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A direct catalytic asymmetric Mannich-type reaction via a dinuclear zinc catalyst: synthesis of either anti- or syn-alpha-hydroxy-beta-amino ketones.
J Am Chem Soc. 2006 Mar 08; 128(9):2778-9.JA

Abstract

The use of imines bearing a hydrolyzable nitrogen substituent in direct asymmetric Mannich reactions with alpha-hydroxyketones is developed. Previous work focused on the use of N-arylimines or nonenolizable imines, and the latter with only methoxy-substituted alpha-hydroxyacetophenones. Using a dinuclear catalyst devised from 2,6-di-(S)-2'-diphenylhydroxymethylpyrrolidino-N-methyl)-4-methylphenol and diethylzinc, a broad array of hydroxyacetylated aromatics, including phenyl, 2-furyl, 1-naphthyl, and 2-naphthyl, react well. In addition, the reactions focused on the use of enolizable imines. With the N-diphenylphosphinoyl, the reactions are anti selective with enantiomeric excesses ranging from 83 to 99%, except for the reaction of the 2-methoxy-2'-hydroxyacetylbenzene. With the N-Boc-imines, the reactions were syn selective with enantiomeric excesses from 90 to 94%. The dependence of the diastereoselectivity on the nature of the N-substituent presumably arises from the steric demands of the diphenylphosphinoyl group.

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Publisher Full Text
ncbi.nlm.nih.gov
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Authors+Show Affiliations

Trost BM
Department of Chemistry, Stanford University, Stanford, CA 94305-5080, USA. bmtrost@stanford.edu
Jaratjaroonphong J
No affiliation info available
Reutrakul V
No affiliation info available

MeSH

Amino AlcoholsCatalysisIminesKetonesNaphtholsOrganometallic CompoundsStereoisomerismZinc

Pub Type(s)

Journal Article
Research Support, N.I.H., Extramural
Research Support, Non-U.S. Gov't
Research Support, U.S. Gov't, Non-P.H.S.

Language

eng

PubMed ID

16506738

Citation

Trost, Barry M., et al. "A Direct Catalytic Asymmetric Mannich-type Reaction Via a Dinuclear Zinc Catalyst: Synthesis of Either Anti- or Syn-alpha-hydroxy-beta-amino Ketones." Journal of the American Chemical Society, vol. 128, no. 9, 2006, pp. 2778-9.
Trost BM, Jaratjaroonphong J, Reutrakul V. A direct catalytic asymmetric Mannich-type reaction via a dinuclear zinc catalyst: synthesis of either anti- or syn-alpha-hydroxy-beta-amino ketones. J Am Chem Soc. 2006;128(9):2778-9.
Trost, B. M., Jaratjaroonphong, J., & Reutrakul, V. (2006). A direct catalytic asymmetric Mannich-type reaction via a dinuclear zinc catalyst: synthesis of either anti- or syn-alpha-hydroxy-beta-amino ketones. Journal of the American Chemical Society, 128(9), 2778-9.
Trost BM, Jaratjaroonphong J, Reutrakul V. A Direct Catalytic Asymmetric Mannich-type Reaction Via a Dinuclear Zinc Catalyst: Synthesis of Either Anti- or Syn-alpha-hydroxy-beta-amino Ketones. J Am Chem Soc. 2006 Mar 8;128(9):2778-9. PubMed PMID: 16506738.
* Article titles in AMA citation format should be in sentence-case
TY - JOUR T1 - A direct catalytic asymmetric Mannich-type reaction via a dinuclear zinc catalyst: synthesis of either anti- or syn-alpha-hydroxy-beta-amino ketones. AU - Trost,Barry M, AU - Jaratjaroonphong,Jaray, AU - Reutrakul,Vichai, PY - 2006/3/2/pubmed PY - 2006/5/5/medline PY - 2006/3/2/entrez SP - 2778 EP - 9 JF - Journal of the American Chemical Society JO - J Am Chem Soc VL - 128 IS - 9 N2 - The use of imines bearing a hydrolyzable nitrogen substituent in direct asymmetric Mannich reactions with alpha-hydroxyketones is developed. Previous work focused on the use of N-arylimines or nonenolizable imines, and the latter with only methoxy-substituted alpha-hydroxyacetophenones. Using a dinuclear catalyst devised from 2,6-di-(S)-2'-diphenylhydroxymethylpyrrolidino-N-methyl)-4-methylphenol and diethylzinc, a broad array of hydroxyacetylated aromatics, including phenyl, 2-furyl, 1-naphthyl, and 2-naphthyl, react well. In addition, the reactions focused on the use of enolizable imines. With the N-diphenylphosphinoyl, the reactions are anti selective with enantiomeric excesses ranging from 83 to 99%, except for the reaction of the 2-methoxy-2'-hydroxyacetylbenzene. With the N-Boc-imines, the reactions were syn selective with enantiomeric excesses from 90 to 94%. The dependence of the diastereoselectivity on the nature of the N-substituent presumably arises from the steric demands of the diphenylphosphinoyl group. SN - 0002-7863 UR - https://www.unboundmedicine.com/medline/citation/16506738/A_direct_catalytic_asymmetric_Mannich_type_reaction_via_a_dinuclear_zinc_catalyst:_synthesis_of_either_anti__or_syn_alpha_hydroxy_beta_amino_ketones_ L2 - https://doi.org/10.1021/ja057498v DB - PRIME DP - Unbound Medicine ER -