Carbanions allylation

The TT-allylpalladium complexes 241 formed from the ally carbonates 240 bearing an anion-stabilizing EWG are converted into the Pd complexes of TMM (trimethylenemethane) as reactive, dipolar intermediates 242 by intramolecular deprotonation with the alkoxide anion, and undergo [3 + 2] cycloaddition to give five-membered ring compounds 244 by Michael addition to an electron-deficient double bond and subsequent intramolecular allylation of the generated carbanion 243. This cycloaddition proceeds under neutral conditions, yielding the functionalized methylenecyclopentanes 244[148], The syn-... 

Allylic conjugation stabilizes carbanions, and pAT values of 43 (in cyclohexylamine) and 47—48 (in THF-HMPA) have been determined for propene. On the basis of exchange rates with cesium cyclohexylamide, cyclohexene and cycloheptene have been found to have pAT values of about 45 in cyclohexylamine. The hydrogens on the sjp-... 

Certain functional groups may be protected from reduction by conversion to anions that resist reduction. Such anions include the alkoxides of allylic and benzylic alcohols, phenoxide ions, mercaptide ions, acetylide ions, ketone carbanions, and carboxylate ions. Except for the carboxylate, phenoxide, and mercaptide ions, these anions are sufficiently basic to be proton-ated by an alcohol, so they are useful for protective purposes only in the... 

Reversible electron addition to the enone forms the radical anion. Rate determining protonation of the radical anion occurs on oxygen to afford an allylic free radical [Eq. (4b) which undergoes rapid reduction to an allylic carbanion [Eq. (4c)]. Rapid protonation of this ion is followed by proton removal from the oxygen of the neutral enol to afford the enolate ion [Eq. (4c)]. 

A variety of conjugated dienones are reduced by lithium-ammonia, presumably via dienyl carbanions analogous to the allyl carbanions encountered in enone reductions. Cross-conjugated l,4-dien-3-ones afford 4-en-3-ones as the major reduction products, indicating that the cyclohexadienyl carbanion (55) protonates largely at C-1. Some protonation at C-5 does occur as shown by examination of the NMR spectrum of the crude reduction product derived from the 17-ethylene ketal of androsta-l,4-diene-3,17-dione. The 17-ethylene ketal of androst-4-ene-3,17-dione is formed in 75%... 

Most dienones that have been reduced have structures such that they cannot give epimeric products. However, reduction of 17 -hydroxy-7,17a-dimethyl-androsta-4,6-dien-3-one (63) affords 17 -hydroxy-7j9,17a-dimethylandrost-4-en-3-one (64), the thermodynamically most stable product, albeit in only 16% yield. The remainder of the reduction product was not identified. Presumably the same stereoelectronic factors that control protonation of the / -carbon of the allyl carbanion formed from an enone control the stereochemistry of the protonation of the (5-carbon of the dienyl carbanion formed from a linear dienone. The formation of the 7 -methyl compound from compound (63) would be expected on this basis. 

The rearrangement of an ether 1 when treated with a strong base, e.g. an organo-lithium compound RLi, to give an alcohol 3 via the intermediate a-metallated ether 2, is called the Wittig rearrangement. The product obtained is a secondary or tertiary alcohol. R R can be alkyl, aryl and vinyl. Especially suitable substrates are ethers where the intermediate carbanion can be stabilized by one of the substituents R R e.g. benzyl or allyl ethers. 

Treatment of 49 with a strong base such as sodium ethoxide serves to remove the last proton on the heterocyclic ring. Alkylation of the resulting carbanion with allyl bromide affords aloxidone (50) methyl sulfate on the carbanion gives trimetha-dione (51), while ethyl sulfate yields paramethadione (52). ... 

The novel cyclizadon takes places by the silane-mediated condensadon of nitroarenes with allylic carbanions, in which a sLx-membered nitrogen-containing ting is constnicted fEq. 9.54. ... 

Benzyl-type carbanions and their metallo compounds, derived from aromatic or hetero-aromatic precursors, bearing carbon- or hetero-substituents, are readily available with variable substitution patterns due to their mesomeric stabilization (see Section 1.3.2.2)2. Even dicarbanions are accessible without difficulty3,4. The equilibrium acidities of many aromatic hydrocarbons have been determined5-7. The acidities of a-hetero-substituted toluenes8 are similar to those of the corresponding allylic compounds and can usually be generated by the same methods. 

One major task is the selection of the optimal cation" for a given carbanion . It determines to a great extent the mechanism of the reaction and the positional and configurational stability of the allyl moiety, and thus, the regioselectivity, EjZ selectivity, and diastereoselectivity. Some reviews cover these topics in general1 " 5. 

For carbanionic addition, the relative negative charge and the electron densities in the 1- and 3-position in the HOMO of the ambident allylic anion determine, in addition to steric effects, the regioselectivity of the hydroxyalkylation. According to the allopolarization principle13 the following generalizations can be made ... 

Freparatively useful induced diastereoselectivities have been reported mainly for 1,1-di-substituted allyllithium derivatives which bear carbanion-stabilizing substituents. l-[Methyl-thio-l-(trimethylsilyl)-2-propenyl]lithium106 and the appropriate 1-phenylthio107 derivative, generated from the allylic sulfide with sec-butyllithium, in the reaction with tetrahydropyranyl-protected pregnolone, furnish a single diastereomer. 

Allyllithium reagents have also been used in the synthesis of (Z)-y-alkoxyallylboronates 23 2 5. Stereoselectivity is excellent in these reactions since the (Z)-y-alkoxyallyl carbanions prepared by metalation of allyl ethers are stabilized by chelation. The (Z)-y-alkoxyallyl(diisopinocam-pheyl)boranes are prepared at low temperature by an analogous procedure and must be used at — 78 "C otherwise reaction diaslereoselectivity suffers owing to the facile isomerization to the -isomer26. 

The addition of anhydrous cadmium iodide or chloride on allylic lithium carbanions causes changes in the regioselectivity, but information on the stereochemical results is scarce31-42-43. 

Sakurai reactions proceed regiospecifically with a large variety of electrophiles due to the so-called /1-effect5-9. However, allylsilanes are also known as masked allyl carbanions, which may be activated by the presence of fluoride ion10-12. 

So far, there is no conclusive evidence that a free allyl carbanion is generated from allylsilanes under fluoride ion catalysis. A hypervalent silyl anion, with the silicon still bonded to the allylic moiety, accounts equally well for the results obtained. Based on a variety of experimental results, it is in fact more likely that a nonbasic hypervalent silyl anion is involved rather than the basic free allyl carbanion first postulated14-23. When allylsilanes are treated with fluoride in the presence of enones. 1,4-addition takes place along with some 1,2-addition13. 

The reaction of the phenylsulphinyl allylic lithium a-carbanion 342 with oxiranes was found by Guittet and Julia to give, after rearrangement and desulphurization, dihydroxy-dienes 343427 (equation 197). Demoute and coworkers have described the alkylation reaction of a very sophisticated 2-alkenyl sulphoxide 344 as a part of the total synthesis of a juvenile hormone 345428 (equation 198). Since the allylic sulphoxide carbanion has an ambident character, the alkylation may occur sometimes also at the y-position. This direction of alkylation is observed in the case of acyclic allylic sulphoxide anions 346, and results in the formation of the corresponding allylic sulphoxide 347 and vinylic sulphoxide 348423 (equation 199). 

The carbanions of 1-alkenyl sulphoxides 400 also react with carbonyl compounds to give the corresponding condensation products384 (equation 237). Solladie and Moine have used this type of reaction in their enantiospecific synthesis of the chroman ring of a-tocopherol 401. Addition of the lithio reagent 402 to the aldehyde 403 affords the allylic alcohol 404 in 75% yield as a sole diastereoisomer481 (equation 238). 

Sulfoxides (R1—SO—R2), which are tricoordinate sulfur compounds, are chiral when R1 and R2 are different, and a-sulfmyl carbanions derived from optically active sulfoxides are known to retain the chirality. Therefore, these chiral carbanions usually give products which are rich in one diastereomer upon treatment with some prochiral reagents. Thus, optically active sulfoxides have been used as versatile reagents for asymmetric syntheses of many naturally occurring products116, since optically active a-sulfinyl carbanions can cause asymmetric induction in the C—C bond formation due to their close vicinity. In the following four subsections various reactions of a-sulfinyl carbanions are described (A) alkylation and acylation, (B) addition to unsaturated bonds such as C=0, C=N or C= N, (C) nucleophilic addition to a, /5-unsaturated sulfoxides, and (D) reactions of allylic sulfoxides. 

Alkylation of carbanions derived from allyl aryl sulfones 236 with alkyl halides is known... 

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