Distortion/interaction analysis of the reactivities and selectivities of halo– and methoxy–substituted carbenes with alkenes

Sader, C. Avery; Houk, K. N.

doi:10.3998/ark.5550190.p008.408

Cited by 11 publications

(5 citation statements)

References 37 publications

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“…The corresponding expressions were E 1 = ω(isatin) + N (ene) and E 2 = ω(ene) + N (isatin), respectively (shown in Table S2). The results of activation strain model (ASM) analysis on transition states in the carbonyl-ene reaction were shown in Table and Table S3, in which activation energy Δ E ⧧ of the transition state was decomposed into strain energy Δ E ⧧ strain and interaction energy Δ E ⧧ int (i.e., Δ E ⧧ = Δ E ⧧ strain + Δ E ⧧ int ). Unless specified, the Gibbs free energies corrected by both solvation and zero-point vibrational effects at the B3LYP-D3(BJ)/6-311G(d,p)(SMD, CH 2 Cl 2 ) level were used in the discussions.…”

Section: Computational Detailssupporting

confidence: 73%

Mechanistic Study of the Asymmetric Carbonyl-Ene Reaction between Alkyl Enol Ethers and Isatin Catalyzed by the N,N′-Dioxide–Mg(OTf)₂ Complex

Wang

Yang

et al. 2016

J. Org. Chem.

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The mechanism and origin of the stereoselectivity of the asymmetric carbonyl-ene reaction between N-methyl-protected isatin and 2-methyloxypropene catalyzed by the N,N'-dioxide-Mg(OTf)2 complex were investigated by DFT and ONIOM methods. The background reaction occurred via a two-stage, one-step mechanism with a high activation barrier of 30.4 kcal mol(-1) at the B3LYP-D3(BJ)/6-311G**(SMD, CH2Cl2)//B3LYP/6-31G*(SMD, CH2Cl2) level at 303 K. Good linear correlations between the global nucleophilicity index (N) and the activation energy barrier (ΔG(⧧)) were found. The chiral N,N'-Mg(II) complex catalyst could enhance the electrophilicity of the isatin substrate by forming hexacoordinate Mg(II) reactive species. The substituent at the ortho positions of aniline combined with the aliphatic ring of the backbone in the chiral N,N'-dioxide ligand played an important role in the construction of a favorable "pocket-like" chiral environment (chiral pocket) around the Mg(II) center, directing the preferential orientation of the incoming substrate. An unfavorable steric arrangement in the re-face attack pathway translated into a more destabilizing activation strain of the ene substrate, enhancing enantiodifferentiation of two competing pathways for the desired R product. This work also suggested a new phosphine ligand (N-L1) for the formation of the Mg(II) complex catalyst for the asymmetric carbonyl-ene reaction. The chiral environment and Lewis acidity of the Mg(II) complex could be fine-tuned by introduction of P-donor units into the ligand for highly efficient asymmetric catalysis.

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Section: Computational Detailssupporting

confidence: 73%

Mechanistic Study of the Asymmetric Carbonyl-Ene Reaction between Alkyl Enol Ethers and Isatin Catalyzed by the N,N′-Dioxide–Mg(OTf)₂ Complex

Wang

Yang

et al. 2016

J. Org. Chem.

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“…The anion–cation type and its possible configurations have a great impact on the interaction energy and physicochemical properties of MILs. The interaction energy ( E int ) emanates from the combination of closed-shell repulsion, polarization effects, charge transfer, electrostatic interactions, and occupied and unoccupied orbital interactions as well as noncovalent interactions. , All energies have been corrected for the basis set superposition error (BSSE) by the Boys and Bernardi function counterpoise method.…”

Section: Resultsmentioning

confidence: 99%

Investigating the Structural, Electronic, and Topological Properties of [BMIm][Fe(NO)₂Cl₂] Magnetic Ionic Liquid: Density Functional Theory Approaches

Safdari

Ghatee

2023

J. Phys. Chem. B

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Magnetic ionic liquids (MILs) show clear superiority over conventional ionic liquids suitably nested in many applications, particularly in medicine and drug delivery engineering. The easy way of collecting them using an external magnet and separating them from the reaction mixture is a favorable and unique technique. A magnetic imidazolium-based IL, including iron coordinated with −NO and chloride ligands ([BMIm][Fe(NO) 2 Cl 2 ]) (BMIm = 1-n-butyl-3-methyl-imidazolium), has been studied using density functional theory. Such dinitrosyl iron compounds are significant as NO-saving sources and carriers because of their longer physiological lifetime compared with molecular NO. The dependability of the calculations was examined and elucidated at three different methods (M06-2X, B3LYP, and B3LYP-D3) to unravel the importance of noncovalent interactions, including dispersion and H-bonding. Also, the effect of a large basis set on different features of this MIL was assessed. This research is a pioneer in theoretically characterizing the type of −NO moiety of this openshell dinitrosyl iron compound. The complicated structure of the dinitrosyliron unit was determined by the geometrical parameters, stretching frequencies, and magnetic moment calculation. Based on these fingerprint data, the predominant form of two NO's in this MIL is the nitroxyl anion NO − , rather than N ̇O or NO + . Unraveling that one of the NO ligands structurally is dangling enhances the application of this MIL as a NO-saving and source compound. Consequently, Fe 3+ is identified as the major oxidation state of the iron atom, leading to the MIL with a strong magnetic moment (of 5.22μ B ).

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“…The electrophilic P k + and nucleophilic P k – Parr functions were obtained by calculating the corresponding radical ion Mulliken atomic spin density . The factors controlling the reactivity trends in O–H insertion process were elucidated using the activation strain model (ASM). − In ASM analysis, the potential energy surface Δ E was decomposed into the two contributors along reaction coordination: strain or (distortion) Δ E strain and interaction Δ E int . Energy decomposition analysis (EDA) was used to probe the interaction Δ E int between the deformed reacting fragments, which was composed of electrostatic interaction (Δ V elstat ), Pauli repulsion (Δ V Pauli ), orbital interaction (Δ E oi ), and dispersion effect (Δ E disp ) .…”

Section: Methodsmentioning

confidence: 99%

Cooperative Catalysis of Chiral Guanidine and Rh₂(OAc)₄ in Asymmetric O–H Insertion of Carboxylic Acid: A Theoretical Investigation

Meng

et al. 2019

J. Org. Chem.

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We reported a mechanistic study on asymmetric O–H insertion reaction of α-diazoester with carboxylic acid using Rh2(OAc)4/chiral guanidine-amide as the cocatalyst by density functional theory [B3LYP-D3(BJ)/def2-TZVP//B3LYP-D3(BJ)/[6-31G**, SDD] (SMD, Et2O)]. The catalytic reaction included two stages: (i) formation of Rh–carbene species, subsequently by the construction of C–O bond forming enol and (ii) chiral guanidinium salt-assisted H-transfer to the enol. In cooperative catalysis, Rh2(OAc)4 helped to form an enol intermediate via high-reactivity Rh–carbene species, while the in situ-formed guanidium carboxylate acted as a chiral proton shuttle to construct a hydrogen bonding net for the stereo-determinant protonation. The repulsions between the phenyl group of the enol intermediate and the cyclohexyl as well as the ortho-substituted isopropyl group of chiral guanidine played important roles in controlling stereoselectivity. A disadvantageous steric arrangement in si-face attack weakened the stabilizing electrostatic and orbital interaction of reacting species in the H-transfer step, enhancing the pathway to form a predominant product with R-configuration in the two competing pathways. A model was proposed to explain the asymmetric induction of chiral guanidine-amide in protonation.

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Distortion/interaction analysis of the reactivities and selectivities of halo– and methoxy–substituted carbenes with alkenes

Cited by 11 publications

References 37 publications

Mechanistic Study of the Asymmetric Carbonyl-Ene Reaction between Alkyl Enol Ethers and Isatin Catalyzed by the N,N′-Dioxide–Mg(OTf)₂ Complex

Mechanistic Study of the Asymmetric Carbonyl-Ene Reaction between Alkyl Enol Ethers and Isatin Catalyzed by the N,N′-Dioxide–Mg(OTf)₂ Complex

Investigating the Structural, Electronic, and Topological Properties of [BMIm][Fe(NO)₂Cl₂] Magnetic Ionic Liquid: Density Functional Theory Approaches

Cooperative Catalysis of Chiral Guanidine and Rh₂(OAc)₄ in Asymmetric O–H Insertion of Carboxylic Acid: A Theoretical Investigation

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Distortion/interaction analysis of the reactivities and selectivities of halo– and methoxy–substituted carbenes with alkenes

Cited by 11 publications

References 37 publications

Mechanistic Study of the Asymmetric Carbonyl-Ene Reaction between Alkyl Enol Ethers and Isatin Catalyzed by the N,N′-Dioxide–Mg(OTf)2 Complex

Mechanistic Study of the Asymmetric Carbonyl-Ene Reaction between Alkyl Enol Ethers and Isatin Catalyzed by the N,N′-Dioxide–Mg(OTf)2 Complex

Investigating the Structural, Electronic, and Topological Properties of [BMIm][Fe(NO)2Cl2] Magnetic Ionic Liquid: Density Functional Theory Approaches

Cooperative Catalysis of Chiral Guanidine and Rh2(OAc)4 in Asymmetric O–H Insertion of Carboxylic Acid: A Theoretical Investigation

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Mechanistic Study of the Asymmetric Carbonyl-Ene Reaction between Alkyl Enol Ethers and Isatin Catalyzed by the N,N′-Dioxide–Mg(OTf)₂ Complex

Mechanistic Study of the Asymmetric Carbonyl-Ene Reaction between Alkyl Enol Ethers and Isatin Catalyzed by the N,N′-Dioxide–Mg(OTf)₂ Complex

Investigating the Structural, Electronic, and Topological Properties of [BMIm][Fe(NO)₂Cl₂] Magnetic Ionic Liquid: Density Functional Theory Approaches

Cooperative Catalysis of Chiral Guanidine and Rh₂(OAc)₄ in Asymmetric O–H Insertion of Carboxylic Acid: A Theoretical Investigation