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Volumn 73, Issue 20, 2008, Pages 8057-8068

1,3-Dipolar cycloadditions of acetylenic sulfones in solution and on solid supports

Author keywords

[No Author keywords available]

Indexed keywords

ABS RESINS; ACETYLENE; ACIDS; CARBOXYLIC ACIDS; CATALYST ACTIVITY; CHEMICAL REACTIONS; CYANIDES; CYCLOADDITION; ESTERIFICATION; ESTERS; LIGHTING; NITROGEN COMPOUNDS; NITROGEN OXIDES; ORGANIC ACIDS; ORGANIC COMPOUNDS; POLYMERS; RESINS; SAMARIUM; SODIUM;

EID: 53849101867     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo801621d     Document Type: Article
Times cited : (76)

References (111)
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    • The esterincation of 5 was performed by a similar method to one used for the preparation of esters from bromomethyl Wang resin and a benzoic acid derivative: (a) Morales, G. A.; Corbett, J. W.; DeGrado, W. F. J. Org. Chem. 1998, 63, 1172-1177.
    • The esterincation of 5 was performed by a similar method to one used for the preparation of esters from bromomethyl Wang resin and a benzoic acid derivative: (a) Morales, G. A.; Corbett, J. W.; DeGrado, W. F. J. Org. Chem. 1998, 63, 1172-1177.
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    • Under rigorously anhydrous conditions, the reaction of 23 with the phenyl-substituted acetylenic sulfone 28b afforded the expected initial cycloadduct analogous to 59a. It was formed in the ratio of 5:1, in a combined yield of 89%, with a minor regio- or diastereomer that could not be identified with certainty and could not be separated from the main product.
    • Under rigorously anhydrous conditions, the reaction of 23 with the phenyl-substituted acetylenic sulfone 28b afforded the expected initial cycloadduct analogous to 59a. It was formed in the ratio of 5:1, in a combined yield of 89%, with a minor regio- or diastereomer that could not be identified with certainty and could not be separated from the main product.
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    • It is doubtful that direct reductive cleavage of the polymer-supported cycloadduct occurred with sodium amalgam, as penetration of the polymer beads by the reagent under the two-phase conditions of the reaction is unlikely. However, it is possible that the relatively basic conditions resulted in prior hydrolysis of the ester linker, followed by reduction of the liberated benzyl alcohol moiety in a subsequent step. The same product 65 was obtained in 53% yield when samarium diiodide-HMPA was employed as the reductant
    • It is doubtful that direct reductive cleavage of the polymer-supported cycloadduct occurred with sodium amalgam, as penetration of the polymer beads by the reagent under the two-phase conditions of the reaction is unlikely. However, it is possible that the relatively basic conditions resulted in prior hydrolysis of the ester linker, followed by reduction of the liberated benzyl alcohol moiety in a subsequent step. The same product 65 was obtained in 53% yield when samarium diiodide-HMPA was employed as the reductant.


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