Alkenes, with acids structure

Acid catalyzed hydration converts alkenes to alcohols with regioselectivity according to Markovnikov s rule Frequently however one needs an alcohol having a structure that corresponds to hydration of an alkene with a regioselectivity opposite to that of Markovnikov s rule The conversion of 1 decene to 1 decanol is an example of such a transformation... 

Osmium tetroxide, reaction with alkenes, 235-236 toxicity of, 235 Oxalic add, structure of, 753 Oxaloacetic acid, structure of, 753 Oxetane, reaction with Grignard reagents, 680 Oxidation, 233, 348 alcohols, 623-626 aldehydes, 700-701 aldoses, 992-994 alkenes, 233-236 biological, 625-626 phenols, 631 sulfides, 670 thiols, 668... 

We will now explore each aspect of this two-step process. In the first step, a peroxyacid (RCO3H), sometimes called a per-acid, reacts with the alkene. Compare the structure of a carboxylic acid with the structure of a peroxy acid ... 

The other acetogenins, shown in Table II, are a varied assortment of small molecule compounds which as a group contain alkene, alcohol, and carbonyl (acid, ester, aldehyde, and ketone) functionality. They are fairly typical substances with common structural features. Again, those compounds possessing an odd number of carbon atoms are less common, and biogenetlcally may be derived from a propionate starter unit. 

At that period of time, this rather primitive transition structure for the peracid epoxidation of ethylene was sufficiently novel to warrant publication as a communication Today, calculating transition structures for epoxidation of a variety of complex alkenes with the actual peracid used experimentally, such as meta-chloroperoxybenzoic acid m-CPBA), is commonplace . ... 

TABLE 8. Differences (A) in the O—Cl and O—C2 calculated distances of transition structures for the epoxidations of alkenes with peroxyformic acid using different methods... 

FIGURE 26. Transition structures for the epoxidation of selected cyclic alkenes with peroxyformic acid (PEA), optimized at the B3LYP/6-31+G(d,p) level of theory. The classical activation barriers are given at B3LYP/6-311+G(3df,2p)//B3LYP/6-31+G(d,p)... 

The high selectivities found in the protonation experiments of the nitronate ions 44 suggested that also allyl anions 54 can be regioselectively protonated by a general acid protonation. Therefore, some lithium allyl compounds (Structures 6) were generated by deprotonation of alkenes with n-butyl lithium. 

KEY CONCEPT PROBLEM 23.19 Draw the structure of the alcohol you would expect to obtain by acid-catalyzed reaction of the following cyclic alkene with H20 ... 

The property of the polymers in question to form nonspherical nanostructures was confirmed in experimental studies. Shih et al. [29] synthesized alternating copolymers of 1-alkenes with maleic anhydride. The maleic anhydride units were hydrolyzed to maleic acid units. Fully hydrolyzed macromolecules associated into microstructures of cylindrical and ellipselike shape. The cylindrical shape was characteristic of copolymers with octadecene and hexadecene moieties, while the copolymers with lower alkene copolymers (tetradecene, dodecene, decene, octene) formed ellipsoidal structures. Wataoka et al. [30] investigated the formation of nonspherical helices in a system of maltopentaose-carrying polystyrene (PS). The polymer was synthesized via the homopolymerization of vinylbenzyl maltopentaose amide (Scheme 3). 

The reaction of alkenes with peroxycarboxylic acids to produce epoxides was discovered by Prilezhaev over 80 years ago.14 It is still the most widely used method for epoxidation, and considerable work has been carried out to elucidate the mechanism. The commonly accepted explanation for oxirane formation involves a cyclic polar process where the proton is transferred intramolecularly to the carbonyl oxygen, with simultaneous attack by the alkene rc-bond. This concerted process was suggested by Bartlett,15 and because of the unique planar transition structure it is referred to as the butterfly mechanism (Figure 3.2). 

According to Eq. (17), AGd° is negative if AG 0 < AG. A value of -50 kJ mol-1 was estimated for AGa° (-70° C) above, so that carbocation salts can only add to olefins to form covalent products if AG > -50 kJ mol-1. As AG depends both on the structure of R+ and on the Lewis acidity of MCI, we can conclude that the thermodynamic driving force for Case d increases with decreasing stabilization of R+ and decreasing chloride-ion affinity of MC1 . Because the magnitude of AG can be estimated from the relative chloride affinities of carbocations and Lewis acidic metal halides in Scheme 7 (Section II.G), one can derive which carbocationic salts might add to alkenes with formation of covalent products. 

Indeed, a transformation of alkenes to a-ketols was found to proceed highly efS-ciently. Thus, the low-valent ruthenium-catalyzed oxidation of alkenes with peracetic acid in an aqueous solution under mild conditions gives the corresponding a-ketols, which are important key structures of various biologically active compounds [127]. Typically, the RuCls-catalyzed oxidation of 3-acetoxy-1-cyclohexene (42a) and 3-azide-1-cyclohexene (42b) with peracetic acid in CH2CI2-CH3CN-H2O (1 1 1) gave (2S, 3R )-3-acetoxy-2-hydroxycyclohexanone (43a) and (2S, 3R )-3-azide-2-hydroxy-cyclohexanone (43b) chemo- and stereoselectively in 70% and 65% yield, respectively... 

MO calculations have been carried out on the isomerization of cyclopropane to propene, and the MNDO method has been used to study the reaction pathway and to optimize the structure of reactant, transition structure, and product of the ring opening reaction of bicyclo[1.1.0]butane. Various methods have been employed to estimate the rate constants for ring opening of the 2-cyclopropyl-2-propyl radical. 1-Acceptor-1-sulfenyl-substituted 2-vinylcyclopropanes of the type (430) have been found to afford 6-sulfenyl-a,jS y, -unsaturated carboxylic esters and nitriles (431) upon treatment with acid, by a process which involves C(l)—C(2) bond fission and a novel 1,5-sulfenyl rearrangement (see Scheme 110). It has been shown that the benzophenone-sensitized photolysis of vinyl norcaradiene derivatives, such as 5-(2-methylprop-l-enyl)-3-oxatricyclo[4.4.0.0 ]deca-7,9-dien-4-ones (432), results in the regioselective cleavage of only one of the cyclopropyl c-bonds to afford isochroman-3-one derivatives (433). It has been reported that the major product obtained from the reaction of structurally diverse a-diazo ketones with an electron-rich alkene in the... 

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