A new synthetic route for axially chiral secondary amines with binaphthyl backbone and their applications in asymmetric Michael reaction of aldehydes to nitroalkenes.
نویسندگان
چکیده
A new synthetic route for binaphthyl-based secondary amines has been developed. The key features of this route include the selective direct esterification of the binaphthyl structure at the 3- or 3,3'-position and the methylation by a Negishi cross-coupling reaction. Based on the new approach, a series of 3-monosubstituted and 3,3'-disubstituted chiral secondary amines with a binaphthyl backbone were synthesized and screened in the Michael reaction of aldehydes to various nitroalkenes. 3-Monosubstituted secondary amine 7c was proved to be the best catalyst, affording high yields (up to 95%), good to excellent enantioselectivities (up to 99%) and diastereoselectivities (syn/anti up to 99:1) under the optimized conditions.
منابع مشابه
Direct asymmetric bromination of aldehydes catalyzed by a binaphthyl-based secondary amine: highly enantio- and diastereoselective one-pot synthesis of bromohydrins.
One-pot stereoselective synthesis of bromohydrins as a useful chiral building block was achieved by the reaction of Grignard reagents with optically active α-bromoaldehydes, which were in situ generated by direct asymmetric bromination of aldehydes catalyzed by a binaphthyl-based secondary amine (S)-3.
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Unusual anti-selectivity was observed in the conjugate addition of aldehydes to nitroalkenes, when a biphenyl-based chiral secondary amine was used as catalyst.
متن کاملDesign of an axially chiral amino acid with a binaphthyl backbone as an organocatalyst for a direct asymmetric aldol reaction.
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Design of novel chiral N,N,O-tridentate phenanthroline ligands and their application to enantioselective addition of organozinc reagents to aldehydes.
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A diastereo- and enantioselective aldol reaction between aldehydes and a synthetically useful ketomalonate 1c as a hydrated form was developed, and either anti- or syn-aldol adducts having a chiral tetrasubstituted carbon center were obtained in high enantioselectivities by use of a tetrazole analogue of L-proline (S)-2 or an axially chiral amino sulfonamide (S)-3 as catalyst.
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ورودعنوان ژورنال:
- Organic & biomolecular chemistry
دوره 10 15 شماره
صفحات -
تاریخ انتشار 2012