Optimisation of catalytic asymmetric intermolecular cyclopropanation of diazo acetoxy acetone and styrene with p-NITRO-Ru(II)-DIPHENYL-PHEOX complex
PDF (Vietnamese)

Keywords

p-nitro-Ru(II)-diphenyl-Pheox
asymmetric chemistry
Ru(II)-Pheox catalyst
diazo ketones
asymmetric cyclopropanation p-nitro-Ru(II)-diphenyl-Pheox
tổng hợp bất đối xứng
diazo ketone
phản ứng tạo sản phẩm đối quang cyclopropane
Ru(II)-Pheox

How to Cite

1.
Lê TLC, Iwasa S. Optimisation of catalytic asymmetric intermolecular cyclopropanation of diazo acetoxy acetone and styrene with p-NITRO-Ru(II)-DIPHENYL-PHEOX complex. hueuni-jns [Internet]. 2025Jun.17 [cited 2025Oct.9];134(1C):101-8. Available from: https://jos.hueuni.edu.vn/index.php/hujos-ns/article/view/7057

Abstract

The chiral cyclopropane ring is an important pharmacophore in pharmaceuticals and bioactive natural products, making libraries of these building blocks a valuable resource for drug discovery and development. Furthermore, the cyclopropyl ketone groups found in natural products have important biochemical properties, but only a-diazo acetophenone is developed as a ketone source, reported with 67% and 86% enantioselectivity yields. Therefore, this study presents a process to synthesise chiral cyclopropane of diazo acetoxy acetone and styrene catalysed by asymmetric p-nitro-Ru-¬dialkyl-pheox complex. This procedure was optimised under suitable solvent and temperature conditions and achieved high yields, excellent stereoisomer selectivity of more than 99:1, and enantioselectivity up to 95%. This is our exclusive published result, demonstrating the effectiveness of this catalyst in the reaction to produce highly stereoselective cyclopropanes. In addition, the study also has sufficient evidence on the mechanism of chiral cyclopropane formation with preferential trans product.

https://doi.org/10.26459/hueunijns.v134i1C.7057
PDF (Vietnamese)

References

  1. Chen DYK, Pouwer RH, Richard J-A. Recent advances in the total synthesis of cyclopropane-containing natural products. Chemical Society Reviews. 2012;41(13):4631-42.
  2. Bouet A, Heller B, Papamicaël C, Dupas G, Oudeyer S, Marsais F, et al. Preparation of new axially chiral bridged 2,2′-bipyridines and pyridyl monooxazolines (pymox). Evaluation in copper(i)-catalyzed enantioselective cyclopropanation. Organic & Biomolecular Chemistry. 2007;5(9):1397-404.
  3. Rosenberg ML, Krivokapic A, Tilset M. Highly cis-Selective Cyclopropanations with Ethyl Diazoacetate Using a Novel Rh(I) Catalyst with a Chelating N-Heterocyclic Iminocarbene Ligand. Organic Letters. 2009;11(3):547-50.
  4. Wang H-X, Guan F-J, Xie M-S, Qu G-R, Guo H-M. Construction of All-Carbon Quaternary Stereocenters via Asymmetric Cyclopropanations: Synthesis of Chiral Carbocyclic Pyrimidine Nucleosides. 2018;360(11):2233-8.
  5. Zhu S, Xu X, Perman JA, Zhang XP. A General and Efficient Cobalt(II)-Based Catalytic System for Highly Stereoselective Cyclopropanation of Alkenes with α-Cyanodiazoacetates. Journal of the American Chemical Society. 2010;132(37):12796-9.
  6. Suematsu H, Kanchiku S, Uchida T, Katsuki T. Construction of Aryliridium−Salen Complexes: Enantio- and Cis-Selective Cyclopropanation of Conjugated and Nonconjugated Olefins. Journal of the American Chemical Society. 2008;130(31):10327-37.
  7. Chanthamath S, Iwasa S. Enantioselective Cyclopropanation of a Wide Variety of Olefins Catalyzed by Ru(II)–Pheox Complexes. Accounts of Chemical Research. 2016;49(10):2080-90.
  8. Chanthamath S, Takaki S, Shibatomi K, Iwasa S. Highly Stereoselective Cyclopropanation of α,β-Unsaturated Carbonyl Compounds with Methyl (Diazoacetoxy)acetate Catalyzed by a Chiral Ruthenium(II) Complex. 2013;52(22):5818-21.
  9. Hao W, Harenberg JH, Wu X, MacMillan SN, Lin S. Diastereo- and Enantioselective Formal [3 + 2] Cycloaddition of Cyclopropyl Ketones and Alkenes via Ti-Catalyzed Radical Redox Relay. Journal of the American Chemical Society. 2018;140(10):3514-7.
  10. Rodríguez AD, Shi J-G. Isolation, Structure Elucidation, and Synthesis of Bisgersolanolide, a Novel Heptacyclic Bis-diterpenoid from the Gorgonian Octocoral Pseudopterogorgia bipinnata. Organic Letters. 1999;1(2):337-40.
  11. Nicolas I, Roisnel T, Maux PL, Simonneaux G. Asymmetric intermolecular cyclopropanation of alkenes by diazoketones catalyzed by Halterman iron porphyrins. Tetrahedron Letters. 2009;50(36):5149-51.
  12. Bauta W, Dodd J, Bullington J, Gauthier D, Leo G, McDonnell P. Stereoselectivity in the rhodium(II) acetate catalysed cyclopropanations of 2-diazo-1-indanone with styrenes. Tetrahedron Letters. 2000;41(10):1491-4.
  13. Le TLC, Iwasa S. A scope of chiral cyclopropane of diazo acetoxy acetone with styrene derivatives, diazo acetoxy acetone derivatives with styrene catalyzed by p-nitro- Ru(ii)-diphenyl-Pheox . Hue University Journal of Science: Natural Science. 2023;132(1C):99-113.
  14. Deng G, Luo J. Silver(I)-catalyzed reaction of terminal alkynes with (diacetoxyiodo)benzene: a convenient, efficient and clean preparation of α-acetoxy ketones. Tetrahedron. 2013;69(29):5937-44.
  15. Toma T, Shimokawa J, Fukuyama T. N,N‘-Ditosylhydrazine: A Convenient Reagent for Facile Synthesis of Diazoacetates. Organic Letters. 2007;9(16):3195-7.
  16. Xia Y, Qiu D, Wang J. Transition-Metal-Catalyzed Cross-Couplings through Carbene Migratory Insertion. Chemical Reviews. 2017;117(23):13810-89.
  17. Chanthamath S, Phomkeona K, Shibatomi K, Iwasa S. Highly stereoselective Ru(ii)–Pheox catalyzed asymmetric cyclopropanation of terminal olefins with succinimidyl diazoacetate. Chemical Communications. 2012;48(62):7750-2.
  18. Chi LTL, Suharto A, Da HL, Chanthamath S, Shibatomi K, Iwasa S. Catalytic Asymmetric Intermolecular Cyclopropanation of a Ketone Carbene Precursor by a Ruthenium(II)-Pheox Complex. 2019;361(5):951-5.
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