Palladium Catalyzed Ring-Opening of Diazabicylic Olefins with 4-Halo-1,3-Dicarbonyl Compounds: Accessing 3(2H)-Furanone-Appended Cyclopentenes
Vishnu K. Omanakuttan, Alisha Valsan, Henning Hopf, Jubi John
Organics · pp. 70–85 · Published 13 Feb 2023
10.3390/org4010006Abstract
We have realized a Pd-catalyzed ring-opening of diazabicyclic olefins with 4-halo-1,3-dicarbonyl compounds. This reaction resulted in the formation of 3(2H)-furanone-appended hydrazino cyclopentenes. The reaction proceeds via the formation of a π-allylpalladium intermediate which is attacked by the active methylene species, and an intramolecular nucleophilic substitution in the 4-halo-1,3-dicarbonyl moiety furnishes the 3(2H)-furanone-substituted cyclopentene. We could extend this methodology to cyclopropane-appended spirotricyclic olefin for synthesizing 3(2H)-furanone-substituted spiro[2.4]hept-5-ene.
References (53)
- 1 1999, The naturally occurring furanones: Formation and function from pheromone to food [DOI]
- 2 Carter, N.B., Nadanya, A.E., and Sweeney, J.B. (2002). Recent developments in the synthesis of furan-2(5H)-ones. J. Chem. Soc. Perkin Trans. 1., 2324. [DOI]
- 3 Fusetani, N., and Clare, A.S. (2006). Marine Molecular Biotechnology, Springer.
- 4 Schwab, W. (2013). Natural 4-Hydroxy-2,5-dimethyl-3(2H)-furanone. Molecules, 18. [DOI]
- 5 Husain, 2019, Insights into the chemistry and therapeutic potential of furanones: A versatile pharmacophore [DOI]
- 6 Smith, 1981, Synthesis and reactions of simple 3(2H)-furanones [DOI]
- 7 Jerris, 1981, Synthesis and configurational assignment of geiparvarin: A novel antitumor agent [DOI]
- 8 Marson, C.M., Edaan, E., Morrell, J.M., Coles, S.J., Hursthouse, M.B., and Davies, D.T. (2007). A catalytic asymmetric protocol for the enantioselective synthesis of 3(2H)-furanones. Chem. Commun., 2494. [DOI]
- 9 Haug, 2009, Synthesis and chemistry of 3(2H)-furanones
- 10 Omanakuttan, 2021, Synthesis of 3(2H)-furanones-a review [DOI]
- 11 Dou, 2012, From the Feist–Bénary Reaction to Organocatalytic Domino Michael–Alkylation Reactions: Asymmetric Synthesis of 3(2H)-Furanones [DOI]
- 12 Yan, 2012, Synthesis of chiral tetronic acid derivatives via organocatalytic conjugate addition of ethyl 4-chloro-3-oxobutanoate to nitroalkenes [DOI]
- 13 Zhou, 2017, Organocatalytic asymmetric domino Michael/O-alkylation reaction for the construction of succinimide substituted 3(2H)-furanones catalyzed by quinine [DOI]
- 14 John, 2013, Substituted 3(2H)-Furanones by a Tandem Michael Addition/Palladium-Catalyzed Ring-Closing Protocol [DOI]
- 15 John, 2014, A tandem Mannich addition–palladium catalyzed ring-closing route toward 4-substituted-3-(2H)-furanones [DOI]
- 16 John, 2019, Tandem α-Arylation/Cyclization of 4-Haloacetoacetates with Arynes: A Metal-Free Approach toward 4-Aryl-3-(2H)-furanones [DOI]
- 17 Omanakuttan, 2022, Tandem Reaction of 4-Halo-1,3-Dicarbonyl Compounds with Alkynes towards 4-Vinyl-3(2H)-Furanones and 3(2H)-Furanone fused 2-Pyridones [DOI]
- 18 Bournaud, 2009, Stereoselective Transformations of meso Bicyclic Hydrazines: Versatile Access to Functionalized Aminocyclopentanes [DOI]
- 19 Sajisha, 2009, Desymmetrization of meso-Bicyclic Hydrazines: An Efficient Strategy towards the Synthesis of Functionalized Cyclopentenes [DOI]
- 20 Pineschi, 2020, The Binomial Copper-Catalysis and Asymmetric Ring Opening of Strained Heterocycles: Past and Future Challenges [DOI]
- 21 Preethalayam, 2020, Diazanorbornene: A Valuable Synthon towards Carbocycles and Heterocycles [DOI]
- 22 Allred, 1966, Hydroboration of 2,3-dicarbomethoxy-2,3-diazabicyclo [2.2.1]hept-5-ene. The elimination mechanism of the organoborane intermediate [DOI]
- 23 Wilson, 1986, Synthesis of allylic alcohol single-chain PGH analogs. A synthetic application of the argon laser [DOI]
- 24 Bournaud, 2008, Desymmetrization of meso-Bicyclic Hydrazines by Rhodium-Catalyzed Enantioselective Hydroformylation [DOI]
- 25 Mellor, J.M., and Smith, N.M. (1984). Reductive cleavage of the nitrogen–nitrogen bond in hydrazine derivatives. J. Chem. Soc., Perkin Trans. 1, 2927–2931. [DOI]
- 26 Grabowski, 1997, Biocatalysis in the chiral recognition of meso-diamides—An efficient route from cyclic olefinic hydrocarbons to optically pure diamino-polyols [DOI]
- 27 Storsberg, 2001, Stereoselective Palladium-Catalyzed C-C Coupling Reactions with a Diazabicyclo [2.2.1]heptane [DOI]
- 28 Yao, 2002, Two-Step, Stereoselective Hydrazidoarylation of 1,3-Cyclopentadiene [DOI]
- 29 Radhakrishnan, 2005, Palladium-Catalyzed Reaction of Bicyclic Hydrazines with Allyl- and Arylstannanes in Ionic Liquid [bmim]PF6: A Facile Method for the Synthesis of Substituted Hydrazinocyclopentene Derivatives [DOI]
- 30 Sajisha, 2006, A facile synthesis of 3-allyl-4-hydrazinocyclopentenes by the palladium/Lewis acid mediated ring opening of bicyclic hydrazines with allyltributyltin and allyltrimethylsilane [DOI]
- 31 Sajisha, 2006, Palladium/Lewis Acid-Catalyzed Reactions of Bicyclic Hydrazines with Organostannanes: A General Methodology for the Stereoselective Synthesis of 3,4-Disubstituted Cyclopentenes [DOI]
- 32 John, J., Sajisha, V.S., Mohanlal, S., and Radhakrishnan, K.V. (2006). Iodine assisted modified Suzuki type reaction of bicyclic hydrazines: Stereoselective synthesis of functionalized cyclopentene. Chem. Commun., 3510–3512. [DOI]
- 33 Bournaud, 2006, On the Use of Phosphoramidite Ligands in Copper-Catalyzed Asymmetric Transformations with Trialkylaluminum Reagents [DOI]
- 34 Anas, 2007, Iodine assisted palladium catalyzed ring opening of bicyclic hydrazines with organoboronic acids: Stereoselective synthesis of functionalized cyclopentenes and alkylidene cyclopentenes [DOI]
- 35 John, 2007, Palladium-catalyzed ring opening of azabicyclic olefins with organoindium reagents: A simple, clean, and efficient synthesis of functionalized cyclopentenes [DOI]
- 36 John, 2010, Palladium catalyzed ring opening of azabicyclic olefins with organoindium and gallium reagents: A facile access towards benzylated cyclopentanoids [DOI]
- 37 Joseph, 2013, An exclusive approach to 3,4-disubstituted cyclopentenes and alkylidene cyclopentenes via the palladium catalyzed ring opening of azabicyclic olefins with aryl halides [DOI]
- 38 John, 2009, Palladium Catalyzed Tandem Ring Opening−Ring Closing Reaction of Diazabicyclic Alkenes: A Facile One Pot Strategy for Cyclopentannulation of Heterocycles [DOI]
- 39 John, 2013, Palladium catalyzed reaction of ortho-functionalized aryl iodides with bicyclic hydrazines: Facile route toward heteroannulated cyclopentenes and azabicycles [DOI]
- 40 Jijy, 2013, Rhodium catalyzed oxidative coupling of salicylaldehydes with diazabicyclic olefins: A one pot strategy involving aldehyde C–H cleavage and π-allyl chemistry towards the synthesis of fused ring chromanones [DOI]
- 41 Santhini, 2017, Pd-Catalyzed oxidative annulation of enamides with diazabicyclic olefins: Rapid access to cyclopentene fused 2-pyrrolines [DOI]
- 42 Santhini, 2018, Accessing highly functionalized cyclopentanoids via a cascade palladation approach: Unprecedented benzylic C–H activation towards cyclopentenoindanes [DOI]
- 43 Luna, 2003, Stereoselective Ring Opening of meso Bicyclic Hydrazines: A Straightforward Approach to Hydrazino Cyclopentenic Cores [DOI]
- 44 Rajan, 2010, Trapping the π-Allylpalladium Intermediate from Fulvene-Derived Azabicyclic Olefin with Soft Nucleophiles [DOI]
- 45 Jijy, 2014, Palladium-Catalyzed Ring Opening of Cyclopropane-Appended Spirotricyclic Olefins with Soft Nucleophiles and Organoboronic Acids: Facile Synthesis of Functionalized Spiro [2.4]heptenes [DOI]
- 46 Negishi, E. (2002). Hand Book of Organopalladium Chemistry for Organic Synthesis, Wiley-Interscience. [DOI]
- 47 Pashkovskii, 2006, Heterocyclic Analogs of Prostaglandins: III. Synthesis of 10-Oxa-13-Aza, 11-Oxa-13-Aza, and 9-Oxa-7-Aza Prostanoids from 3-Acyl-and 3-(3-Arylprop-2-enoyl)Furan-2,4-Diones [DOI]
- 48 Katritzky, A.R., Rees, C.W., and Scriven, E.F.V. (1996). 9.18—Eight-membered Rings with One Nitrogen Atom, Comprehensive Heterocyclic Chemistry II.
- 49 Listratova, 2017, Recent Advances in the Synthesis of Hydrogenated Azocine-Containing Molecules [DOI]
- 50 Mack, 1988, Drug-induced modifications of the immune response. 12. 4,5-Dihydro-4-oxo-2-(substituted amino)-3-furancarboxylic acids and derivatives as novel antiallergic agents [DOI]
- 51 Choi, 2003, Nonselective bromination-selective debromination strategy: Selective bromination of unsymmetrical ketones on singly activated carbon against doubly activated carbon [DOI]
- 52 Takaaki, K., and Katsumasa, H. (2000). Preparation of γ-Halogeno-β-keto esters, Japan. (Patent Application No. JP1999-56383; Patent No. JP2000256262).
- 53 Hu, 2012, Rotamers or diastereomers?
Cited by 0
No indexed citations yet.
Related research
- A Novel Catalytic Synthesis of Flavones under Autoclave Conditions and Comparative Study of Anti-cancer Activity — shares topic coverage
- Thermostability and in-vitro Antibacterial Activity of Aqueous Extracts of Tetrapleura tetraptera Pods on Multidrug Resistant Clinical Isolates — shares topic coverage
- Acute Toxicity, Phytochemistry and Anti-diarrheal Effects of Celtis integrifolia Lam. Aqueous Leaf Extract in Wistar Albino Rats — shares topic coverage
- Understanding the Reactivity of Trimethylsilyldiazoalkanes Participating in [3+2] Cycloaddition Reactions towards Diethylfumarate with a Molecular Electron Density Theory Perspective — shares topic coverage
- Understanding the Origin of the Regioselectivity in Non-Polar [3+2] Cycloaddition Reactions through the Molecular Electron Density Theory — shares topic coverage
Article metrics
Real usage data collected on this platform.
0
Page views
0
PDF downloads
0
Outbound clicks
0
Citations
Views by country
Approximate, from request IP at view time — not citizenship or institution. Countries with fewer than 5 views are grouped as "Other".
No views recorded yet.
Traffic sources
Referring site, by host.
No traffic recorded yet.
Views and downloads exclude known bots/crawlers. Citations combines this platform's own DOI-resolved index with each external source's own reported total — see Cited by above for individually listed citing works. Last refreshed 0 seconds ago.