The Sterimol Approach: Further Development of the Method and New Applications

Verloop, A.

doi:10.1016/b978-0-08-029222-9.50051-2

Cited by 80 publications

(54 citation statements)

References 18 publications

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“…41 They have recently found application in asymmetric catalysis, correlating more strongly than empirically-determined (isotropic) Charton or Taft parameters in several linear and non-linear structure-selectivity relationships. 42 Verloop developed the Sterimol program 43 to describe the anisotropic nature of a substituent’s steric demands through a combination of subparameters, three of which remain in current use: two width parameters (B 1 and B 5 ) and a length parameter (L).…”

Section: Resultsmentioning

confidence: 99%

Correlating Reactivity and Selectivity to Cyclopentadienyl Ligand Properties in Rh(III)-Catalyzed C–H Activation Reactions: An Experimental and Computational Study

et al. 2017

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CpXRh(III)-catalyzed C-H functionalization reactions are a proven method for the efficient assembly of small molecules. However, rationalization of the effects of cyclopentadienyl (CpX) ligand structure on reaction rate and selectivity has been viewed as a black box, and a truly systematic study is lacking. Consequently, predicting the outcomes of these reactions is challenging because subtle variations in ligand structure can cause notable changes in reaction behavior. A predictive tool is, nonetheless, of considerable value to the community as it would greatly accelerate reaction development. Designing a data set in which the steric and electronic properties of the CpXRh(III) catalysts were systematically varied allowed us to apply multivariate linear regression algorithms to establish correlations between these catalyst-based descriptors and the regio-, diastereoselectivity, and rate of model reactions. This, in turn, led to the development of quantitative predictive models that describe catalyst performance. Our newly-described cone angles and Sterimol parameters for CpX ligands served as highly correlative steric descriptors in the regression models. Through rational design of training and validation sets, key diastereoselectivity outliers were identified. Computations reveal the origins of the outstanding stereoinduction displayed by these outliers. The results are consistent with partial η5−η3 ligand slippage that occurs in the transition state of the selectivity-determining step. In addition to the instructive value of our study, we believe that the insights gained are transposable to other Group 9 transition metals and pave the way toward rational design of C-H functionalization catalysts.

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Section: Resultsmentioning

confidence: 99%

Correlating Reactivity and Selectivity to Cyclopentadienyl Ligand Properties in Rh(III)-Catalyzed C–H Activation Reactions: An Experimental and Computational Study

et al. 2017

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“…Equation (15) indicates that the substituents ortho to the group, ionized under assay condi-SO 2 Nt ions, exert an electron-attracting Ðeld e †ect. Equation (16) suggests an electron-donating meta substituent e †ect on the group, since the colinearity SO 2 Nb etween and for 17 substituents is quite high p p p m (r \ 0É89). The higher the electron density of the ion, the higher is the inhibitory activity.…”

Section: Discussionmentioning

confidence: 99%

Dimethoxypyrimidines as novel herbicides. Part 4. Quantitative structure-activity relationships of dimethoxypyrimidinyl(thio)salicylic acids

Nezu¹,

Wada²,

Yoshida³

et al. 1998

Pestic. Sci.

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:The activity of a number of O-(4,6-dimethoxypyrimidin-2-yl)salicylic acids and their thio analogs inhibiting acetolactate synthase (ALS) preparation was measured. The e †ects of substituents on the salicylic-benzene ring on the inhibitory activity were analyzed quantitatively with physicochemical substituent parameters. For 6-substituted (thio)salicylic acids, the activity was shown to vary parabolically with the "intramolecularÏ steric parameterIn addition, the (E s ). higher steric dimension of substituents in terms of the STERIMOL width or length parameter lowered the activity. The Ðeld-inductive electron-withdrawing property of the 6-substituents in terms of the SwainÈLuptonÈHansch F was favorable for the activity of salicylic acid series. In 5-substituted salicylic acids, the activity was increased by electron-donating substituents with smaller size. The relationships between ALS inhibitory and herbicidal activities were also analyzed with some weed species. Both pre-and post-emergence activities against barnyard grass, Echinochloa crus-galli, were linearly related to the ALS inhibitory activity after allowing for the hydrophobic factor that may contribute to the transport processes. Those against two broad-leaved weed species, Polygonum convolvulus and Abutilon theophrasti were linearly related to the in-vitro activity with no signiÐcant participation of the hydrophobic factor.1998 SCI ( Pestic. Sci., 52, 343È353 (1998)

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“…Uchida et al also measured the rate of disappearance of the compounds in the entire system. The rate followed approximately the zero-order kinetics, and the rate constant, log k, tended to increase with decreasing bulkiness of the ester substituents in terms of the STERIMOL width (Verloop, 1983) and with increasing log P value. This was taken to indicate that the hydrolytic degradation would occur under conditions "reacting" with fish.…”

Section: IXmentioning

confidence: 93%

Hydrophobicity as a Key Physicochemical Parameter of Environmental Toxicology of Pesticides

Fujita¹,

Nishimura

Takayama

et al. 2001

Handbook of Pesticide Toxicology

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The Sterimol Approach: Further Development of the Method and New Applications

Cited by 80 publications

References 18 publications

Correlating Reactivity and Selectivity to Cyclopentadienyl Ligand Properties in Rh(III)-Catalyzed C–H Activation Reactions: An Experimental and Computational Study

Correlating Reactivity and Selectivity to Cyclopentadienyl Ligand Properties in Rh(III)-Catalyzed C–H Activation Reactions: An Experimental and Computational Study

Dimethoxypyrimidines as novel herbicides. Part 4. Quantitative structure-activity relationships of dimethoxypyrimidinyl(thio)salicylic acids

Hydrophobicity as a Key Physicochemical Parameter of Environmental Toxicology of Pesticides

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