Combination tables alkenes

It has been pointed out earlier that the anti/syn ratio of ethyl bicyclo[4.1,0]heptane-7-carboxylate, which arises from cyclohexene and ethyl diazoacetate, in the presence of Cul P(OMe)3 depends on the concentration of the catalyst57). Doyle reported, however, that for most combinations of alkene and catalyst (see Tables 2 and 7) neither concentration of the catalyst (G.5-4.0 mol- %) nor the rate of addition of the diazo ester nor the molar ratio of olefin to diazo ester affected the stereoselectivity. Thus, cyclopropanation of cyclohexene in the presence of copper catalysts seems to be a particular case, and it has been stated that the most appreciable variations of the anti/syn ratio occur in the presence of air, when allylic oxidation of cyclohexene becomes a competing process S9). As the yields for cyclohexene cyclopropanation with copper catalysts [except Cu(OTf)2] are low (Table 2), such variations in stereoselectivity are not very significant in terms of absolute yields anyway. 

With few exceptions, products are formed which result from a combination of alkenes in a head-to-head maimer, or a correspondingly regiospecific manner in codimerisations (see Table 7.13). Furthermore, the reactions are not stereospecific. 

The behavior of strained,/Zuorimiret/ methylenecyelopropanes depends upon the position and level of fluorination [34], l-(Difluoromethylene)cyclopropane is much like tetrafluoroethylene in its preference for [2+2] cycloaddition (equation 37), but Its 2,2-difluoro isomer favors [4+2] cycloadditions (equation 38). Perfluoromethylenecyclopropane is an exceptionally reactive dienophile but does not undergo [2+2] cycloadditions, possibly because of stenc reasons [34, 45] Cycloadditions involving most possible combinations of simple fluoroalkenes and alkenes or alkynes have been tried [85], but kinetic activation enthalpies (A/f j for only the dimerizations of tetrafluoroethylene (22 6-23 5 kcal/mol), chlorotri-fluoroethylene (23 6 kcal/mol), and perfluoropropene (31.6 kcal/mol) and the cycloaddition between chlorotnfluoroethylene and perfluoropropene (25.5 kcal/mol) have been determined accurately [97, 98] Some cycloadditions involving more functionalized alkenes are listed in Table 5 [99. 100, 101, 102, 103]... 

The scope of reactions involving hydrogen peroxide and PTC is large, and some idea of the versatility can be found from Table 4.2. A relatively new combined oxidation/phase transfer catalyst for alkene epoxidation is based on MeRe03 in conjunction with 4-substituted pyridines (e.g. 4-methoxy pyridine), the resulting complex accomplishing both catalytic roles. 

The reactivity of different alkenes toward mercuration spans a considerable range and is governed by a combination of steric and electronic factors.24 Terminal double bonds are more reactive than internal ones. Disubstituted terminal alkenes, however, are more reactive than monosubstituted cases, as would be expected for electrophilic attack. (See Part A, Table 5.6 for comparative rate data.) The differences in relative reactivities are large enough that selectivity can be achieved with certain dienes. 

The determination of large values of the rate constant ratio ks/kpfrom the low yields of alkene product that forms by partitioning of carbocations in nucleophilic solvents. These rate constant ratios may then be combined with absolute rate constants for the overall decay of the carbocation to give absolute values of kp (s ).14 16 For example, the reaction of the l-(4-methylphenyl)ethyl carbocation in 50/50 (v/v) trifluoroethanol/water gives mainly the solvent adducts and a 0.07% yield of 4-methylstyrene from proton transfer to solvent, which corresponds to kjkp = 1400. This can be combined with ks = 6 x 109 s V4 to give kp = 4.2 x 106 s l (Table 1). 

The regioselectivity in radical addition reactions to alkenes in general has successfully been interpreted by a combination of steric and electronic effects1815,47. In the absence of steric effects, regiochemical preferences can readily be explained with FMO theory. The most relevant polyene orbital for the addition of nucleophilic radicals to polyenes will be the LUMO for the addition of electrophilic orbitals it will be the HOMO. Table 10 lists the HOMO and LUMO coefficients (without the phase sign) for the first three members of the polyene family together with those for ethylene as calculated from Hiickel theory and with the AMI semiempirical method48. 

Table 4.39. Non-radical reaction types for interactions of transition metals (M) with alkenes ( ), showing principal donor-acceptor combinations in each case (the symbol denotes a vacant valence orbital [formal hypovalency] on the...

Selected examples are given in Table 9 for bromofluorinations of alkenes using A-bromosuccin-imide in combination with 70% hydrogen fluoride/pyridine (Method A) and hydrogen fluo-ride/polyvinylpyridine (Method B), respectively. Table 10 shows examples of the selective monoaddition of in situ produced halofluorides (70 % hydrogen fluoride/pyridine and A-iodo-. A-bromo- or /V-ehloro-succinimide) to symmetrically substituted alkynes. 

Nitronium tetrafluoroborate dissolved in 70% hydrogen fluoride/pyridine is a suitable reagent combination for the preparation of a-fluoro-/i-nitroalkanes from alkenes.31,207 The products are useful precursors for the synthesis of /Tfluoroalkylamines (Table 13). 

To a mixture of KH4F5 (1.1 mmol), DBH (1.1 mmol), and CH2C1, (3mL) in a Teflon vessel was added a solution of an alkene (sec Table 2) in C H,CI2 (2 mL). The mixture was stirred for 4h at rt and then quenched with aq NaHC03 and Na2S,03. The aqueous phase was extracted with CH2C12 (3x5 mL) and (he combined extracts were dried (MgS04). After evaporation of the solvent, the product was purified by chromatography (silica gel). 

The structure of the sex pheromone for the Fucus species, fucoserratene (11), was elucidated in 1973.16 The positions and geometries of alkenes were revealed by comparison of the gas chromatographic behavior with those of the isomeric conjugated 1,3,5- and 2,4,6-octatrienes. To date, a series of hydrocarbons and epoxides 1-11 and their stereoisomers have been identified within the pheromone bouquets of more than 100 different species of brown algae.17-23 Identification of these compounds was based on a combination of gas chromatography-mass spectrometry (GC-MS) analysis and by comparison with authentic synthetic compounds. These sex pheromones were all lipophilic, volatile compounds that consisted of C8 or Cn linear or monocyclic hydrocarbons or their epoxides. The monocyclic compounds have a cyclopropane, cyclopentene, or cyclo-heptadiene structure. Interestingly, the relationships between the chemical structures of pheromones and the taxonomical classifications of algae are unclear (Table 1). 

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