Aryl ethers, cleavage preparation

Multiple reactions. The reagent is prepared from chromium(III) chloride and 4 equiv of BuLi in THF. It can be isolated as a dark red-brown LiCrH2-THF complex, free from LiCl. As shown in the following diagram, it can perform hydrodehalogenation, aryl ether cleavage, coupling reactions, and polymerization. 

The Pd-catalyzed electro-cleavage of the C—O bond of allyl aryl ether proceeds smoothly in a DMF-Bu4NBp4-(Mg)-(Stainless Steel) system, giving depro-tected products in 73 99% yield [437]. The sp-sp intermolecular coupling reaction with the Pd water-soluble catalyst prepared in situ from Pd(II) acetate and sul-fonated triphenylphosphine in an MeCN-H2O system yields diynes in 45 65% yields [438]. Similarly, the sp -sp coupling of 2-iodophenols or 2-iodoanilines and terminal alkynes followed by intramolecular cyclization gives indol and furan... 

R" may be alkyl or aryl. For dialkyl ethers, the reaction does not end as indicated above, since R OH is rapidly converted to R OR by the sulfonic acid (reaction 0-16), which in turn is further cleaved to R 0S02R" so that the product is a mixture of the two sulfonates. For aryl alkyl ethers, cleavage always takes place to give the phenol, which is not converted to the aryl ether under these conditions. Ethers can also be cleaved in a similar manner by mixed anhydrides of sulfonic and carboxylic acids733 (prepared as in 0-33). p-Hydroxy alkyl perchlorates734 and sulfonates can be obtained from epoxides.735 Epoxides and oxetanes give dinitrates when treated with N2Os,736 e.g.,... 

Cleavage conditions for alkyl benzyl ethers prepared from acid-labile benzyl alcohols are similar to those for the corresponding benzyl esters (Table 3.30). Aryl benzyl ethers, however, are generally cleaved more easily by acidolysis than esters or alkyl ethers. Phenols etherified with hydroxymethyl polystyrene, for instance, can even be released by treatment with TFA (Entry 1, Table 3.31). It has also been shown that Wang resin derived phenyl ethers are less stable than Wang resin derived esters towards refluxing acetic acid [29]. Alternatively, boron tribromide may be used to cleave aryl ethers from hydroxymethyl polystyrene [573],... 

The cleavage of alkyl aryl ethers is more important as a preparative method for phenols than for alkyl halides (method 97). The procedure has been employed as the final step in a synthesis proposed as a means for increasing the carbon chain of an alkyl halide, viz., ... 

Aryl ethers in the presence of a solvent can be preferentially halo-genated in the nucleus. Thus, anisole with phosphorus pentabromide or with iodine monochlotide yields p-bromoanisole (90%) and p-iodo-anisole (46%), respectively. Phosphorus pentachloride has also been used for the halogenation of the nucleus as in the preparation of 4-chloro-biphenyl ether (90%). The action of this reagent with aliphatic and aryl-aliphatic ethers is very complex, giving both cleavage and halogenation products. ... 

Condensation of resin bound ketones with hydrazines followed by cyclizative cleavage was used in a synthesis of pyrazolinones [67]. Samarium iodide induced radical cyclization of allyl aryl ethers led to benzofuran derivatives [68]. Kurth et al. have reported a two reaction iterative process for the construction of polyisoxazolines [69] and polyisoxazoles [70]. An intramolecular Heck reaction has been employed to prepare 2-oxindole derivatives [71]. 

CHROMIUM TRIOXIDE-PYRIDINE COMPLEX, preparation in situ, 55, 84 Chrysene, 58,15, 16 fzans-Cinnamaldehyde, 57, 85 Cinnamaldehyde dimethylacetal, 57, 84 Cinnamyl alcohol, 56,105 58, 9 2-Cinnamylthio-2-thiazoline, 56, 82 Citric acid, 58,43 Citronellal, 58, 107, 112 Cleavage of methyl ethers with iodotri-methylsilane, 59, 35 Cobalt(II) acetylacetonate, 57, 13 Conjugate addition of aryl aldehydes, 59, 53 Copper (I) bromide, 58, 52, 54, 56 59,123 COPPER CATALYZED ARYLATION OF /3-DlCARBONYL COMPOUNDS, 58, 52 Copper (I) chloride, 57, 34 Copper (II) chloride, 56, 10 Copper(I) iodide, 55, 105, 123, 124 Copper(I) oxide, 59, 206 Copper(ll) oxide, 56, 10 Copper salts of carboxylic acids, 59, 127 Copper(l) thiophenoxide, 55, 123 59, 210 Copper(l) trifluoromethanesulfonate, 59, 202... 

Because of the special structural requirements of the resin-bound substrate, this type of cleavage reaction lacks general applicability. Some of the few examples that have been reported are listed in Table 3.19. Lactones have also been obtained by acid-catalyzed lactonization of resin-bound 4-hydroxy or 3-oxiranyl carboxylic acids [399]. Treatment of polystyrene-bound cyclic acetals with Jones reagent also leads to the release of lactones into solution (Entry 5, Table 3.19). Resin-bound benzylic aryl or alkyl carbonates have been converted into esters by treatment with acyl halides and Lewis acids (Entry 6, Table 3.19). Similarly, alcohols bound to insoluble supports as benzyl ethers can be cleaved from the support and simultaneously converted into esters by treatment with acyl halides [400]. Esters have also been prepared by treatment of carboxylic acids with an excess of polystyrene-bound triazenes here, diazo-nium salts are released into solution, which serve to O-alkylate the acid (Entry 7, Table 3.19). This strategy can also be used to prepare sulfonates [401]. 

In the morphinan series, the preparation of 3-alkyl-morphinans222 and 3-mercapto-morphinans223 has been described. In the benzomorphan series, a novel cleavage of aryl benzyl ethers and of aryl allyl ethers has been described and used in an improved synthesis of pentazocine. The lactam (162), on hydrogenolysis, gives the benzomorphan (163 R1 = R2 = H). Treatment of this with dimethylallyl... 

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