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Triptophenolide methyl ether (5) is also a natural product isolated from TWHf. See ref 3b
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Triptophenolide methyl ether (5) is also a natural product isolated from TWHf. See ref 3b.
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0342303333
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note
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2) was found to react with the C=C double bond, hence interfering with the chlorination process. Attempts to introduce an a-chloro substituent to β-keto esters by using TfCl/KHMDS produced dichloro compound D as the major product. (equation presented)
-
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58
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Standard dianion displacement did not give satisfactory yield (ca. 30%). See: Snider, B. B.; McCarthy, B. A. Tetrahedron 1993, 49, 9447.
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0343608381
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note
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(b) In our case, the dianion needs to be prepared at -10 to 0°C for 0.5 h in order to achieve high yield (80-87% yield).
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60
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0343172878
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note
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Our initial studies on asymmetric radical cyclization involved the use of the following chiral auxiliaries. Compound 17b was cyclized into trans products in poor diastereomer ratio (1.2:1 dr). Amide 17c bearing chiral pyrrolidine auxiliary was cyclized in less than 30% yield. As the cyclization of amides usually affords low chemical yields, the use of chiral amines as auxiliaries in Mn(III)-based oxidative free-radical cyclization becomes extremely limited. (equation presented)
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61
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0343172876
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note
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The trans-ring junction products 24 are a mixture of diastereomers, which are inseparable by flash column chromatography. Therefore, the diastereomer ratio was determined after the removal of an a-chloro group.
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0342303331
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note
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In the presence of lanthanide triflates, acyclic precursor 17a was decomposed.
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0342303329
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-
note
-
The authentic sample of (-)-triptonide (2) was obtained from Shanghai Institute of Materia Medica, Academia Sinica, P. R. China.
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