Evaluating continuous chirality measure as a 3D descriptor in chemoinformatics applied to asymmetric catalysis

Abstract

Continuous Chirality Measure (CCM) is a computational metric by which to quantify the chirality of a compound. In enantioselective catalysis, prior work has postulated that CCM is correlated to selectivity and can be used to understand which structural features dictate catalyst efficacy. Herein, the investigation of CCM as a metric capable of guiding catalyst optimization is explored. Conformer-dependent CCM is also explored. Finally, CCM is used with Sterimol parameters to significantly improve the performance of Random Forest models.

Morphometric Analysis of Surface Utricles in Halimeda tuna (Bryopsidales, Ulvophyceae) Reveals Variation in Their Size and Symmetry within Individual Segments

“…The continuous symmetry measure (CSM) was originally developed for morphometric evaluation of symmetry in convex polygons of chemical structures [17,18]. It has mostly been used in studies evaluating the symmetry or chirality of cyclic molecules [18][19][20], but current applications include a wide array of different scientific topics, such as for the quantification of the bilateral asymmetry of leaves [21] or Paleolithic handaxes [22]. CSM indicates the magnitude of difference to perfect symmetry for each individual polygon.…”

Dynamic Control of Chiral Space Through Local Symmetry Breaking in a Rotaxane Organocatalyst

“…Whether or not an object has a superimposable mirror image is formally a binary issue . Often, however, it is the extent to which chirality is expressed on the space surrounding a key region of a molecular structure that is important for the effective transmission of asymmetry . Fledgling artificial molecular machines have been developed that can transfer sequence and polydispersity information through to products, and that can be programmed to stereoselectively deliver different outcomes when promoting successive chemical reactions.…”

“…[1] Often, however, it is the extent to which chirality is expressed on the space surrounding akey region of amolecular structure that is important for the effective transmission of asymmetry. [2] Fledgling artificial molecular machines have been developed [3] that can transfer sequence [4] and polydispersity [5] information through to products,a nd that can be programmed to stereoselectively deliver different outcomes [6] when promoting successive chemical reactions.E nantiodivergent asymmetric catalysis has been demonstrated with solvent-responsive helical polymers, [7] redox-sensitive metal complexes [8] and overcrowded alkene rotary motors [9] . [10][11][12] Thetrapping of amacrocycle to one side of aprochiral center with asteric barrier (a form of atropisomerism [13] )h as previously been used [14] to break symmetry [15] and induce mechanical point-chirality [16] in rotaxanes.W er easoned that combining an extension of the latter principle with the controllable change of macrocycle position possible in stimuli-responsive molecular shuttles [17] could provide as trategy for achieving dynamic control over the effective "handedness" of the chiral space around acatalytic site on arotaxane axle.…”

Binding Mode Multiplicity and Multiscale Chirality in the Supramolecular Assembly of DNA and a π‐Conjugated Polymer

“…They can also be used as measures of shape, [22,23] and as measures of linearity or planarity even in the lack of perfect symmetry. Since their original developments, these metrics have been proven useful for various studies of reactive [24] and catalytic processes, [25,26] as well as physical and chemical processes. [27][28][29][30][31][32] Here, we used the CSM to study the various global shapes of the P3HTÀ PMe 3 conformations in order to underline how local organizational effects influence the macromolecular shapes of CPT around DNA.…”