Catalytic Enantioselective Synthesis of β‐Lactams: Intramolecular Kinugasa Reactions and Interception of an Intermediate in the Reaction Cascade
10.1002/anie.200352103
Crossref journal-article
Wiley
Angewandte Chemie International Edition (311)
Bibliography

Shintani, R., & Fu, G. C. (2003). Catalytic Enantioselective Synthesis of β‐Lactams: Intramolecular Kinugasa Reactions and Interception of an Intermediate in the Reaction Cascade. Angewandte Chemie International Edition, 42(34), 4082–4085. Portico.

Authors 2
  1. Ryo Shintani (first)
  2. Gregory C. Fu (additional)
References 56 Referenced 173
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  5. For reviews on the synthetic organic chemistry of β‐lactams see:
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  42. Similarly in the only study by others of a catalytic asymmetric Kinugasa reaction Miura et al. found bisoxazoline4to be only modestly effective as a chiral ligand for copper‐catalyzed intermolecular couplings of alkynes with nitrones (maximumeevalue: 57 %).[7]
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  46. The data for ligands5 aand6in Table 1 (entries 3 and 5) indicate that the central chirality of the oxazoline subunit is the dominant stereocontrol element and that the planar chirality of the phosphaferrocene subunit plays a subordinate although significant role.
  47. The absolute configuration of the product was determined through X‐ray crystallographic analysis of the bis(amide) that is produced upon the reaction of β‐lactam3with excess 2‐bromobenzylamine (see Supporting Information).
  48. Notes for Table 2 entry 1: 1) When CuBr is used the product is furnished with somewhat highereevalues than with CuCl CuI Cu(OTf) Cu(MeCN)4BF4 or Cu(SCN). 2) The course of the coupling is highly dependent on the (C6H11)2NMe/Cu ratio (e.g. a 20:1 ratio leads to a substantial increase in side reactions). 3) The use of bases such as K3PO4⋅H2O K2CO3 1 4‐diazabicyclo[2.2.2]octane (dabco) 2 6‐lutidine KF NEt3 1 8‐diazabicyclo[5.4.0]undec‐7‐ene (DBU) and KOH results in an erosion in enantioselectivity and/or yield. 4) The use of MeCN as the solvent gives rise to much cleaner reactions than the use of CH2Cl2 THF dioxane N N‐dimethylformamide (DMF) acetone or 2‐methylbutan‐2‐ol. 5) Kinugasa reactions ofN‐phenyl andN‐(4‐carboethoxyphenyl)‐substituted nitrones lead to β‐lactams with similareevalues but couplings ofN‐(4‐carboethoxyphenyl)‐substituted nitrones generally proceed in somewhat better yield. In the case of anN‐benzyl‐ rather than anN‐(4‐carboethoxyphenyl)‐substituted nitrone theeevalue and the yield of the β‐lactam are lower. We have not attempted to optimize these processes. 6) Recrystallization of the β‐lactam from Et2O enhances theeevalue (>99 %ee; 53 % recovery).
  49. Ligands5 aand5 bpromote similar enantioselectivity in the synthesis of 6 4 bicyclic systems (Table 2 entries 1–4). However the yields are generally higher when5 ais employed. For the synthesis of 7 4 bicyclic systems (Table 2 entries 5 and 6) comparable yields were observed when ligands5 aor5 bwere used but somewhat bettereevalues (up to 15 % higher) were observed in the presence of ligand5 b.
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  55. Another potential complication is the reaction of a nucleophilic Brønsted base (e.g. a tertiary amine) with the electrophile (E+).
  56. When KOAc/Ph(Me3SiO)CCH2is used instead of (C6H11)2NMe acetophenone is presumably generated rather than a trialkylammonium salt. Acetophenone is a poor proton donor compared to a trialkylammonium salt.
Dates
Type When
Created 21 years, 11 months ago (Sept. 10, 2003, 9:32 a.m.)
Deposited 1 year, 10 months ago (Oct. 10, 2023, 4:12 p.m.)
Indexed 1 week ago (Aug. 26, 2025, 2:48 a.m.)
Issued 21 years, 11 months ago (Sept. 5, 2003)
Published 21 years, 11 months ago (Sept. 5, 2003)
Published Online 21 years, 11 months ago (Sept. 5, 2003)
Published Print 21 years, 11 months ago (Sept. 5, 2003)
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@article{Shintani_2003, title={Catalytic Enantioselective Synthesis of β‐Lactams: Intramolecular Kinugasa Reactions and Interception of an Intermediate in the Reaction Cascade}, volume={42}, ISSN={1521-3773}, url={http://dx.doi.org/10.1002/anie.200352103}, DOI={10.1002/anie.200352103}, number={34}, journal={Angewandte Chemie International Edition}, publisher={Wiley}, author={Shintani, Ryo and Fu, Gregory C.}, year={2003}, month=sep, pages={4082–4085} }