Stereoselective Oxidative Rearrangement of 2-Aryl Tryptamine Derivatives

Movassaghi, Mohammad; Schmidt, Michael A.; Ashenhurst, James A.

doi:10.1021/ol8015176

Cited by 96 publications

(87 citation statements)

References 32 publications

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“…17,18 Our continued interest in this area yielded an efficient and stereocontrolled synthetic strategy involving oxidation and rearrangement of 2,3-disubstituted indoles, especially those with an aryl substituent at the 2-position, for efficient access to oxindole products. 19 Despite outstanding advancements in the area of asymmetric oxidation, 20 enantioselective oxidation of 2,3-disubstituted indoles remains a challenging problem. 21,22 Recently, in collaboration with the Miller group, we reported an asymmetric oxidation of 2,3-disubstituted indole for the formation of enantiomerically enriched hydroxyindolenines using an aspartyl based peptide catalyst.…”

Section: Resultsmentioning

confidence: 99%

Total Synthesis, Stereochemical Assignment, and Biological Activity of All Known (−)-Trigonoliimines

et al. 2013

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A full account of our concise and enantioselective total syntheses of all known (−)-trigonoliimine alkaloids is described. Our retrobiosynthetic analysis of these natural products enabled identification of a single bistryptamine precursor as a precursor to all known trigonoliimines through a sequence of transformations involving asymmetric oxidation and reorganization. Our enantioselective syntheses of these alkaloids enabled the revision of the absolute stereochemistry of (−)-trigonoliimines A, B, and C. We report that trigonoliimines A, B, C, and structurally related compounds showed weak anticancer activities against HeLa and U-937 cells.

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Section: Resultsmentioning

confidence: 99%

Total Synthesis, Stereochemical Assignment, and Biological Activity of All Known (−)-Trigonoliimines

et al. 2013

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“…A similar diastereomeric ratio (dr) value is observed in the oxidation of 21 using stoichiometric quantities of DMDO. 6 On the other hand, a significant amplification of diastereoselectivity of the reaction is observed when peptide 22 is used as a catalyst. In this case, a striking “matched” case of double asymmetric induction is observed, with the formation of 23 and 24 as a 92:8 mixture of diastereomers (75% combined yield; Figure 3, eq 6).…”

Section: Resultsmentioning

confidence: 99%

Chemoselective and Enantioselective Oxidation of Indoles Employing Aspartyl Peptide Catalysts

et al. 2011

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Catalytic enantioselective indole oxidation is a process of particular relevance to the chemistry of complex alkaloids, as it has been implicated in their biosynthesis. In the context of synthetic methodology, catalytic enantioselective indole oxidation allows a rapid and biomimetic entry into several classes of alkaloid natural products. Despite this potentially high utility in the total synthesis, reports of catalytic enantioselective indole oxidation remain sparse. Here we report a highly chemoselective catalytic system for the indole oxidation that delivers 3-hydroxy-indolenines with good chemical yields and moderate to high levels of enantio- and diastereoselectivity (up to 95:5 er and up to 92:8 dr. These results represent, to our knowledge, the most selective values yet reported in the literature for catalytic asymmetric indole oxidation). Furthermore, the utility of enantioenriched hydroxy-indolenines in stereospecific rearrangements is demonstrated.

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“…Hydroxyindolenine 28 rearranges with heating using Sc(OTf) 3 over 2 hours to afford pseudoindoxyl 33 (Figure 4C) instead of the desired spirooxindole. The equilibrium between pseudoindoxyls and spirooxindoles is well recognized and has been studied for the migration of C2 alkyl substituents by Borschberg 28 and recently for C2 aryl substituents by Movassaghi and coworkers 29 . However, despite prolonged heating, further rearrangement of pseudoindoxyl 33 to the desired spirooxindole was not observed.…”

Section: Resultsmentioning

confidence: 99%

Total synthesis and isolation of citrinalin and cyclopiamine congeners

Mercado-Marin

García-Reynaga

Romminger

et al. 2014

Nature

151

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It is said that carbon, the most abundant element in organic matter, supplies life’s quantity, whereas nitrogen supplies its quality. It is therefore unsurprising that many natural products that contain basic nitrogens (alkaloids) are coveted for their benefit to human health. However, nitrogen is known to mire many chemical syntheses because of its basicity and susceptibility to oxidation. This challenge may be heightened by the presence of more than one nitrogen atom in a targeted complex alkaloid, but can be met by the selective introduction and removal of functional groups that mitigate basicity, as highlighted herein with the first chemical syntheses of citrinalin B and cyclopiamine B. The chemical connections that have been realized as a result of these syntheses, in addition to the isolation of both 17-hydroxycitrinalin B and citrinalin C through 13C feeding studies, supports the existence of a common bicyclo[2.2.2]diazaoctane containing biogenetic precursor to these compounds as has been proposed previously.

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Stereoselective Oxidative Rearrangement of 2-Aryl Tryptamine Derivatives

Cited by 96 publications

References 32 publications

Total Synthesis, Stereochemical Assignment, and Biological Activity of All Known (−)-Trigonoliimines

Total Synthesis, Stereochemical Assignment, and Biological Activity of All Known (−)-Trigonoliimines

Chemoselective and Enantioselective Oxidation of Indoles Employing Aspartyl Peptide Catalysts

Total synthesis and isolation of citrinalin and cyclopiamine congeners

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