Antarafacial examples

Cycloaddition reactions are those in which two unsaturated molecules add together to yield a cyclic product. For example, Diels-AJder reaction between a diene (four tt electrons) and a dienophile (two tt electrons) yields a cyclohexene. Cycloadditions can take place either by suprafacial or antarafacial pathways. Suprafacial cycloaddition involves interaction between lobes on the same face of one component and on the same face of the second component. Antarafacial cycloaddition involves interaction between lobes on the same face of one component ancl on opposite faces of the other component. The reaction course in a specific case can be found by looking at the symmetry of the HOMO of one component and the lowest unoccupied molecular orbital (LUMO) of the other component. 

The following reaction is an example of a [2,3] sigmatropic rearrangement. Would you expect the reaction to be supra facial or antarafacial Explain. 

Ar-Arylbenzimidoyl)tetrazoles t, prepared from JV-arylbenzimidoyl chlorides and 5-(dimethylamino)- or 5-aryltetrazole, give 3//-l,3,4-benzotriazepines 4 on thermolysis. It has been proposed that the reaction proceeds by way of the dipolar compounds 2, which undergo [l,7]-antarafacial 871-electrocyclization to 3. The process is completed by a symmetry-allowed [1.5]-hydrogen shift. Selected examples are given.349-350... 

Dihydrothiophene-1,1-dioxides (42) and 2,17-dihydrothiepin-1,1-dioxides (43) undergo analogous 1,4 and 1,6 eliminations, respectively (see also 17-38). These are concerted reactions and, as predicted by the orbital-symmetry rules (p. 1067), the former is a suprafacial process and the latter an antarafacial process. The rules also predict that elimination of SO2 from episulfones cannot take place by a concerted mechanism (except antarafacially, which is unlikely for such a small ring), and the evidence shows that this reaction occurs by a non-concerted pathway.The eliminations of SO2 from 42 and 43 are examples of cheletropic reactions, which are defined as reactions in which two a bonds that terminate at a single atom (in this case the sulfur atom) are made or broken in concert. 

The actual reported results bear out this analysis. Thus a thermal [1,3] migration is allowed to take place only antarafacially, but such a transition state would be extremely strained, and thermal [1,3] sigmatropic migrations of hydrogen are unknown." On the other hand, the photochemical pathway allows suprafacial [1,3] shifts, and a few such reactions are known, an example being " ... 

The rare [1,4] hydrogen transfer has been observed in radical cyclizations. With respect to [1,7] hydrogen shifts, the rules predict the thermal reaction to be antarafacial. Unlike the case of [1,3] shifts, the transition state is not too greatly strained, and such rearrangements have been reported, for example,... 

Such 1,3-shifts are, indeed, found to be relatively common. 1,5-Photochemical shifts in (36, x = 1) should be antarafacial, but this is likely to involve a strained T.S. and no examples are known. 1,7-Photochemical shifts in (36, x = 2) should be allowed and suprafacial, and the example (47 — 48) has in fact been observed ... 

In what is one of the few examples of utilization of a higher order sigmatropic hydrogen shift in the synthesis of complex molecules, Eschenmoser, in studies directed toward the synthesis of Vitamin B12, found that an antarafacial [1,16] H-shift could be utilized to effect closure of secocorrin 63 to corrin 65 (Scheme 16)31. An intermediate biradical... 

Figure 12.3. Examples of suprafacial and antarafacial reactions of n systems. Notice that the examples serve to describe the stereochemical course of the reaction only. No mechanism is implied by these examples.

The outcome of all this for photochemical sigmatropic shifts is that those most commonly observed are of order (1.3) or (1.7) these involve 4 or 8 electrons, respectively, and occur in a suprafacial manner. Examples of photochemical 1.3-shifts of hydrogen are found for monoalkenes (2.25) and for conjugated dienes 2.26). In the case of dienes a 1,3-shift is favoured over a 1,5-shift, because for the latter to occur photochemically it would have to take place in an antarafacial manner. Note that in both examples the direction of... 

Anomeric effect, 82, 310-311, 305 Antarafacial, 163 examples, 164 sigma bonds, 167 Anti-Bredt olefin, 102 Approximations of MO theory Born-Oppenheimer, 22 Hartree-Fock, 222 Huckel, 35, 86 independent electron, 35 LCAO, 229 nonrelativistic, 22 SHMO, 87... 

When antarafacial elimination is rendered difficult by the inability of the reacting groups to acquire the desired trans arrangement, then suprafacial elimination can occur, although less readily. An example is chlorocyclopen-tane, in which H and X cannot assume a trans configuration without very considerable strain but which does undergo suprafacial elimination at a reasonable rate ... 

The stereochemistry of addition depends largely on the structure of the alkene, but for simple alkenes and cycloalkenes, addition occurs predominantly in an antarafacial manner. For example, hydrogen bromide reacts with 1,2-dimethylcyclohexene to give the antarafacial addition product ... 

The alkynes behave in many ways as if they were doubly unsaturated alkenes. For example, bromine adds to ethyne in two stages —first to give trans-1,2-dibromoethene by antarafacial addition, and finally to give 1,1,2,2,-tetra-bromoethane ... 

The principles of radical addition reactions of alkenes appear to apply equally to alkynes, although there are fewer documented examples of radical additions to triple bonds. Two molecules of hydrogen bromide can add to propyne first to give cis-1 -bromopropene (by antarafacial addition) and then 1,2-dibromopropane ... 

Conformation has a major influence on the chemical reactivity of cycloalkanes. To understand its effect in any one reaction, we first need to know what the conformation is of the transition state, and this requires a knowledge of the reaction mechanism. Next, we have to decide what amount of energy is required for the reactants to achieve transition-state conformations. For example, consider the E2 elimination discussed in Section 8-8D. The preferred transition state requires the leaving groups to be antarafacial and coplanar ... 

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