Syn Additions

Catalytic hydrogenation is mostly used to convert C—C triple bonds into C C double bonds and alkenes into alkanes or to replace allylic or benzylic hetero atoms by hydrogen (H. Kropf, 1980). Simple theory postulates cis- or syn-addition of hydrogen to the C—C triple or double bond with heterogeneous (R. L. Augustine, 1965, 1968, 1976 P. N. Rylander, 1979) and homogeneous (A. J. Birch, 1976) catalysts. Sulfur functions can be removed with reducing metals, e. g. with Raney nickel (G. R. Pettit, 1962 A). Heteroaromatic systems may be reduced with the aid of ruthenium on carbon. 

Stereochemical features in the oxidative addition and the elimination of /3-hydrogen of cyclic and acyclic alkenes are different. The insertion (palladation) is syn addition. The syn addition (carbopalladation) of R—Pd—X to an acyclic alkene is followed by the syn elimination of 3-hydrogen to give the trans-a ksne 6, because free rotation of 5 is possible with the acyclic alkene. On the other hand, no rotation of the intermediate 7 is possible with a cyclic alkene and the syn elimination of /3-hydrogen gives the allylic compound 8 rather than a substituted alkene. 

The term syn addition describes the stereochemistry of reactions such as this m which two atoms or groups add to the same face of a double bond When atoms or groups add to opposite faces of the double bond the process is called anti addition... 

Overall the reaction leads to syn addition of H and OH to the double bond This fact has an important bearing on the mechanism of the process... 

Epoxidation of alkenes with peroxy acids is a syn addition to the double bond Substituents that are cis to each other in the alkene remain cis in the epoxide substituents that are trans in the alkene remain trans m the epoxide... 

Epoxidation (Section 6 18) Peroxy acids transfer oxygen to the double bond of alkenes to yield epoxides The reaction IS a stereospecific syn addition... 

There are two products that can be formed by syn addition of hydrogen to 2 3 dimethylbi cyclo[2 2 1] 2 heptene Write or make molecular models of their structures... 

Construct a molecular model of the product formed by catalytic hydrogenation of 1 2 dimethylcyclohexene Assume syn addition occurs... 

Epoxidation of alkenes is a stereospecific syn addition Which stereoisomer of 2 butene reacts with peroxyacetic acid to give meso 2 3 epoxybu tane Which one gives a racemic mixture of (2/ 3/ ) and (25 35) 2 3 epoxybutane ... 

Like the hydrogenation of alkenes hydrogenation of alkynes is a syn addition CIS alkenes are intermediates in the hydrogenation of alkynes to alkanes... 

The reaction of dihalocarbenes with alkenes is stereospecific and syn addition is observed... 

Methylene transfer from lodo methylzinc iodide converts alkenes to cyclopropanes The reaction is a stereo specific syn addition of a CH2 group to the double bond... 

Overall the reaction leads to addition of two hydroxyl groups to the double bond and IS referred to as hydroxylation Both oxygens of the diol come from osmium tetraox ide via the cyclic osmate ester The reaction of OSO4 with the alkene is a syn addition and the conversion of the cyclic osmate to the diol involves cleavage of the bonds between oxygen and osmium Thus both hydroxyl groups of the diol become attached to the same face of the double bond syn hydroxylation of the alkene is observed... 

The reaction is easy to carry out and yields are usually high Epoxidation is a stereo specific syn addition... 

Syn addition (Section 6 3) Addition reaction in which the two portions of the reagent that add to a multiple bond add from the same side... 

Hydroboration - regloseiective and stereoselective (syn) addition of BH3 (RBH2, R2BH) to olefins. Synthesis of alcohol including optically active alcohols from olefins. Also useful In synthesis of ketones by stitching ot olefins and CO... 

Entries 1 and 2 in Scheme 2.9 are typical of concerted syn addition to alkene double bonds. On treatment with peroxyacetic acid, the Z-alkene affords the cis-oxirane, whereas the -alkene affords only the iraws-oxirane. Similarly, addition of dibromocarbene to Z-2-butene yields exclusively l,l-dibromo-cw-2,3-dimethylcyclopropane, whereas only 1,1-dibromo-/ra 5-2,3-dimethylcyclopropane is formed from -2-butene. There are also numerous stereospecific anti additions. Entiy 3 shows the anti stereochemistry typical of bromination of simple alkenes. 

These effects are attributed to differences in the c-donor character of the C—C bonds as a result of substitution. Electron-attracting groups diminish the donor capacity and promote syn addition. An alternative explanation invokes a direct electrostatic effect arising from the C-X bond dipole. 

A significant modification in the stereochemistry is observed when the double bond is conjugated with a group that can stabilize a carbocation intermediate. Most of the specific cases involve an aryl substituent. Examples of alkenes that give primarily syn addition are Z- and -l-phenylpropene, Z- and - -<-butylstyrene, l-phenyl-4-/-butylcyclohex-ene, and indene. The mechanism proposed for these additions features an ion pair as the key intermediate. Because of the greater stability of the carbocations in these molecules, concerted attack by halide ion is not required for complete carbon-hydrogen bond formation. If the ion pair formed by alkene protonation collapses to product faster than reorientation takes place, the result will be syn addition, since the proton and halide ion are initially on the same side of the molecule. 

Again, the chloride is almost exclusively the exo isomer. The distribution of deuterium in the product was determined by NMR spectroscopy. The fact that 1 and 2 are formed in unequal amoimts excludes the symmetrical bridged ion as the only intermediate. The excess of 1 over 2 indicates fliat some syn addition occurs by ion-pair collapse before the bridged ion achieves symmetry with respect to the chloride ion. If the amount of 2 is taken as an indication of the extent of bridged-ion involvement, one would conclude that 82% of the reaction proceeds through this intermediate, which must give equal amoimts of 1 and 2. 

On the other hand, a freely rotating open carbocation would be expected to give both the syn and anti addition products. If the principal intermediate were an ion pair that collapsed faster than rotation about the C—C bond, syn addition could predominate. 

The stereochemistry of chlorination can be explained in similar terms. Chlorine would be expected to be a somewhat poorer bridging group than bromine because it is less polarizable and more resistant to becoming positively charged. Comparison of the data for bromination and chlorination of E- and Z-l-phenylpropene confirms this trend (see Table 6.2). Although anti addition is dominant in bromination, syn addition is slightly preferred... 

The stereochemistry of both chlorination and bromination of several cyclic and acyclic dienes has been determined. The results show that bromination is often stereo-specifically anti for the 1,2-addition process, whereas syn addition is preferred for 1,4-addition. Comparable results for chlorination show much less stereospeciftcity. It appears that chlorination proceeds primarily through ion-pair intermediates, whereas in bromina-hon a stereospecific anfi-l,2-addition may compete with a process involving a carbocation mtermediate. The latter can presumably give syn or anti product. 

For alkyl-substituted alkynes, there is a difference in stereochemistry between mono-and disubstituted derivatives. The former give syn addition whereas the latter react by anti addition. The disubstituted (internal) compounds are considerably ( 100 times) more reactive than the monosubstituted (terminal) ones. This result suggests that the transition state of the rate-determining step is stabilized by both of the alkyl substituents and points to a bridged intermediate. This would be consistent with the overall stereochemistry of the reaction for internal alkynes. 

The monosubstituted intermediate does not seem to be effectively bridged, since syn addition predominates. Avery short-lived vinyl cation appears to be the best description of the intermediate in this case. ... 

When indene (4) is brominated in carbon tetrachloride, it gives some syn addition ( 15%), but indenone (5) gives only anti addition under the same conditions. 

The stereochemistry of the 1,3-dipolar cycloaddition reaction is analogous to that of the Diels-Alder reaction and is a stereospecific syn addition. Diazomethane, for example, adds stereospecifically to the diesters 43 and 44 to yield the pyrazolines 45 and 46, respectively. 

Terminal (perfluoroalkyl)alkynes react with iodine or iodine chloride to yield syn addition products bearing iodine on the terminal carbon [16 (equation 9). 

Perfluoroalkylalkynes undergo unidirectional syn addition of iodine cyanide [M] (equation 43)... 

Alkynyl trifluoromethyl sulfones add dimethylformamide and dimethylsul-foxide to give products in good yields The consistent stereospeciticity of the reaction syn addition product only) suggests that an unstable [2+2] cycloaddition intermediate is initially formed [J4] (equation 12). 

Thermal insertion reactions of dihydndobis(T) - cyclopentadienyl)molybdenum with tnfluoromethylacetylene give exclusively syn addition At —40 °C, hexafluoro-2-butyne inserts to the Mo-H bond to give anti addition [40] equation 30)... 

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