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The following general method was used to prepare 23: Turk, C.; Svete, J.; Stanovnik, B.; Golic, L.; GolicGrdadolnik, S.; Golobic, A.; Selic, L. Helv. Chim. Acta 2001, 84, 146-156.
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(b) The following general method was used to prepare 23: Turk, C.; Svete, J.; Stanovnik, B.; Golic, L.; GolicGrdadolnik, S.; Golobic, A.; Selic, L. Helv. Chim. Acta 2001, 84, 146-156.
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109
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53849147430
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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.
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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.
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110
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0027953195
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See the following and references cited therein
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See the following and references cited therein: Coppola, B. P.; Noe, M. C.; Schwartz, D. J.; Abdon, R. L.; Trost, B. M. Tetrahedron 1994, 50, 93-116.
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Coppola, B.P.1
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Abdon, R.L.4
Trost, B.M.5
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111
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53849136790
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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
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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.
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