Theoretical Investigation of Pd-catalyzed Carbo-aminative Annulation of 1,6-enyne with 2-Iodoaniline Via 6-Endo-Trig Mode
Nan Lu*, Chengxia Miao and Xiaozheng Lan
College of Chemistry and Material Science, Shandong Agricultural University, Taian City, P.R. China
*Corresponding Author: Nan Lu, College of Chemistry and Material Science, Shandong Agricultural University, Taian City, P.R. China.
Received:
March 13, 2023; Published: May 24, 2023
Abstract
The mechanism is investigated for Pd-catalyzed carbo-aminative cyclization of 1,6-enyne with 2-iodoaniline. The regioselective addition of Pd-inserted 2-iodoaniline across alkyne and intermolecular insertion of olefin leads to alkyne-to-alkene adducts. After olefin isomerization, a pallado intermediate is obtained upon aza-conjugate addition. The β-hydride is eliminated with the help of Pd. The oxidative aromatization promoted by carbonate ion makes the oxidation level consistent with desired product. The regioselectivity of 6-endo-trig cyclization is determined through the superiority over other two modes in Heck-type intramolecular coupling. The promotion of active Pd(0) lies in the barrier decrease of rate-limiting olefin isomerization and aza-conjugate addition especially the β-hydride elimination. These results are supported by Multiwfn analysis on FMO of specific TSs and MBO value of vital bonding, breaking.
Keywords: Annulation; 1,6-enynes; Regioselectivity; 6-endo-trig; Aryl Palladation
References
- Marinetti , et al. “Enantioselective, transition metal catalyzed cycloisomerizations”. Chemical Society Reviews 41.14 (2012): 4884-4908.
- Deng , et al. “Enantioselective Rhodium-Catalyzed Cycloisomerization of 1,6-Allenynes to access 5/6-Fused Bicycle[4.3.0]-nonadienes”. Nature Communication 10.1 (2019): 949 (1-10).
- Liang RX., et al. “Palladium-Catalyzed Enantioselective Heteroarenyne Cycloisomerization Reaction”. Angewandte Chemie Int. Ed. 60.13 (2021): 7412-7417.
- Park JH., et al. “Rh-Catalyzed Reductive Cyclization of Enynes using Ethanol as a Source of Hydrogen”. Chemistry: A European Journal 17.39 (2011): 10852-10856.
- Ren X., et al. “Enantioselective Hydroesterificative Cyclization of 1,6-Enynes to Chiral γ-Lactams Bearing a Quaternary Carbon Stereocenter”. Organic Letters 23.9 (2021): 3561-3566.
- Dong M., et al. “PhI (OAc)2-Mediated Dihalogenative Cyclization of 1,6-Enyne with Lithium Halide”. Organic Letters 23.9 (2021): 3588-3592.
- Whyte A., et al. Journal of the American Chemical Society 142.20 (2020): 9510-9517.
- Xuan J., et al. Organic Letters 18.24 (2016): 6372-6375.
- Ding L.,et al. “Merging Hydrogen Atom Transfer and Halogen Atom Transfer for Iodide-Catalyzed Radical Reductive Cyclization of 1,6-Enynes”. Organic Letters 24.17 (2022): 3113-3117.
- Yu XC.,et al. “Metal-Catalyst-Free Radical Cyclization of 1,6-Enynes for the Selective and Switchable Synthesis of Lactams in Water”. ACS Sustainable Chemistry and Engineering 10.18 (2022): 6057-6062.
- Kong D.,et al. “Mechanism and Origins of Enantioselectivity of Cobalt-Catalyzed Intermolecular Hydroarylation/Cyclization of 1,6-Enynes with N-Pyridylindoles”. The Journal of Organic Chemistry 87.9 (2022): 6438-6443.
- Goulart HA., et al. “Synthesis of Seleno-Dibenzocycloheptenones/Spiro[5.5]Trienones by Radical Cyclization of Biaryl Ynones”. The Journal of Organic Chemistry 87.6 (2022): 4273-4283.
- Zhuo LS., et al. “Structure reactivity relationship study of novel quinazoline-based 1,6-naphthyr-idinones as MET inhibitors with potent antitumor efficacy”. European Journal of Medicinal Chemistry 208 (2020): 112785-112801.
- Heravi MM., et al. “Prescribed drugs containing nitrogen heterocycles: an overview”. RSC Advances 10.72 (2020): 44247-44311.
- Saldívar-González FI., et al. “Exploring the Chemical Space and the Bioactivity Profile of Lactams: a Chemo-informatic Study. Exploring the chemical space and the bioactivity profile of lactams: a chemoinformatic study”. RSC Advances 9.46 (2019): 27105-27116.
- Wang MS., et al. “Efficient Arylation of 2,7-Naphthyridin-1 (2H)-one with Diaryliodonium Salts and Discovery of a New Selective MET/AXL Kinase Inhibitor”. ACS Combinatorial Science 22.9 (2020): 457-467.
- Lu LQ., et al. “Development of Cascade Reactions for the Concise Construction of Diverse Heterocyclic Architectures”. Accounts of Chemical Research 45.8 (2012): 1278-1293.
- Walsh T., et al. “Enzymatic Cascade Reactions in Biosynthesis”. Angewandte Chemie Int. Ed. 58.21 (2019): 6846-6879.
- Zhang C.,et al. “Controlling Enantioselectivity and Diastereoselectivity in Radical Cascade Cyclization for Construction of Bicyclic Structures”. Journal of the American Chemical Society 143.29 (2021): 11130-11140.
- Holman KR., et al. “Palladium-catalyzed cascade cyclizations involving C−C and C−X bond formation: strategic applications in natural product synthesis”. Chemical Society Reviews 50.14 (2021): 7891-7908.
- Taskesenligil Y., et al. “Directed C−H Functionalization of C3-Aldehyde, Ketone, and Acid/Ester-Substituted Free (NH) Indoles with Iodoarenes via a Palladium Catalyst System”. The Journal of Organic Chemistry 88.3 (2023): 1299-1318.
- Rakshit A., et al. “Pd (II)-Catalyzed Synthesis of Furo[2,3‑b]pyridines fromβ‑Ketodinitriles and Alkynes via Cyclization and N−H/C Annulation”. Organic Letters 24.20 (2022): 3741-3746.
- Singam MKR., et al. “Harnessing Rhodium-Catalyzed C-H Activation: Regioselective Cascade Annulation for Fused Polyheterocycles”. The Journal of Organic Chemistry 86.12 (2021): 8069-8077.
- Singam MKR., et al. “Rhodium-Catalyzed Annulation of Phenacyl Ammonium Salts with Propargylic Alcohols via a Sequential Dual C−H and a C−C Bond Activation: Modular Entry to Diverse Isochromenones”. Organic Letters 23.20 (2021): 7888-7893.
- Babu US., et al. “Palladium-Catalyzed Carbo-Aminative Cyclization of 1,6-Enynes: Access to Napthyridinone Derivatives”. Organic Letters 24.8 (2022): 1598-1603.
- Zhu S., et al. “Three-Component Radical Iodonitrosylative Cyclization of 1,6-Enynes under Metal-Free Conditions”. Organic Letters 23.13 (2021): 5044-5048.
- Petrone DA., et al. “Palladium-Catalyzed Hydrohalogenation of 1,6-Enynes: Hydrogen Halide Salts and Alkyl Halides as Convenient HX Surrogates”. Journal of the American Chemical Society 139.9 (2017): 3546-3557.
- Frisch, MJ., et al. Gaussian 09, Revision B.01, Gaussian, Inc, Wallingford, CT (2009).
- Hay PJ., et al. “Ab initio effective core potentials for molecular calculations-potentials for the transition-metal atoms Sc to Hg”. The Journal of Chemical Physics 82.1 (1985): 270-283.
- Lv H., et al. “Ionic Liquid Catalyzed C-C Bond Formation for the Synthesis of Polysubstituted Olefins”. European Journal of Organic Chemistry 45 (2022): e202201222.
- Zhuang H., et al. “Bu4NHSO4‐Catalyzed Direct N‐Allylation of Pyrazole and its Derivatives with Allylic Alcohols in Water: A Metal‐free, Recyclable and Sustainable System”. Advanced Synthesis and Catalysis 363.24 (2021): 5461-5472.
- Lu N., et al. “Theoretical investigation on transformation of Cr (II) to Cr (V) complexes bearing tetra-NHC and group transfer reactivity”. International Journal of Quantum Chemistry 120 (2020): e26340.
- Lu N., et al. “Theoretical investigation on the mechanism and enantioselectivity of organocatalytic asymmetric Povarov reactions of anilines and aldehydes”. International Journal of Quantum Chemistry 120 (2020):
- Frenking, G., et al. “The Nature of the Bonding in Transition-Metal Compounds”. Chemical Review 100.2 (2000): 717-774.
- Becke AD. “Density-functional thermochemistry. IV. A new dynamical correlation functional and implications for exact-exchange mixing”. The Journal of Chemical Physics 104.3 (1996): 1040-1046.
- Lee CT., et al. “Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density”. Physical Review B 37.2 (1988): 785-789.
- Tapia O. “Solvent effect theories: Quantum and classical formalisms and their applications in chemistry and biochemistry”. Journal of Mathematical Chemistry 10.1 (1992): 139-181.
- Tomasi, J., et al. “Molecular Interactions in Solution: An Overview of Methods Based on Continuous Distributions of the Solvent”. Chemical Review 94.7 (1994): 2027-2094.
- Simkin BY., et al. “Quantum Chemical and Statistical Theory of Solutions—A Computational Approach”. Ellis Horwood, London (1995).
- Tomasi J., et al. “Quantum Mechanical Continuum Solvation Models”. Chemical Review 105.8 (2005): 2999-3093.
- Marenich AV., et al. “Universal slovation model based on solute electron density and on a continuum model of the solvent defined by the bulk dielectric constant and atomic surface tensions”. The Journal of Physical Chemistry. B 113.18 (2009): 6378-6396.
- Reed AE., et al. “Natural population analysis”. The Journal of Chemical Physics 83.2 (1985): 735-746.
- Reed AE., et al. “Intermolecular interactions from a natural bond orbital donor-acceptor view point”. Chemical Review 88.6 (1988): 899-926.
- Foresman, JB., et al. “Exploring Chemistry with Electronic Structure Methods”. 2nd, Gaussian, Inc., Pittsburgh (1996).
- Lu T., et al. “Multiwfn: A multifunctional wavefunction analyzer”. Journal of Computational Chemistry 33.5 (2012): 580-592.
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