- Total syntheses of indolactam alkaloids (-)-indolactam V, (-)-pendolmycin, (-)-lyngbyatoxin A, and (-)-teleocidin A-2
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We report the total syntheses of (-)-indolactam V and the C7-substituted indolactam alkaloids (-)-pendolmycin, (-)-lyngbyatoxin A, and (-)-teleocidin A-2. The strategy for preparing indolactam V relies on a distortion-controlled indolyne functionalization reaction to establish the C4-N linkage, in addition to an intramolecular conjugate addition to build the conformationally-flexible nine-membered ring. The total synthesis of indolactam V then sets the stage for the divergent synthesis of the other targeted alkaloids. Specifically, late-stage sp2-sp3 cross-couplings on an indolactam V derivative are used to introduce the key C7 substituents and the necessary quaternary carbons. These challenging couplings, in addition to other delicate manipulations, all proceed in the presence of a basic tertiary amine, an unprotected secondary amide, and an unprotected indole. Thus, our approach not only enables the enantiospecific total syntheses of four indolactam alkaloids, but also serves as a platform for probing complexity-generating and chemoselective transformations in the context of alkaloid total synthesis. This journal is the Partner Organisations 2014.
- Fine Nathel, Noah F.,Shah, Tejas K.,Bronner, Sarah M.,Garg, Neil K.
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p. 2184 - 2190
(2014/05/20)
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- Synthesis of Teleocidins A, B and Their Congeners. Part 2. Synthesis of Lyngbyatoxin A (Teleocidin A-1), Teleocidin A-2, Pendolmycin, and (R,E)- and (S,E)-7-(3,7,11-Trimethyl-1,6,10-dodecatrien-3-yl)-(-)-indolactams V
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Details of the synthesis method of the tumor promoters, lyngbyatoxin A (= teleocidin A-1) (1) and teleocidin A-2 (2) from (R)- and (S)-methyl N--N-methyl-L-valinate (3 and 4) are presented.Other titled compounds, 6, 7a, and 7b, were prepared analogously. Key words: alkaloid synthesis; lyngbyatoxin A, teleocidin A-2; pendolmycin; teleocidin analogs.
- Muratake, Hideaki,Okabe, Kazuaki,Natsume, Mitsutaka
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p. 8545 - 8558
(2007/10/02)
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- The Second Generation Synthesis of a Tumor Promoter Pendolmycin
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Total synthesis of a tumor promoter pendolmycin (1) was accomplished in the stereospecific manner using a D-serine derivative 7 and an L-valine derivative 16 as chiral sources.Methyl 2-(bromomethyl)benzoate was used for the critical step of the indole cyc
- Okabe, Kazuaki,Natsume, Mitsutaka
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p. 7615 - 7624
(2007/10/02)
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- BIOSYNTHESIS OF INDOLE ALKALOID TUMOR PROMOTERS TELEOCIDINS (I) POSSIBLE BIOSYNTHETIC PATHWAY OF THE MONOTERPENOID MOIETIES OF TELEOCIDINS
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Possible biosynthetic pathway of monoterpenoid moieties of teleocidins shown in Fig. 8 was proposed by feeding experiments with several D or 13C-labelled precursors and isolation of new telecidin-related metabolites named blastmycetin D (6) and E (7).
- Irie, Kazuhiro,Kajiyama, Shin-ichiro,Funaki, Atsushi,Koshimizu, Koichi,Hayashi, Hideo,Arai, Motoo
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p. 2773 - 2788
(2007/10/02)
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- Total synthesis of indole alkaloid pendolmycin
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The teleocidin class of an indole alkaloid, pendolmycin (1) was synthesized from 1-(4-methylphenylsulfonyl)pyrrole in thirteen steps by way of the indole derivative (16), the amino- diester compound (6), and the ethyl carboxylate (5).
- Okabe, Kazuaki,Muratake, Hideaki,Natsume, Mitsutaka
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p. 5113 - 5120
(2007/10/02)
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