Origins of reversing diastereoselectivity of α,β-dichloro-γ-butenolides and γ-butyrolactams in direct vinylogous aldol addition: a computational study

Khan, Abdul Shafeeuulla; Zhang, Ji; Sarma, Koushik Das; Ganguly, Bishwajit

doi:10.1039/c2ra21203j

Cited by 8 publications

(4 citation statements)

References 54 publications

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“…MESP is an important tool and has been a widely used topographical quantity for understanding molecular reactivity, making coarse guesses about intermolecular interactions, molecular recognition, electrophilic reactions and substituent effects. [35][36][37][38][39][40][41][42][43] MESP analysis gives the most negative potential point (V min ) in the electron-rich regions obtained through topography calculations in any molecular system (Fig. 4).…”

Section: Dft Studiesmentioning

confidence: 91%

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Probing the compatibility of energetic binder poly-glycidyl nitrate with energetic plasticizers: thermal, rheological and DFT studies

et al. 2015

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Section: Dft Studiesmentioning

confidence: 91%

“…In general, electron-dense regions are expected to show a high negative MESP, whereas electron-decient regions are characterized by a positive MESP. [35][36][37][38][39][40] The most negative point (V min ) in the electron rich regions can be obtained from the MESP topography calculation. [41][42][43] 3 Results and discussion…”

Section: Computationalmentioning

confidence: 99%

Probing the compatibility of energetic binder poly-glycidyl nitrate with energetic plasticizers: thermal, rheological and DFT studies

et al. 2015

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“…Conveniently, there is no special computer code required to perform activation strain analyses: all necessary quantities can be computed using any of the regular quantum‐chemical software packages available. As a result, the activation strain model has been applied by various research groups, on a range of chemical processes, such as nucleophilic substitution, cycloaddition, oxidative addition, isomerization, and many other processes from organic and organometallic chemistry.…”

Section: Introductionmentioning

confidence: 99%

The activation strain model and molecular orbital theory

Wolters

Bickelhaupt

2015

WIREs Comput Mol Sci

309

229

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The activation strain model is a powerful tool for understanding reactivity, or inertness, of molecular species. This is done by relating the relative energy of a molecular complex along the reaction energy profile to the structural rigidity of the reactants and the strength of their mutual interactions: ΔE(ζ) = ΔEstrain(ζ) + ΔEint(ζ). We provide a detailed discussion of the model, and elaborate on its strong connection with molecular orbital theory. Using these approaches, a causal relationship is revealed between the properties of the reactants and their reactivity, e.g., reaction barriers and plausible reaction mechanisms. This methodology may reveal intriguing parallels between completely different types of chemical transformations. Thus, the activation strain model constitutes a unifying framework that furthers the development of cross-disciplinary concepts throughout various fields of chemistry. We illustrate the activation strain model in action with selected examples from literature. These examples demonstrate how the methodology is applied to different research questions, how results are interpreted, and how insights into one chemical phenomenon can lead to an improved understanding of another, seemingly completely different chemical process. WIREs Comput Mol Sci 2015, 5:324–343. doi: 10.1002/wcms.1221

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“…Highly functionalized and inexpensive mucohalic acids have found usage in organic synthesis. 1 In recent times, mucohalic acids chemistry has been extended toward the synthesis of compounds of biological interest. For example, derivatives of mucohalic acids have been reported for their antibacterial and antiprotozoal activities.…”

Section: Introductionmentioning

confidence: 99%

β-Substituted γ-butyrolactams from mucochloric acid: synthesis of (±)-baclofen and other γ-aminobutyric acids and useful building blocks

et al. 2014

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In the course of our exploration of the application of mucohalic acids in organic synthesis, we reported the synthesis of a,b-dihalo-a,b-unsaturated g-butyrolactams by reductive amination of a suitable mucohalic acid and a suitable amine. However, the functionalization of the aand/or b-halogen was found to be elusive under Suzuki conditions that worked well with the corresponding g-lactones. Although the corresponding b-aryl derivative was obtained under some of the modified Suzuki conditions tried, the yields were found to be very low. Next, the Suzuki coupling was performed on mucochloric acid prior to the reductive amination step. By careful control of the reaction conditions, only b-substitution was achieved to yield the corresponding b-aryl mucochloric acid. This could then be converted to the corresponding b-substituted g-butyrolactam by reductive amination with 2,4-dimethoxybenzylamine (DMB-NH 2 ) followed by reduction by nickel boride and subsequent deprotection of the DMB group. The resulting g-butyrolactam could either be alkylated or hydrolyzed resulting in the corresponding b-substituted g-aminobutyric acid. This methodology was extended to synthesize (AE)-baclofen in five steps starting from mucochloric acid.Scheme 1 Potential use of b-substituted g-butyrolactams and proposed retrosynthetic analysis.

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Origins of reversing diastereoselectivity of α,β-dichloro-γ-butenolides and γ-butyrolactams in direct vinylogous aldol addition: a computational study

Cited by 8 publications

References 54 publications

Probing the compatibility of energetic binder poly-glycidyl nitrate with energetic plasticizers: thermal, rheological and DFT studies

Probing the compatibility of energetic binder poly-glycidyl nitrate with energetic plasticizers: thermal, rheological and DFT studies

The activation strain model and molecular orbital theory

β-Substituted γ-butyrolactams from mucochloric acid: synthesis of (±)-baclofen and other γ-aminobutyric acids and useful building blocks

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