Allyl hydrogenation

All the allylic hydrogens m the starting alkene must be equivalent... 

Protons on caibons adjacent to a caibonyl group are deshielded slightly more than allylic hydrogens. 

Addition of a double bond to an alkene with allylic hydrogen... 

The ene reaction as a reaction principle has been first recognized and systematically investigated by Alder It is a thermal addition reaction of a double bond species 2—the enophile—and an alkene 1—the ene—that has at least one allylic hydrogen. The intramolecular variant is of greater synthetic importance than is the intermolecular reaction. 

The overall reaction includes allylic transposition of a double bond, migration of the allylic hydrogen and formation of a bond between ene and enophile. Experimental findings suggest a concerted mechanism. Alternatively a diradical species 4 might be formed as intermediate however such a species should also give rise to formation of a cyclobutane derivative 5 as a side-product. If such a by-product is not observed, one might exclude the diradical pathway ... 

A primary allylic hydrogen at the ene 1 is especially reactive a secondary hydrogen migrates less facile, and a tertiary one is even less reactive. The enophile unit should be of an electron-poor nature it can consist of a carbon-carbon double or triple bond, a carbonyl group or an azo group. Mixtures of regioisomeric products may be obtained with substituted enophiles. The acrylic ester 6 reacts with... 

Olefins react with bromine by addition of the latter to the carbon-carbon double bond. In contrast the Wohl-Ziegler bromination reaction using N-bromosuccinimide (NBS) permits the selective substitution of an allylic hydrogen of an olefinic substrate 1 by a bromine atom to yield an allylic bromide 2. 

The allylic bromination of an olefin with NBS proceeds by a free-radical chain mechanism. The chain reaction initiated by thermal decomposition of a free-radical initiator substance that is added to the reaction mixture in small amounts. The decomposing free-radical initiator generates reactive bromine radicals by reaction with the N-bromosuccinimide. A bromine radical abstracts an allylic hydrogen atom from the olefinic subsfrate to give hydrogen bromide and an allylic radical 3 ... 

As with vinyl compounds, the outcome of an allylic hydrogenation is the resultant of two competing reactions. 

A proposed mechanism for the oxidation of propylene to acrolein is by a first step abstraction of an allylic hydrogen from an adsorbed propylene by an oxygen anion from the catalytic lattice to form an allylic intermediate ... 

Ammoxidation refers to a reaction in which a methyl group with allyl hydrogens is converted to a nitrile group using ammonia and oxygen in the presence of a mixed oxides-hased catalyst. A successful application of this reaction produces acrylonitrile from propylene ... 

The production of allyl chloride could be effected by direct chlorination of propylene at high temperatures (approximately 500°C and one atmosphere). The reaction substitutes an allylic hydrogen with a chlorine atom. Hydrogen chloride is a by-product from this reaction ... 

This allylic bromination with NBS is analogous to the alkane halogenation reaction discussed in the previous section and occurs by a radical chain reaction pathway. As in alkane halogenation, Br- radical abstracts an allylic hydrogen atom of the alkene, thereby forming an allylic radical plus HBr. This allylic radical then reacts with Br2 to yield the product and a Br- radical, which cycles back... 

Draw the alkene reactant, and identify the allylic positions. In this case, there are two different allylic positions we ll label them A and B. Now abstract an allylic hydrogen... 

Transfer to monomer is of particular importance during the polymerization of allyl esters (113, X=()2CR), ethers (113, X=OR), amines (113, X=NR2) and related monomcrs.iw, 8, lb2 The allylic hydrogens of these monomers arc activated towards abstraction by both the double bond and the heteroatom substituent (Scheme 6.31). These groups lend stability to the radical formed (114) and are responsible for this radical adding monomer only slowly. This, in turn, increases the likelihood of side reactions (i.e. degradative chain transfer) and causes the allyl monomers to retard polymerization. 

Alkenes. When the substrate molecule contains a double bond, treatment with chlorine or bromine usually leads to addition rather than substitution. However, for other radicals (and even for chlorine or bromine atoms when they do abstract a hydrogen) the position of attack is perfectly clear. Vinylic hydrogens are practically never abstracted, and allylic hydrogens are greatly preferred to other positions of the moleeule. Allylic hydrogen abstraction from a cyclic alkenes is usually faster than abstraction from an acyclic alkene. ... 

When NBS is used to brominate non-alkenyl substrates such as alkanes, another mechanism, involving abstraction of the hydrogen of the substrate by the succinimidyl radical " 14 can operate. " This mechanism is facilitated by solvents (such as CH2CI2, CHCI3, or MeCN) in which NBS is more soluble, and by the presence of small amounts of an alkene that lacks an allylic hydrogen (e.g., ethene). 

The mechanism is usually electrophilic (see p. 972), but when free-radical initiators (or UV light) are present, addition can occur by a free-radical mechanism. Once Br-or Cl- radicals are formed, however, substitution may compete (14-1 and 14-2). This is espiecially important when the alkene has allylic hydrogens. Under free-radical conditions (UV light) bromine or chlorine adds to the benzene ring to give, respectively, hexabromo- and hexachlorocyclohexane. These are mixtures of stereoisomers (see p. 161). ... 

Katsumura, Kitaura and their coworkers [74] found and discussed the high reactivity of vinylic vs allylic hydrogen in the photosensitized reactions of twisted 1,3-dienes in terms of the interaction in the perepoxide structure. Yoshioka and coworkers [75] investigated the effects of solvent polarity on the product distribution in the reaction of singlet oxygen with enolic tautomers of 1,3-diketones and discussed the role of the perepoxide intermediate or the perepoxide-Uke transition state to explain their results. A recent review of the ene reactions of was based on the significant intervention of the perepoxide structure [76], which can be taken as a quasi-intermediate. 

In the photooxygenation of electron-rich olefins with allylic hydrogen atoms, ene reactivity usually dominates [96]. Nevertheless, other reactions become the preferred reaction mode. Inagaki et al. [92] attributed the exclusive [2h-2] cycloaddition... 

The argument of the directing effect of lone pairs on the substiment [92] easily extends to the alkyl cases. The orbital interaction (Scheme 20) [103] in the pere-poxide quasi-intermediate suggests the stabilization occurs by the simultaneous interaction of O with two allylic hydrogens on the same side of the alkene. Photooxygenation of trisubstituted olefins revealed a strong preference for H-abstraction from disubstituted side of the double bond [104, 105],... 

Peroxides cross-linking of the more highly unsaturated polymers is more efficient due to higher concentration of allylic hydrogen. These are readily abstracted and efficiently converted to cross-link. 

The formation of ROO and RO radicals, and M" =0 species is expected when phthalocyanines and porphyrins are used as catalysts (21, 22). The formation of the epoxide, Fignre 49.1, may be associated with the attack of metal oxo species (Fe = O) to the double bond (23). For a-pinene this attack is possibly favored by its rigid structure that causes an orbital overlapping, making the allylic hydrogen abstraction difficult (24). 

It has been reported that molecnlar oxygen plays an important role in the allylic oxidation of olefins with TBHP (25, 26). Rothenberg and coworkers (25) proposed the formation of an alcoxy radical via one-electron transfer to hydroperoxide, Equation 4, as the initiation step of the allylic oxidation of cyclohexene in the presence of molecnlar oxygen. Then, the alcoxy radical abstracts an allylic hydrogen from the cyclohexene molecnle. Equation 5. The allylic radical (8) formed reacts with molecular oxygen to yield 2-cyclohexenyl hydroperoxide... 

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