Gerald F. Koser

The Synthesis of Heterocyclic Compounds with Hypervalent Organoiodine Reagents

Publisher Summary This chapter reviews the synthesis of heterocyclic compounds with hypervalent organo-iodine reagents. The utility of hypervalent organoiodine reagents for the synthesis of heterocyclic compounds, ranging from classical ring structures to natural products is surveyed in the chapter. The information is organized by reagent and reaction types. The hypervalent iodine reagents are derived from iodoarenes for the clarity of treatment is separated into standard structural categories—namely, the aryl-λ 3 -iodanes, the iodonium salts, the iodonium ylides, and the aryl-λ 5 -iodanes. Some specific hypervalent organoiodine reagents are tabulated in the chapter. The synthesis of heterocyclic compounds using aryl-λ 3 -iodanes involves oxidations at α-carbon, SET reactions, and biaryl couplings. The synthesis of heterocyclic compounds using iodonium salts involves diaryliodonium salts and alkynyl iodonium salts. The synthesis of heterocyclic compounds using iodonium ylides involves iodine (III) –carbon ylides and iodine (III) –nitrogen ylides. The Dess–Martin periodane (DMP) and o -iodoxybenzoic acid (IBX) with N-arylalkenamides in two fundamentally different heterocyclization pathways are also illustrated in the chapter.

Tosyloxylactonization of alkenoic acids with [hydroxy(tosyloxy)iodo] benzene

Abstract [Hydroxy(tosyloxy)iodo]benzene( 1 ) reacts with 3-butenoic, 4-pentenoic, 5- hexenoic and 2-methyl-4-pentenoic acids in CH2Cl2 to give tosyloxylactones and with trans -3- hexenoic and 2-cyclopenteneacetic acids to give unsaturated lactones. 5 -Norbornene- endo -2- carboxylic acid with 1 gives a rearranged lactone while 5-norbornene- endo -2.3-dicarboxylic acid gives a bis -lactone.

Application of [Hydroxy(tosyloxy)iodo]benzene in the Wittig-Ring Expansion Sequence for the Synthesis of β-Benzocyclo-alkenones from α-Benzocycloalkenones

The conversion of α-benzocycloalkenones to homologous β-benzocyclo-alkenones containing six, seven and eight-membered rings is reported. This was accomplished via a Wittig olefination-oxidative rearrangement sequence using [hydroxy(tosyloxy)iodo]-benzene (HTIB) is the oxidant, that enables the synthesis of regioisomeric pairs of methyl-substituted β-benzocycloalkenones. The incorporation of carbon-13 at C-1 of the β-tetralone nucleus was also demonstrated. The Wittig-HTIB approach is a useful alternative to analogous sequences in which Tl(NO3)3·3H2O or the Prevost combination (AgNO3/I2) are employed in the oxidation step.

Facile synthetic entry into the 1,3-dihydro-3-methyl-3-phenyl-1,2-benziodoxole family of λ3-lodanes

Abstract The synthesis of series of 1,3-dihydro-3-methyl-3-phenyl-1,2-benziodoxoles, 7, containing chloro, tosyloxy, acetoxy, trifluoroacetoxy and azido ligands and the optical resolution of 2-iodo-α-methylbenzhydrol, the starting material for the synthesis of 7, are reported.

Direct functionalization of sulfides with hypervalent iodine reagents: Methoxysulfonium and amidosulfonium tosylates

Abstract [Methoxy(tosyloxy)iodo]benzene(1) and N-phenyliodonio carboxamide tosylates( 3 ) react with sulfides in dichloromethane to give methoxysulfonium and amidosulfonium tosylates.

Bislactonizations of olefinic diacids with [hydroxy(tosyloxy)iodo]benzene

Abstract The reactions of [hydroxy(tosyloxy)iodo]benzene with a series of olefinic diacids to produce bislactones are reported. The products are the result of a stereospecific cis -addition of the two carboxylic acid functions to the double bond.

C-Heteroatom-Bond Forming Reactions

Recent progress on the use of hypervalent iodine reagents for the construction of carbon-heteroatom (N,O,P, S,Se,Te, X) bonds is reviewed. Reactions of aryl-λ3-iodanes with organic substrates are considered first and are loosely organized by functional group, separate sections being devoted to carbon-azide and carbon-fluorine bond formation. Arylations and alkenylations of nucleophilic species with diaryliodonium and alkenyl(aryl)iodonium salts, and a variety of transformations of alkynyl(aryl)iodonium salts with heteroatom nucleophiles are then detailed. Finally, the use of sulfonyliminoiodanes as aziridination and amidation reagents, and reactions of iodonium enolates formally derived from monoketones are summarized.

Regiospecific conversion of terminal alkynes to ketol phosphates with an iodine (III)-phosphate reagent

Abstract Terminal alkynes undergo regiospecific conversion to ketol phosphates when treated with the iodine(III)-phosphate 2 in acetonitrile containing water.

Crystal and molecular structure of 1-chloro-1,2-benziodoxolin-3(1H)-one·tetra-n-butylammonium chloride

AbstractThe title compound,6, a novel 1∶1 complex of 1-chloro-1,2-benziodoxolin-3(1H)-one (5) andtetra-n-butylammonium chloride, was prepared from tetra-n-butylammoniumo-iodoxybenzoate (7) and acetyl chloride. A single crystal of6 was subjected to X-ray analysis: triclinic, space group