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Direct catalytic asymmetric Mannich-type reaction of hydroxyketone using a Et2Zn/linked-BINOL complex: synthesis of either anti- or syn-beta-amino alcohols.
J Am Chem Soc. 2004 Jul 21; 126(28):8777-85.JA

Abstract

Full details of a direct catalytic asymmetric Mannich-type reaction of a hydroxyketone using a Et2Zn/(S,S)-linked-BINOL complex are described. By choosing the proper protective groups on imine nitrogen, either anti- or syn-beta-amino alcohol was obtained in good diastereomeric ratio, yield, and excellent enantiomeric excess using the same zinc catalysis. N-Diphenylphosphinoyl (Dpp) imine 3 gave anti-beta-amino alcohols in anti/syn = up to >98/2, up to >99% yield, and up to >99.5% ee, while Boc-imine 4 gave syn-beta-amino alcohols in anti/syn = up to 5/95, up to >99% yield, and up to >99.5% ee. The high catalyst turnover number (TON) is also noteworthy. Catalyst loading was successfully reduced to 0.02 mol % (TON = up to 4920) for the anti-selective reaction and 0.05 mol % (TON = up to 1760) for the syn-selective reaction. The Et2Zn/(S,S)-linked-BINOL complex exhibited far better TON than in previous reports of catalytic asymmetric Mannich-type reactions. Mechanistic studies to clarify the reason for the high catalyst efficiency as well as transformations of Mannich adducts are also described.

Authors+Show Affiliations

Graduate School of Pharmaceutical Sciences, The University of Tokyo, Hongo, Bunkyo-ku, Tokyo 113-0033, Japan.No affiliation info availableNo affiliation info availableNo affiliation info availableNo affiliation info available

Pub Type(s)

Journal Article
Research Support, Non-U.S. Gov't

Language

eng

PubMed ID

15250731

Citation

Matsunaga, Shigeki, et al. "Direct Catalytic Asymmetric Mannich-type Reaction of Hydroxyketone Using a Et2Zn/linked-BINOL Complex: Synthesis of Either Anti- or Syn-beta-amino Alcohols." Journal of the American Chemical Society, vol. 126, no. 28, 2004, pp. 8777-85.
Matsunaga S, Yoshida T, Morimoto H, et al. Direct catalytic asymmetric Mannich-type reaction of hydroxyketone using a Et2Zn/linked-BINOL complex: synthesis of either anti- or syn-beta-amino alcohols. J Am Chem Soc. 2004;126(28):8777-85.
Matsunaga, S., Yoshida, T., Morimoto, H., Kumagai, N., & Shibasaki, M. (2004). Direct catalytic asymmetric Mannich-type reaction of hydroxyketone using a Et2Zn/linked-BINOL complex: synthesis of either anti- or syn-beta-amino alcohols. Journal of the American Chemical Society, 126(28), 8777-85.
Matsunaga S, et al. Direct Catalytic Asymmetric Mannich-type Reaction of Hydroxyketone Using a Et2Zn/linked-BINOL Complex: Synthesis of Either Anti- or Syn-beta-amino Alcohols. J Am Chem Soc. 2004 Jul 21;126(28):8777-85. PubMed PMID: 15250731.
* Article titles in AMA citation format should be in sentence-case
TY - JOUR T1 - Direct catalytic asymmetric Mannich-type reaction of hydroxyketone using a Et2Zn/linked-BINOL complex: synthesis of either anti- or syn-beta-amino alcohols. AU - Matsunaga,Shigeki, AU - Yoshida,Takamasa, AU - Morimoto,Hiroyuki, AU - Kumagai,Naoya, AU - Shibasaki,Masakatsu, PY - 2004/7/15/pubmed PY - 2004/10/14/medline PY - 2004/7/15/entrez SP - 8777 EP - 85 JF - Journal of the American Chemical Society JO - J. Am. Chem. Soc. VL - 126 IS - 28 N2 - Full details of a direct catalytic asymmetric Mannich-type reaction of a hydroxyketone using a Et2Zn/(S,S)-linked-BINOL complex are described. By choosing the proper protective groups on imine nitrogen, either anti- or syn-beta-amino alcohol was obtained in good diastereomeric ratio, yield, and excellent enantiomeric excess using the same zinc catalysis. N-Diphenylphosphinoyl (Dpp) imine 3 gave anti-beta-amino alcohols in anti/syn = up to >98/2, up to >99% yield, and up to >99.5% ee, while Boc-imine 4 gave syn-beta-amino alcohols in anti/syn = up to 5/95, up to >99% yield, and up to >99.5% ee. The high catalyst turnover number (TON) is also noteworthy. Catalyst loading was successfully reduced to 0.02 mol % (TON = up to 4920) for the anti-selective reaction and 0.05 mol % (TON = up to 1760) for the syn-selective reaction. The Et2Zn/(S,S)-linked-BINOL complex exhibited far better TON than in previous reports of catalytic asymmetric Mannich-type reactions. Mechanistic studies to clarify the reason for the high catalyst efficiency as well as transformations of Mannich adducts are also described. SN - 0002-7863 UR - https://www.unboundmedicine.com/medline/citation/15250731/Direct_catalytic_asymmetric_Mannich_type_reaction_of_hydroxyketone_using_a_Et2Zn/linked_BINOL_complex:_synthesis_of_either_anti__or_syn_beta_amino_alcohols_ L2 - https://dx.doi.org/10.1021/ja0482435 DB - PRIME DP - Unbound Medicine ER -