solid KOH, toluene, -40 °C) in the presence of (S,S)-3,4,5-trifluorophenyl-NAS bromide (5 mol%) afforded diphenylmethyl tert-butyl α-halo-α-alkylmalonates in very high chemical yields (up to 99%) and optical yields ...

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Enantioselective organocatalytic reductive amination.

The first enantioselective organocatalytic reductive amination reaction has been accomplished. The development of a new chiral phosphoric acid catalyst has provided a convenient strategy for the enantioselective construction of protected primary amines and provided a highly stereoselective method for the reductive amination of heterocyclic amines. A diverse spectrum of ketone and amine substrat...

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A Nucleophilic Strategy for Enantioselective Intermolecular α-Amination: Access to Enantioenriched α-Arylamino Ketones.

The enantioselective addition of anilines to azoalkenes was accomplished through the use of a chiral phosphoric acid catalyst. The resulting α-arylamino hydrazones were obtained in good yields and excellent enantioselectivities and provide access to enantioenriched α-arylamino ketones. A serendipitous kinetic resolution of racemic α-arylamino hydrazones is also described.

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Enantioselective direct aldol reaction of α-keto esters catalyzed by (S(a))-binam-D-prolinamide under quasi solvent-free conditions.

(S(a))-Binam-D-prolinamide (20 mol%), instead of (S(a))-binam-L-prolinamide, in combination with chloroacetic acid (100 mol%) is an efficient organocatalyst for the direct aldol reaction between α-keto esters as electrophiles and alkyl and α-functionalised ketones, under quasi solvent-free conditions, providing access to highly functionalised chiral quaternary γ-keto α-hydroxyesters with up to ...

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ژورنال

عنوان ژورنال: Chemical Science

سال: 2015

ISSN: 2041-6520,2041-6539

DOI: 10.1039/c4sc02494j