Achirality, definition

The same kind of spontaneous racemization oc curs for any as 1 2 disubstituted cyclohexane in which both substituents are the same Because such compounds are chiral it is incorrect to speak of them as meso compounds which are achiral by definition Rapid chair-chair interconversion however converts them to a 1 1 mixture of enantiomers and this mix ture IS optically inactive... 

Achiral (Section 7 1) Opposite of chiral An achiral object is supenmposable on its mirror image Acid According to the Arrhenius definition (Section 1 12) a substance that ionizes in water to produce protons Accord mg to the Br0nsted-Lowry definition (Section 1 13) a sub stance that donates a proton to some other substance According to the Lewis definition (Section 1 17) an electron pair acceptor... 

In a chiral class, which by definition contains chiral molecules with exclusively achiral ligands, all these chiral molecules are -chiral. In an achiral class the chirality is only due to jS -chirality. Therefore, we have for any class... 

By definition, a molecule is achiral if it is left invariant by some improper operation (reflection or rotary reflection) of the point group of the skeleton. Writing the permutation s corresponding to a given improper operation in cyclic form,... 

The equilibrium ensemble of the configurations of meso-tartaric acid 10 a—c has umin = 0. From the definition of umm follows immediately that for all achiral molecules min = 0 holds. This applies also to those cases where asymmetric C-atoms are present but cancel each other because of overall molecular symmetry. 

The optical yield was found to be very sensitive to structural modifications of the achiral agent. For example, use of the more bulky FV or Bu substituents in the 3,5-positions of phenol resulted in lower optical yields. In some cases a reversal of the sense of asymmetric induction was observed. Systematic variation of reaction conditions using the best achiral component, 3,5-xylenol, established that optimum results were obtained in ether solvent at about - 15°C. There was also a minor but definite influence of the rate of addition of ketone as well as an effect of concentration on optical yield, with a slower rate being advantageous. The results of reduction of aryl alkyl ketones are shown in Table 9, along with comparative results of reduction with similar chiral auxiliary reagents. 

So far we have looked at chain-end control and site control if they were independent. As already mentioned, a site-control-o /y mechanism does not exist. Since we are, by definition, making a chiral chain-end and since chain-end control does occur as found in achiral catalyst systems, site control must be accompanied by chain-end influences, or a(n) (a)symmetric site may amplify specific chain end influences. Recent results have shown that this is indeed the case [18,19,21,26], The simple explanation given above has to be modified. We limit ourselves to two issues, (a) the stereochemistry of the coordinating propene and (b) reinforcement of the two mechanisms. 

The third approach is the main topic of this volume. According to the definition given above it involves enantiomerically pure starting materials which at some point must be provided by resolution or ex-chiral-pool synthesis. It is more or less equivalent to the term asymmetric synthesis defined by Marckwald in 19047 as follows Asymmetric syntheses are those reactions which produce optically active substances from symmetrically constituted compounds with the intermediate use of optically active materials but with the exclusion of all analytical processes . In today s language, this would mean that asymmetric syntheses are those reactions, or sequences of reactions, which produce chiral nonracemic substances from achiral compounds with the intermediate use of chiral nonracemic materials, but excluding a separation operation. 

In retrospect, it seems unfortunate that in 1971 Morrison and Mosher8 generalized the definition, while keeping the term, an asymmetric synthesis is a reaction in which an achiral unit in an ensemble of substrate molecules is converted by a reactant into a chiral unit in such a manner that the stereoisomeric products arc produced in unequal amounts ( Footnote The substrate molecule must have either enantiotopic or diastereotopic groups or faces) . Obviously the phrase "an achiral unit in an ensemble of substrate molecules is too inexact and requires a great deal of additional explanation, which was partially given by the footnote (note that molecule, i.e., singular, was used ). Currently, the Morrison-Mosher term appears to be equivalent to stereoselective reaction. Unfortunately, this term was only defined in the modem sense by Izumi in 1971, i.e., in the same year the Morrison-Mosher definition was published. 

C is correct, Meso compounds are (by definition) achiral although they do contain chiral carbons. They are not optically active (do not rotate plane-polarized light). 

Although the term prochirality is frequently used, especially by biochemists, it suffers from a limitation which arises from a corresponding limitation in the definition of chirality. Molecules may display purely stereochemical differences without being chiral cis-tram isomers of olefins and certain achiral cis-trans isomers of cyclanes are examples. Thus (Fig. 2) (Z)- and ( )-1,2-dichloroethylene (4, 5) are achiral diastereomers, as are cis- and /rtww-1,3-dibromocyclobutanes (6, 7) being devoid of chirality these compounds have no chiral centers (or other chiral elements). Thus it is inappropriate to associate stereoisomerism with the occurrence of chiral... 

An interesting phenomenon whereby achiral compounds occupy chiral cavities has been reported. Steroidal host compounds give rise to the attachment of definite chiral conformations of achiral compounds within cavities, making it possible to observe solid-state circular dichroism spectra. Gdaniec and Polonski reported this type of property for the inclusion compounds of DCA and CA with various aromatic ketones [40a] and benzil [40c], Furthermore, it is possible for the selected conformers to maintain their chiral state temporarily in solution. That is, soon after the inclusion compounds are dissolved, the chirality may be retained for some time. /V-Nitrosopiperidines were found to display this type of dynamic chiral recognition in DCA and CA inclusion compounds [40b], In this case, one can observe the decay of the circular dichroism signal after dissolution of these inclusion compounds in methanol. 

Definition An ensemble of molecules is chemically achiral under given observation conditions if and only if it is composed of racemic pairs of enantiomers and achiral molecules. 

In all the other cases, with either a linear or a nonlinear recycling process or with both, the coefficients A and B are no longer zero at the same time, and a definite value of the order parameter

0, B becomes nonzero since /xqi,oo > 0. If the linear recycling exists as X > 0, not all the achiral substrate transform to chiral products but a finite amount remains asymptotically as a(t = oo) > 0. Therefore, nonzero values of ko, k or k2 k 2 give contributions to the coefficients A or B. 

In these definitions, object refers to any rigid array, such as a set of points, or to a geometrical figure, or to a model of a molecule ideally realized (of which more below) properly congruent can be replaced by superposable and homomorphs, which may be either chiral or achiral, are congruent counterparts in Kant s terminology. 

In summary, failure to detect a rigidly achiral presentation does not mean that such a presentation cannot be found among the infinitely many presentations of a knot failure to interconvert enantiomorphous presentations by ambient isotopy does not exclude the possibility that an interconversion pathway can be found among the infinitely many pathways that are available and a palindromic knot polynomial does not necessarily mean that the knot is amphicheiral. Consequently, it may be impossible in certain cases to determine with complete certainty whether a knot is topologically chiral or not. The fundamental task of the theory of knots was stated over a hundred years ago by its foremost pioneer Given the number of its double points, to find all the essentially different forms which a closed curve can assume. 15 Yet to find invariants that will definitively determine whether or not a knot is chiral remains an unsolved problem to this day.63a Vassiliev invariants have been conjectured to be such perfect invariants.63b... 

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