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Volumn 44, Issue 8, 2005, Pages 1232-1236

Metal-free cross-coupling reactions of aryl sulfonates and phosphates through photoheterolysis of aryl-oxygen bonds

Author keywords

Aryl cations; Aryl esters; Arylation; Cross coupling; Photochemistry

Indexed keywords

CHARGE TRANSFER; CHEMICAL BONDS; ESTERS; OLEFINS; REACTION KINETICS; SUBSTITUTION REACTIONS;

EID: 15444374961     PISSN: 14337851     EISSN: None     Source Type: Journal    
DOI: 10.1002/anie.200461444     Document Type: Article
Times cited : (68)

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    • Palladium-catalyzed arylation of allyltrimethylsilane starting from aryl iodides led to allyl aromatic compounds in low to good selectivities according to the conditions used,[20] whereas aryl triflates afforded arylated allylsilanes.[21]
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    • -1).
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    • Some irradiations with mesylate 5 in the presence of ATMS were carried out under nonsensitized conditions at 254 nm and gave the same product distribution, although product 13 was not stable under prolonged irradiation. The use of the lamps at a wavelength of 310 nm prevented both product photodegradation and competititve absorption by benzene when this was used as the trap. A possible wavelength dependence of the reaction is under investigation.
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    • The presence of a protic polar medium (for example, water) could dramatically favor the photoheterolytic process, see: M. Freccero, M. Fagnoni, A. Albini, J. Am. Chem. Soc. 2003, 125, 13 182-13 190.
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    • 4-Methoxybiphenyl was obtained only in 7% yield in aprotic solvent after irradiation of 4-chloroanisole in the presence of benzene (1M). In TFE the yield did not exceed 70%.
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    • Triethylamine (0.05M) buffers the acid liberated in the photolysis of the esters and avoids degradation and polymerization of the photoproducts, as indicated by experiments using cesium carbonate instead which led to the same product distribution. However, the use of the MeCN/water mixed solvent made the use of a base unnecessary, thus supporting the idea that electron transfer between the amine and the triplet state of the aromatic reagents (very short lived in the halides, reference [25] and presumably also of the esters) is not involved in the arylation reaction.
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    • 3, in the same proportion as from 4-chloroanisole (see reference [12]). This reaction is difficult to envisage other than involving loss of a proton from (or solvent addition to) an adduct cation. (Further evidence is the fact that a cationic Wagner-Meerwein rearrangement has taken place in the last product).
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    • The role of solvents, and in particular of alcohols, as hydrogen donors (and not as n nucleophiles) in the reaction with the triplet phenyl cation has been previously demonstrated, see Refs. [10-12].
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    • In rare instances, the Suzuki coupling occurred under microwave irradiation in the absence of a catalyst, see: N. E. Leadbeater, M. Marco, Angew. Chem. 2003, 115, 1445-1447; Angew. Chem. Int. Ed. 2003, 42, 1407-1409.
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    • In rare instances, the Suzuki coupling occurred under microwave irradiation in the absence of a catalyst, see: N. E. Leadbeater, M. Marco, Angew. Chem. 2003, 115, 1445-1447; Angew. Chem. Int. Ed. 2003, 42, 1407-1409.
    • (2003) Angew. Chem. Int. Ed. , vol.42 , pp. 1407-1409
  • 52
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    • note
    • Quartz allowed the absorption of all of the light emitted by the lamp.


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