Allenes carbon atom reactions

Me3SnPPh2 will add to allenes under photochemical conditions, giving two regioiso-meric products32. The predominant species is that in which the phosphine residue attaches to the central carbon atom (reaction 23). The overall yield, and relative proportions of 16 and 17 produced, depends on the nature of the substituent R. For R = H, yield = 78%, ratio 16 17 = 89 11 for R = Me, yield = 67%, ratio = 73 27 for R = Bu, yield = 58%, ratio = 88 12. 

A nucleophilic attack at an allene system of the type of 417 was described for the first time by Cainelli et al. [172], namely at 444 with the chloride ion as the nucleophile (Scheme 6.91). After the treatment of the mesylate 443 with triethylamine in the presence of lithium, sodium or tetrabutylammonium chloride, mixtures of the vinyl chlorides 445 and 447 were isolated in high yields. Since the reaction did not proceed in the absence of triethylamine, the first step should be a /3-elimination of methanesulfonic acid from 443 to generate 444, which would accept a chloride ion at the central allene carbon atom. A proton transfer to either allyl terminus of the anion thus formed (446) would lead to the products 445 and 447. 

An analogous mechanism was proposed for the conversion of the triflate 416 to the vinyl-, allyl- and allenyl-A2-cephems 448 in yields of 47-71% by the respective tributyltin compounds in the presence of cuprous chloride (Scheme 6.91) [176]. Accordingly, the cyclic allene 417 should be liberated from 416 in the first step. Then, the organocopper species would transfer a hydrocarbon group to the central allene carbon atom of 417, leading to an allyl anion derivative, which is protonated during the workup. These reactions of 416 and 443 indicate that the cyclic allenes 417 and 444 behave toward nucleophiles as 1,2-cyclohexadiene (6) (Schemes 6.11— 13) and its non-polar derivatives such as 215 (Scheme 6.51), 221 (Scheme 6.52), 311 (Scheme 6.67) and 333 (Schemes 6.71 and 6.73), that is, they interact with nucleophiles at the central carbon atom of the allene system exclusively. 

Free radical addition of HBr to buta-1,2-diene (lb) affords dibromides exo-6b, (E)-6b and (Z)-6b, which consistently originate from Br addition to the central allene carbon atom [37]. The fact that the internal olefins (E)-6b and (Z)-6b dominate among the reaction products points to a thermodynamic control of the termination step (see below). The geometry of the major product (Z)-(6b) has been correlated with that of the preferred structure of intermediate 7b. The latter, in turn, has been deduced from an investigation of the configurational stability of the (Z)-methylallyl radical (Z)-8, which isomerizes with a rate constant of kiso=102s 1 (-130 °C) to the less strained E-stereoisomer (fc)-8 (Scheme 11.4) [38]. 

Nitronium fluoborate also reacts with silylallenes, as indicated in Eq. 13.40(38], Attack of the electrophile at the allene carbon atom distal to the silicon atom, 1,2-silicon migration and ring closure lead to a silyloxazole. Exposure of this material to bromine in a second step gives 124 in 72% overall yield from 123. This annula-tion is best performed with tert-butyldimethylsilylallenes. With trimethylsilyl compounds, protodesilylation is a competing side reaction. 

Treatment of 1-bromoallenyl ethyl ester 869 with bromine leads to 3,4,5-tribromo-6,6-dimethyl-3,6-dihydropyran-2-one 871. The reaction proceeds through initial electrophilic addition of bromine to the central allene carbon atom and cyclization of the resulting carbenium bromide furnishing the intermediate 870. Further reaction with bromine followed by loss of FIBr affords the 3,6-dihydropyran-2-one 871 (Scheme 240) <1996LA171>. 

Under the same reaction conditions, -keto esters which have been alkylated on the a-carbon atom (thus leading to 3,4-disubstituted 5-pyrazolones upon treatment with hydrazine) give allenic esters in good (50-70%) yield (158). The mechanism (Scheme 36) again appears to involve thallation of the enamine tautomer of the 5 -pyrazolone, but deprotonation now takes place... 

The lactam 145, bearing a terminal triple bond, is transformed into the corresponding allene derivative 146 through a Crabbe reaction (Equation 7). Using Pd(PPh ()4 as the catalyst and in the presence of phenyl iodide, the corresponding indolizine is obtained. The lactam nitrogen atom is added to the central carbon atom of the allene... 

Fig. 8 shows a plot of the calculated 48) reaction path for the reaction of 1S carbon atoms with ethylene. It will be seen that the intermediate carbene (28) is formed exothermically, but that its rearrangement to allene (29) requires much activation (50 kcal/mole). At first sight this seems inconsistent with the evidence that the reaction takes place readily at -190 °C. 

The concept of employing three components, all of which contribute one carbon atom to the final allene unit (see Scheme 5.4), is illustrated in its purest form by the reaction of carbon dioxide (165) with 2 equiv. of an alkylidenetriphenylphosphorane 166, the process very likely involving the generation in the first step of a ketene intermediate 167, which subsequently reacts with further 166 to yield the allene product 168 (Scheme 5.25) [66]. 

In analogy with reactions discussed with the examples of Schemes 6.12 and 6.13, 74 and 82 were trapped by enolates. Without exception, the enolate /3-carbon atom attacked the central carbon atom of the allene moiety with eventual formation of 3-methylenecyclobutanol derivatives as major products in most cases [64, 77]. This type of reaction is illustrated in Scheme 6.23 by two examples. 

Unusual transallenation reactions were discovered by Saalfrank et al. [29] during the reaction of the substituted malonyl chlorides 13 with the nucleophilic allene 14 (Scheme 7.3). In this case, 14 contributes only one and 13 the remaining two carbon atoms to the allene framework of the product 15. 

Several trivial but highly useful reactions are known to convert one acceptor-substituted allene into another. For example, the transformation of allenic carboxylic acids is possible both via the corresponding 2,3-allenoyl chlorides or directly to 2,3-allen-amides [182,185], Allenylimines were prepared by condensation of allenyl aldehydes with primary amines [199]. However, the analogous reaction of allenyl ketones fails because in this case the nucleophilic addition to the central carbon atom of the allenic unit predominates (cf. Section 7.3.1). Allenyl sulfoxides can be oxidized by m-CPBA to give nearly quantitatively the corresponding allenyl sulfones [200]. The reaction of the ketone 144 with bromine yields first a 2 1 mixture of the addition product 145 and the allene 146, respectively (Scheme 7.24). By use of triethylamine, the unitary product 146 is obtained [59]. The allenylphosphane oxides and allene-... 

The reactions of acceptor-substituted allenes are as manifold as their syntheses. The electron deficiency of the inner C=C double bond prove to be the predominating property of these allenes. Therefore, nucleophilic addition at the central carbon atom is an important first step inducing many reactions of the electron-deficient allenes. 

It was recognized in early examples of nucleophilic addition to acceptor-substituted allenes that formation of the non-conjugated product 158 is a kinetically controlled reaction. On the other hand, the conjugated product 159 is the result of a thermodynamically controlled reaction [205, 215]. Apparently, after the attack of the nucleophile on the central carbon atom of the allene 155, the intermediate 156 is formed first. This has to execute a torsion of 90° to merge into the allylic carbanion 157. Whereas 156 can only yield the product 158 by proton transfer, the protonation of 157 leads to both 158 and 159. 

The attack of the nucleophile on the acceptor-substituted allene usually happens at the central sp-hybridized carbon atom. This holds true also if no nucleophilic addition but a nucleophilic substitution in terms of an SN2 reaction such as 181 — 182 occurs (Scheme 7.30) [245]. The addition of ethanol to the allene 183 is an exception [157]. In this case, the allene not only bears an acceptor but shows also the substructure of a vinyl ether. A change in the regioselectivity of the addition of nucleophilic compounds NuH to allenic esters can be effected by temporary introduction of a triphenylphosphonium group [246]. For instance, the ester 185 yields the phos-phonium salt 186, which may be converted further to the ether 187. Evidently, the triphenylphosphonium group induces an electrophilic character at the terminal carbon atom of 186 and this is used to produce 187, which is formally an abnormal product of the addition of methanol to the allene 185. This method of umpolung is also applicable to nucleophilic addition reactions to allenyl ketones in a modified procedure [246, 247]. 

Intermediates such as 224 resulting from the nudeophilic addition of C,H-acidic compounds to allenyl ketones such as 222 do not only yield simple addition products such as 225 by proton transfer (Scheme 7.34) [259]. If the C,H-acidic compound contains at least one carbonyl group, a ring dosure is also possible to give pyran derivatives such as 226. The reaction of a similar allenyl ketone with dimethyl mal-onate, methyl acetoacetate or methyl cyanoacetate leads to a-pyrones by an analogous route however, the yields are low (20-32%) [260], The formation of oxaphos-pholenes 229 from ketones 227 and trivalent phosphorus compounds 228 can similarly be explained by nucleophilic attack at the central carbon atom of the allene followed by a second attack of the oxygen atom of the ketone at the phosphorus atom [261, 262], Treatment of the allenic ester 230 with copper(I) chloride and tributyltin hydride in N-methylpyrrolidone (NMP) affords the cephalosporin derivative 232 [263], The authors postulated a Michael addition of copper(I) hydride to the electron-... 

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