Atom Exchange Radical Cyclization: A Sustainable Synthetic Approach towards New Functionalized Targets
Source abstract
Abstract
In this study, we demonstrate the direct preparation of dihalo-γ-lactams featuring two distinct halogens from dichloroamides using a novel atom exchange radical cyclization (AERC) procedure. This method integrates the established atom transfer radical cyclization (ATRC) with halogen exchange in solution. The technique operates under mild conditions and requires small amounts of metallic copper, serving as both a supplemental activator and reducing agent.
Source: crossref · Quality: baseline
Research context
OpenAlex topics: Radical Photochemical Reactions · Oxidative Organic Chemistry Reactions · Catalytic C–H Functionalization Methods
SciVX discovery tags are terminology-based. OpenAlex topics are source-provided classifications.
Affiliations
Department of Chemical and Geological Sciences, University of Modena and Reggio Emilia, Via G. Campi 103, 41125 Modena, Italy
Department of Engineering “Enzo Ferrari”, University of Modena and Reggio Emilia, Via Vivarelli 10, 41125 Modena, Italy
INSTM Research Unit of Modena, Via G. Campi 103, 41125 Modena, Italy
References (31)
Show source-provided references
1. Atom Transfer Radical Polymerization10.1021/cr940534g ↗
2. Catalyst Regeneration in Transition-Metal-Mediated Atom-Transfer Radical Addition (ATRA) and Cyclization (ATRC) Reactions10.1002/ejic.201000234 ↗
3. Copper Catalyzed Atom Transfer Radical Cyclization Reactions10.1002/ejoc.201501571 ↗
4. Arylsulfonyl Groups: The Best Cyclization Auxiliaries for the Preparation of ATRC γ-Lactams Can Be Acidolytically Removed10.1002/ejoc.201402769 ↗
5. The Persistent Radical Effect: A Principle for Selective Radical Reactions and Living Radical Polymerizations10.1021/cr990124y ↗
6. A Green Way to γ-Lactams through a Copper Catalyzed ARGET-ATRC in Ethanol and in the Presence of Ascorbic Acid10.1016/j.tet.2010.11.025 ↗
7. Synthesis and Antihypertensive Activity of 4-(1,2-Dihydro-2-Oxo-1-Pyridyl)-2H-1-Benzopyrans and Related Compounds, New Potassium Channel Activators10.1021/jm00164a005 ↗
8. Stereospecific Synthesis of 4-Alkylglutamates and 4-Alkylprolines10.1016/0040-4039(94)85381-9 ↗
9. Total Synthesis and Biological Activity of Lactacystin, Omuralide and Analogs10.1248/cpb.47.1 ↗
10. Base-Catalyzed Cyclization of N-propargylamides to Oxazoles10.1002/jhet.5570260201 ↗
11. Oda, K., Moriyasu, K., Hayashi, M., Nishida, M., Oyamada, M., Fujiwara, A., and Watanabe, J. (1990). 1-(3-Substituted Benzyl)-3-Halogenoalkyl)-2-Pyrrolidinone Derivatives and Herbicides Containing Them. (EP0402893 A1), pp. 1–34.
12. Woolard, F.X. (1994). N-Benzyl-4-Alkyl-Pyrrolidinone Herbicides. (US5302726), pp. 1–5.
13. Preparation of the Maleic Anhydride Nucleus from Dichloro γ-Lactams: Focus on the Role of the N-Substituent in the Functional Rearrangement and in the Hydrolytic Steps10.1055/s-2008-1067273 ↗
14. (Ph3P)3RuCl2 Catalyzed Equilibration and Elimination of α-Chloro-N-Tosyl-2-Pyrrolidinones: A Unique Route to Unsaturated 2-Pyrrolidinones10.1016/S0040-4039(00)91805-7 ↗
15. A New and Selective Method of Oxidation. The Conversion of Alkyl Halides and Alkyl Tosylates to Aldehydes10.1021/ja01524a080 ↗
16. Efficient and Convenient Oxidation of Organic Halides to Carbonyl Compounds by H2O2 in Ethanol10.1016/j.tetlet.2007.01.084 ↗
17. Direct and Selective Conversion of Benzyl Bromides to Benzaldehydes with Aqueous H2O2 Without Catalyst10.1080/00397911.2010.515347 ↗
18. Oxidation of Alcohols Using H2O2 as Oxidant Catalyzed by AlCl310.1016/j.catcom.2007.08.012 ↗
19. A Green Procedure for the Oxidation of Benzyl Halides to Aromatic Aldehydes or Ketones in Aqueous Media10.1080/00397910903531623 ↗
20. Smith, M.B. (2020). March’s Advanced Organic Chemistry: Reactions, Mechanisms, and Structure, John Wiley & Sons. [8th ed.]. Section 10.45.
21. A Versatile Radical Based Synthesis of γ-Lactams Using Nickel Powder/Acetic Acid10.1016/S0040-4039(00)77265-0 ↗
22. Mechanism of Halogen Exchange in ATRP10.1021/ma201035u ↗
23. Observations on the Synthesis of Functionalised Methyleneaziridines10.1016/0040-4020(96)00308-0 ↗
24. Breakthrough in the α-Perchlorination of Acyl Chlorides10.1055/s-0031-1289678 ↗
25. Efficient and Green Route to γ-Lactams by Copper-Catalysed Reversed Atom Transfer Radical Cyclisation of α-Polychloro-N-allylamides, Using a Low Load of Metal (0.5 mol%)10.1002/adsc.201300132 ↗
26. Halogen Atom Transfer Radical Cyclization of N-Allyl-N-Benzyl-2,2-Dihaloamides to 2-Pyrrolidinones, Promoted by Fe0-FeCl3 or CuCl-TMEDA10.1016/S0040-4020(97)00908-3 ↗
27. Computationally Efficient Methodology to Calculate C−H and C−X (X = F, Cl, and Br) Bond Dissociation Energies in Haloalkanes10.1021/jp993275d ↗
28. Reversible-Deactivation Radical Polymerization in the Presence of Metallic Copper. Activation of Alkyl Halides by Cu010.1021/ma400150a ↗
29. Cu0-Promoted Cyclisation of Unsaturated α-Halogeno Amides to Give β-and γ-Lactams10.1002/ejoc.201600249 ↗
30. ARGET ATRP of Styrene in EtOAc/EtOH Using Only Na2CO3 to Promote the Copper Catalyst Regeneration10.1080/10601325.2020.1866434 ↗
31. ‘Ligand-Free-Like’ CuCl-Catalyzed Atom Transfer Radical Cyclization of N-Substituted N-Allyl Polychloroamides to γ-Lactams10.1055/s-0029-1218583 ↗