Predicting hydration propensities of biologically relevant α-ketoamides

Wedler, Henry B.; Palazzo, Teresa A.; Pemberton, Ryan P.; Hamann, Christian S.; Kurth, Mark J.; Tantillo, Dean J.

doi:10.1016/j.bmcl.2015.08.010

Cited by 7 publications

(5 citation statements)

References 43 publications

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“…Noncovalent interaction (NCI) plots were generated using Multiwfn version 3.7 with a medium-quality grid . Natural bond orbital (NBO) analysis (version 3.1) was carried out in Gaussian 09 to obtain second-order perturbation NBO energies. , Hydration propensities of our substrates were calculated using electronic energies ( E ) in a formula based on thermodynamic data– hydration data may also be determined kinetically, , –with the following equations (eqs and ), where E is the nonhydrated species and E hyd is the hydrated species: …”

Section: Methodsmentioning

confidence: 99%

The Role of Through-Bond Stereoelectronic Effects in the Reactivity of 3-Azabicyclo[3.3.1]nonanes

2022

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Hyperconjugation/conjugation through-bond stereoelectronic effects were studied with density functional theory in the context of 3-azabicyclo[3.3.1]nonanes to unravel puzzling differences in reactivity between a vinylogous chloride (4) and a vinylogous ester (5). These compoundswhose structures differ only by one substituentwere found to display strikingly different reactivities in hydrochloric acid by Risch and co-workers (J. Am. Chem. Soc.199111394119412). Computational analyses of substituent effects, noncovalent interactions, natural bond orbitals, isodesmic reactions, and hydration propensities lead to a model for which the role of remote, through-bond stereoelectronic effects is the key to explaining 4 and 5’s diverging reactivity.

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Section: Methodsmentioning

confidence: 99%

The Role of Through-Bond Stereoelectronic Effects in the Reactivity of 3-Azabicyclo[3.3.1]nonanes

2022

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“…60 Natural bond orbital (NBO) analysis (version 3.1) was carried out in Gaussian 09 to obtain second-order perturbation NBO energies. 61,62 Hydration propensities of our substrates were calculated using electronic energies (E) in a formula based on thermodynamic data 63 -hydration data may also be determined kinetically 64,65 -with the following equations (3 and 4), where E is the non-hydrated species, and Ehyd is the hydrated species:…”

Section: 𝐴 + 𝐻 + → 𝐴𝐻 +mentioning

confidence: 99%

The Role of Through-Bond Stereoelectronic Effects in the Reactivity of 3-Azabicyclo[3.3.1]nonanes

Laconsay

Rho

Tantillo

2021

Preprint

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Hyperconjugation/conjugation through-bond stereoelectronic effects were studied with density functional theory (DFT) in the context of 3-azabicyclo[3.3.1]nonanes to unravel puzzling differences in reactivity between a vinylogous chloride (4) and a vinylogous ester (5). These compounds—whose structures differ only by one substituent—were found to display strikingly different reactivities in hydrochloric acid by Risch and co-workers (J. Am. Chem. Soc. 1991, 113, 9411–9412). Computational analyses of substituent effects, noncovalent interactions, natural bond orbitals, isodesmic reactions, and hydration propensities lead to a model for which the role of remote, through-bond stereoelectronic effects is key to explaining 4 and 5’s diverging reactivity.

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“…The significant features of visible light, such as its eco-compatibility, inexpensive nature, universal availability, nontoxicity, and operational simplicity, show increasing demand for sustainable synthetic conversions . α-Ketoamides and their derivatives are commonly found in numerous natural products and biologically significant compounds, spanning antiviral, anti-HRV, anti-inflammatory, and antibacterial drugs . In addition, α-ketoamides and their derivatives are commonly used for the preparation of fluorescent probes for the monitoring of pathological conditions, such as cancer or Parkinson’s disease, including prodrugs, and for the synthesis of some photolabeling agents or fluorophores/components of functional materials .…”

Section: Introductionmentioning

confidence: 99%

Visible-Light-Triggered Synthesis of N-α-Ketoacylated Sulfoximines by Denitrogenative and Oxidative Functionalization of Vinyl Azides

Sarkar,

Pal,

Santra

et al. 2024

J. Org. Chem.

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We have introduced a sulfoximidation reaction initiated by visible light between α-phenyl vinyl azides and NHsulfoximines. The cost-effective and readily accessible hypervalent iodine reagent (PIDA) easily promoted the oxidative sulfoximidation process to afford N-α-ketoacylated sulfoximines in good to high yields, involving the formation of two new C−O bonds and one C−N bond. Additionally, the protocol offers noteworthy advantages, including its metal-free and photocatalyst-free reaction and its broad substrate compatibility.

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Predicting hydration propensities of biologically relevant α-ketoamides

Cited by 7 publications

References 43 publications

The Role of Through-Bond Stereoelectronic Effects in the Reactivity of 3-Azabicyclo[3.3.1]nonanes

The Role of Through-Bond Stereoelectronic Effects in the Reactivity of 3-Azabicyclo[3.3.1]nonanes

The Role of Through-Bond Stereoelectronic Effects in the Reactivity of 3-Azabicyclo[3.3.1]nonanes

Visible-Light-Triggered Synthesis of N-α-Ketoacylated Sulfoximines by Denitrogenative and Oxidative Functionalization of Vinyl Azides

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