The preparation, structure, and chemistry of hypervalent iodine compounds are reviewed with emphasis on their synthetic application. Compounds of iodine possess reactivity similar to that of transition metals, but have the advantage of environmental sustainability and efficient utilization of natural resources. These compounds are widely used in organic synthesis as selective oxidants and environmentally friendly reagents. Synthetic uses of hypervalent iodine reagents in halogenation reactions, various oxidations, rearrangements, aminations, C–C bond-forming reactions, and transition metal-catalyzed reactions are summarized and discussed. Recent discovery of hypervalent catalytic systems and recyclable reagents, and the development of new enantioselective reactions using chiral hypervalent iodine compounds represent a particularly important achievement in the field of hypervalent iodine chemistry. One of the goals of this Review is to attract the attention of the scientific community as to the benefits of...

Advances in Synthetic Applications of Hypervalent Iodine Compounds

Occurrence, Biogenesis, and Synthesis of Biologically Active Carbazole Alkaloids

Asymmetric Organocatalytic Cyclization and Cycloaddition Reactions

Taxonomy of Aspergillus section Flavi and their production of aflatoxins, ochratoxins and other mycotoxins

Organohypervalent iodine reagents have attracted significant recent interest as versatile and environmentally benign oxidants with numerous applications in organic synthesis. This Perspective summarizes synthetic applications of hypervalent iodine(V) reagents: 2-iodoxybenzoic acid (IBX), Dess−Martin periodinane (DMP), pseudocyclic iodylarenes, and their recyclable polymer-supported analogues. Recent advances in the development of new catalytic systems based on the generation of hypervalent iodine species in situ are also overviewed.

Organoiodine(V) Reagents in Organic Synthesis

The first total synthesis of anominine has been achieved, and the absolute configuration of the product has been determined. The key features include the development of a new, highly efficient organocatalyzed method for the asymmetric synthesis of Wieland-Miescher ketone building blocks, an unusual selenoxide [2,3]-sigmatropic rearrangement, and a ZrCl(4)-catalyzed indole coupling as well as several chemoselective transformations controlled by the structurally congested nature of the bicyclic core.

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Total synthesis of (-)-anominine.

This research was supported by the Ministerio de Ciencia e Innovacion (Spain)-FEDER through projects CTQ2007-
61338/BQU, CTQ2007-62771/BQU and Consolider Ingenio 2010 CSD2007-00006. Thanks are also due to the Comissionat per a Universitats i Recerca (Catalonia) for Grant 2005SGR-00442, Generalitat Valenciana for Grant (GVPRE/
2008/006) and the University of Alicante (GRJ06-05).

Efficient Solvent-Free Robinson Annulation Protocols for the Highly Enantioselective Synthesis of the Wieland–Miescher Ketone and Analogues

A highly congested decalin embodying an α-methylene ketone is synthesized in 11 steps from the Wieland–Miescher ketone and efficiently converted to the polycyclic frameworks of anominine and tubingensin A, which constitutes the first approach to the skeleton of these indole diterpenoids.

Polycyclic framework synthesis of anominine and tubingensin A indole diterpenoids.

Additions of lactams, imides, (S)-4-benzyl-1,3-oxazolidin-2-one, 2-pyridone, pyrimidine-2,4-diones (AZT derivatives), or inosines to the electron-deficient triple bonds of methyl propynoate, tert-butyl propynoate, 3-butyn-2-one, N-propynoylmorpholine, or N-methoxy-N-methylpropynamide in the presence of many potential catalysts were examined. DABCO and, second, DMAP appeared to be the best (highest reaction rates and E/Z ratios), while RuCl3, RuClCp*(PPh3)2, AuCl, AuCl(PPh3), CuI, and Cu2(OTf)2 were incapable of catalyzing such additions. The groups incorporated (for example, the 2-(methoxycarbonyl)ethenyl group that we name MocVinyl) serve as protecting groups for the above-mentioned heterocyclic CONH or CONHCO moieties. Deprotections were accomplished via exchange with good nucleophiles: the 1-dodecanethiolate anion turned out to be the most general and efficient reagent, but in some particular cases other nucleophiles also worked (e.g., MocVinyl-inosines can be cleaved with succinimide anion). Some structural and mechanistic details have been accounted for with the help of DFT and MP2 calculations.

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Nucleophile-Catalyzed Additions to Activated Triple Bonds. Protection of Lactams, Imides, and Nucleosides with MocVinyl and Related Groups

(S)-8a-Methyl-3,4,8,8a-tetrahydro-1,6(2H,7H)-naphtalenedione




2-Methyl-2-(3-oxobutyl)-1,3-cyclohexanedione




2-Methyl-1,3-cyclohexanedione




N-Tosyl-(Sa)-binam-L-prolinamide




Methyl vinyl ketone





Keywords:

Wieland Miescher ketone (WMK);
fractional crystallization;
natural product synthesis;
2- methylcyclohexane-1,3-dione;
(S)-8a-Methyl-3,4,8,8a-tetrahydro-1,6(2H,7H)-naphtalenedione;
N-tosyl-(Sa)-binam-L-prolinamide organocatalysis

Gorka Etxebarria‐Jardi

Papers

Total synthesis of (-)-anominine.

Efficient Solvent-Free Robinson Annulation Protocols for the Highly Enantioselective Synthesis of the Wieland–Miescher Ketone and Analogues

Polycyclic framework synthesis of anominine and tubingensin A indole diterpenoids.

Nucleophile-Catalyzed Additions to Activated Triple Bonds. Protection of Lactams, Imides, and Nucleosides with MocVinyl and Related Groups

Synthesis of (S)-8a-Methyl-3,4,8,8a-Tetrahydro-1,6-(2H,7H)-Naphthalenedione via N-tosyl-(Sa)-binam-l-prolinamide Organocatalysis