- Catalyst-Controlled Regiodivergence in Rearrangements of Indole-Based Onium Ylides
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We have developed catalyst-controlled regiodivergent rearrangements of onium-ylides derived from indole substrates. Oxonium ylides formed in situ from substituted indoles selectively undergo [2,3]- and [1,2]-rearrangements in the presence of a rhodium and a copper catalyst, respectively. The combined experimental and density functional theory (DFT) computational studies indicate divergent mechanistic pathways involving a metal-free ylide in the rhodium catalyzed reaction favoring [2,3]-rearrangement, and a metal-coordinated ion-pair in the copper catalyzed [1,2]-rearrangement that recombines in the solvent-cage. The application of our methodology was demonstrated in the first total synthesis of the indole alkaloid (±)-sorazolon B, which enabled the stereochemical reassignment of the natural product. Further functional group transformations of the rearrangement products to generate valuable synthetic intermediates were also demonstrated.
- Nair, Vaishnavi N.,Kojasoy, Volga,Laconsay, Croix J.,Kong, Wang Yeuk,Tantillo, Dean J.,Tambar, Uttam K.
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supporting information
p. 9016 - 9025
(2021/06/30)
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- Anti-Cytokine Heterocyclic Compounds
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Heterocyclic compounds and analogues thereof and their use as inhibitors of Mitogen-Activated Protein Kinase-Activated Protein kinase-2 (MAPKAP-k2), and also to a method for preventing or treating a disease or disorder that can be treated or prevented by
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Page/Page column 48; 49
(2010/11/25)
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- Thromboxane A2 synthetase inhibitors with histamine H1-blocking activity: Synthesis and evaluation of a new series of indole derivatives
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A novel series of N-substituted 3-(1H-imidazol-1-ylmethyl)indole carboxylic acid derivatives were prepared and evaluated for thromboxane A2 (TXA2) synthetase-inhibitory and histaminergic H1-blocking activity. Among the compounds synthesized, indole-6-carboxylic acid derivatives showed higher activities than the other positional isomers of carboxylic acid. 1-[3-(4- Benzhydryl-1-piperazinyl)propyl]-3-(1H-imidazol-1-ylmethyl)-1H-indole-6- carboxylic acid (12) had the strongest thromboxane synthetase inhibitory activity (IC50 = 5 x 10-8 M) and H1-blocking activity (IC50 = 8 x 10- 9 M).
- Kamiya,Matsui,Shirahase,Nakamura,Wada,Kanda,Shimaji,Kakeya
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p. 1692 - 1695
(2007/10/03)
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