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Review

Hypervalent iodine reagents for heterocycle synthesis and functionalization

Jiyun Sun1 Tianjin Key Laboratory for Modern Drug Delivery and High-Efficiency, School of Pharmaceutical Science and Technology, Tianjin University, Tianjin
,
Daisy Zhang-Negrerie2 Concordia International School Shanghai, Shanghai, People’s Republic of China
,
Yunfei Du1 Tianjin Key Laboratory for Modern Drug Delivery and High-Efficiency, School of Pharmaceutical Science and Technology, Tianjin University, TianjinCorrespondence[email protected]
&
Kang Zhao1 Tianjin Key Laboratory for Modern Drug Delivery and High-Efficiency, School of Pharmaceutical Science and Technology, Tianjin University, Tianjin
Pages 25-45 | Published online: 09 Aug 2016

Figures & data

Figure 1 Representative reactions involving hypervalent iodine reagents.

Figure 1 Representative reactions involving hypervalent iodine reagents.

Figure 2 Representative hypervalent iodine (III) reagents.

Abbreviations: PhIO, iodosobenzene; PIDA, phenyliodine diacetate; PIFA, phenyliodine bis(trifluoroacetate); HTIB, [hydroxy(tosyloxy)iodo]benzene.
Figure 2 Representative hypervalent iodine (III) reagents.

Figure 3 (A) PhIO-mediated construction of thiaozles, imidazoles, and imidazo[1,2-a]pyridines. (B) Proposed mechanism of the oxidation reaction in step I.

Abbreviations: PhIO, iodosobenzene; eq., equivalent; h, hours.
Figure 3 (A) PhIO-mediated construction of thiaozles, imidazoles, and imidazo[1,2-a]pyridines. (B) Proposed mechanism of the oxidation reaction in step I.

Figure 4 (A) (a) PhIO-mediated synthesis of three-membered ring 12 and five-membered ring 13. (b) PhIO-mediated synthesis of oxetane 15. (c) PhIO-mediated synthesis of azetidine 17 (B) Proposed mechanism of (a) and (c).

Abbreviations: PhIO, iodosobenzene; eq., equivalent; TBAI, tetra-butylammonium iodide; THF, tetrahydrofuran; rt, room temperature; h, hours.
Figure 4 (A) (a) PhIO-mediated synthesis of three-membered ring 12 and five-membered ring 13. (b) PhIO-mediated synthesis of oxetane 15. (c) PhIO-mediated synthesis of azetidine 17 (B) Proposed mechanism of (a) and (c).

Figure 5 PhIO-mediated functionalization of cyclic amines.

Abbreviations: PhIO, iodosobenzene; rt, room temperature; h, hours.
Figure 5 PhIO-mediated functionalization of cyclic amines.

Figure 6 PhIO-mediated oxidation affording α-methoxylated carbonyl compounds.

Abbreviation: PhIO, iodosobenzene.
Figure 6 PhIO-mediated oxidation affording α-methoxylated carbonyl compounds.

Figure 7 PhIO-mediated oxidation of dihydropyran.

Abbreviation: PhIO, iodosobenzene.
Figure 7 PhIO-mediated oxidation of dihydropyran.

Figure 8 Synthesis of the homochiral 7-oxa-2-azabicyclo[2.2.1]heptane ring system.

Abbreviations: PhIO, iodosobenzene; IHA, intramolecular hydrogen abstraction reaction.
Figure 8 Synthesis of the homochiral 7-oxa-2-azabicyclo[2.2.1]heptane ring system.

Figure 9 PhIO-mediated conversion of proline into 2-pyrrolidone in nonpolar solvent.

Abbreviations: PhIO, iodosobenzene, rt, room temperature; d, days.
Figure 9 PhIO-mediated conversion of proline into 2-pyrrolidone in nonpolar solvent.

Figure 10 Synthesis of various 1-fluoroglycosides with TolIF2.

Abbreviations: rt, room temperature; DCM, dichloromethane.
Figure 10 Synthesis of various 1-fluoroglycosides with TolIF2.

Figure 11 Ring-expansion reactions induced by TolIF2.

Abbreviations: eq., equivalent; rt, room temperature; h, hour; DCM, dichloromethane.
Figure 11 Ring-expansion reactions induced by TolIF2.

Figure 12 Synthesis of α-hydroxy-β,β-dichloropyrrolidine with 4-NO2PhICl2.

Abbreviation: eq., equivalent.
Figure 12 Synthesis of α-hydroxy-β,β-dichloropyrrolidine with 4-NO2PhICl2.

Figure 13 PhICl2/Pb(SCN)2-mediated thiocyanation of enol silyl ethers leading to lactone 42.

Abbreviations: rt, room temperature; DCM, dichloromethane.
Figure 13 PhICl2/Pb(SCN)2-mediated thiocyanation of enol silyl ethers leading to lactone 42.

Figure 14 Lewis base-catalyzed chlorination facilitated by PhICl2.

Abbreviations: eq., equivalent; rt, room temperature; min, minutes; DCM, dichloromethane.
Figure 14 Lewis base-catalyzed chlorination facilitated by PhICl2.

Figure 15 (A) Direct synthesis of oxazolidin-2-ones and imidazolidin-2-ones using PhICl2 and NaN3. (B) Proposed mechanism.

Abbreviations: eq., equivalent; h, hours.
Figure 15 (A) Direct synthesis of oxazolidin-2-ones and imidazolidin-2-ones using PhICl2 and NaN3. (B) Proposed mechanism.

Figure 16 PIDA-mediated synthesis of 2H-azirine derivatives from enamines.

Abbreviations: PIDA, phenyliodine diacetate; rt, room temperature; DCE, 1,2-dichloroethane.
Figure 16 PIDA-mediated synthesis of 2H-azirine derivatives from enamines.

Figure 17 PIFA-mediated synthesis of polysubstituted pyrroles 52.

Abbreviation: PIFA, phenyliodine bis(trifluoroacetate).
Figure 17 PIFA-mediated synthesis of polysubstituted pyrroles 52.

Figure 18 (A) I (III)-mediated synthesis of indoles from enamines 53. (B) I (III)-mediated synthesis of indoles from enamines 55.

Abbreviations: PIDA, phenyliodine diacetate; PIFA, phenyliodine bis(trifluoroacetate); rt, room temperature; DCM, dichloromethane; DCE, 1,2-dichloroethane.
Figure 18 (A) I (III)-mediated synthesis of indoles from enamines 53. (B) I (III)-mediated synthesis of indoles from enamines 55.

Figure 19 (A) PIDA-mediated synthesis of imidazoles via condensation of α-hydroxy ketones with aldehydes and NH4OAc. (B) Proposed mechanism.

Abbreviations: PIDA, phenyliodine diacetate; min, minutes.
Figure 19 (A) PIDA-mediated synthesis of imidazoles via condensation of α-hydroxy ketones with aldehydes and NH4OAc. (B) Proposed mechanism.

Figure 20 PIDA-mediated synthesis of aminoindazole derivatives.

Abbreviation: PIDA, phenyliodine diacetate.
Figure 20 PIDA-mediated synthesis of aminoindazole derivatives.

Figure 21 PIFA/TMSOTf-mediated synthesis of benzoxazole derivatives.

Abbreviations: PIFA, phenyliodine bis(trifluoroacetate); rt, room temperature; TMSOTf, trimethylsilyl trifluoromethanesulfonate.
Figure 21 PIFA/TMSOTf-mediated synthesis of benzoxazole derivatives.

Figure 22 (A) PIFA-mediated synthesis of 2-trifluoromethyl oxazole derivatives. (B) Proposed mechanism.

Abbreviation: PIFA, phenyliodine bis(trifluoroacetate); DCE, 1,2-dichloroethane.
Figure 22 (A) PIFA-mediated synthesis of 2-trifluoromethyl oxazole derivatives. (B) Proposed mechanism.

Figure 23 PIDA-mediated synthesis of 2,5-disubstituted oxazoles in AcOH or AcOH-HFIP.

Abbreviations: PIDA, phenyliodine diacetate; rt, room temperature.
Figure 23 PIDA-mediated synthesis of 2,5-disubstituted oxazoles in AcOH or AcOH-HFIP.

Figure 24 PIDA/KOH-mediated synthesis of 2-benzimidazolones and 2-benzoxazolones.

Abbreviation: PIDA, phenyliodine diacetate.
Figure 24 PIDA/KOH-mediated synthesis of 2-benzimidazolones and 2-benzoxazolones.

Figure 25 (A) PIFA-mediated intramolecular synthesis of benzothiazoles. (B) PIDA-mediated intermolecular synthesis of benzothiazoles.

Abbreviations: PIDA, phenyliodine diacetate; PIFA, phenyliodine bis(trifluoroacetate); PS, polymer-supported.
Figure 25 (A) PIFA-mediated intramolecular synthesis of benzothiazoles. (B) PIDA-mediated intermolecular synthesis of benzothiazoles.

Figure 26 PIDA/KBr-mediated synthesis of aryl lactones.

Abbreviation: PIDA, phenyliodine diacetate.
Figure 26 PIDA/KBr-mediated synthesis of aryl lactones.

Figure 27 (A) Metal-free synthesis of spirooxindoles via PIFA-mediated cascade oxidation. (B) Proposed mechanism.

Abbreviations: PIFA, phenyliodine bis(trifluoroacetate); rt, room temperature; TFE, 2,2,2-Trifluoroethanol.
Figure 27 (A) Metal-free synthesis of spirooxindoles via PIFA-mediated cascade oxidation. (B) Proposed mechanism.

Figure 28 (A) PIFA-mediated conversion of internal alkynes to spiro heterocycles via cascade annulation. (B) Proposed mechanism.

Abbreviations: PIFA, phenyliodine bis(trifluoroacetate); rt, room temperature; h, hours; DCM, dichloromethane.
Figure 28 (A) PIFA-mediated conversion of internal alkynes to spiro heterocycles via cascade annulation. (B) Proposed mechanism.

Figure 29 (A) PIDA-mediated synthesis of bisindolines via cascade intramolecular oxidative deamination. (B) Proposed mechanism.

Abbreviations: PIDA, phenyliodine diacetate; rt, room temperature; h, hours; DMF, N,N-dimethylformamide.
Figure 29 (A) PIDA-mediated synthesis of bisindolines via cascade intramolecular oxidative deamination. (B) Proposed mechanism.

Figure 30 PIFA-mediated synthesis of benzo[c]phenanthridine and phenanthridinone.

Abbreviation: PIFA, phenyliodine bis(trifluoroacetate); DCM, dichloromethane.
Figure 30 PIFA-mediated synthesis of benzo[c]phenanthridine and phenanthridinone.

Figure 31 PIFA-mediated synthesis of 3-arylquinolin-2-ones from N-methyl-N-phenylcinnamamides through oxidative C–C bond formation/1,2-aryl migration.

Abbreviations: PIFA, phenyliodine bis(trifluoroacetate); rt, room temperature; TFA, trifluoroacetic acid; DCE, 1,2-dichloroethane.
Figure 31 PIFA-mediated synthesis of 3-arylquinolin-2-ones from N-methyl-N-phenylcinnamamides through oxidative C–C bond formation/1,2-aryl migration.

Figure 32 PIFA-mediated direct intramolecular cyclization of α-(aryl)alkyl-β-dicarbonyl compounds.

Abbreviations: PIFA, phenyliodine bis(trifluoroacetate); TFE, 2,2,2-Trifluoroethanol.
Figure 32 PIFA-mediated direct intramolecular cyclization of α-(aryl)alkyl-β-dicarbonyl compounds.

Figure 33 PIFA-mediated synthesis of N-aryl-N-methoxyamides via an intramolecular oxidative C–N bond formation.

Abbreviation: PIFA, phenyliodine bis(trifluoroacetate).
Figure 33 PIFA-mediated synthesis of N-aryl-N-methoxyamides via an intramolecular oxidative C–N bond formation.

Figure 34 Synthesis of isoquinolones from N-methoxybenzamide and diphenyl acetylene mediated by PIDA generated in situ.

Abbreviations: PIDA, phenyliodine diacetate; rt, room temperature.
Figure 34 Synthesis of isoquinolones from N-methoxybenzamide and diphenyl acetylene mediated by PIDA generated in situ.

Figure 35 (A) PIFA-mediated synthesis of the fused indeno-1,4-diazepinones. (B) Proposed mechanism.

Abbreviations: PIFA, phenyliodine bis(trifluoroacetate); rt, room temperature.
Figure 35 (A) PIFA-mediated synthesis of the fused indeno-1,4-diazepinones. (B) Proposed mechanism.

Figure 36 I (III)-mediated formation of dibenzodihydro-1,3-diazepin-2-ones and dibenzo[d,f][1,3]oxazepin-6(7H)-ones.

Abbreviation: rt, room temperature.
Figure 36 I (III)-mediated formation of dibenzodihydro-1,3-diazepin-2-ones and dibenzo[d,f][1,3]oxazepin-6(7H)-ones.

Figure 37 PIFA/I2-mediated iodination of indole derivatives to 3-iodoindoles 103.

Abbreviations: PIFA, phenyliodine bis(trifluoroacetate); rt, room temperature; h, hours; DCM, dichloromethane.
Figure 37 PIFA/I2-mediated iodination of indole derivatives to 3-iodoindoles 103.

Figure 38 PIFA/TMSCN-mediated selective cyanation of N-tosylpyrroles at the C2 position.

Abbreviations: PIFA, phenyliodine bis(trifluoroacetate); rt, room temperature; TMSCN, trimethylsilyl cyanide; DCM, dichloromethane.
Figure 38 PIFA/TMSCN-mediated selective cyanation of N-tosylpyrroles at the C2 position.

Figure 39 PIDA-mediated homogeneous azidization and selenylation of glycals.

Abbreviations: PIDA, phenyliodine diacetate; h, hours; DCM, dichloromethane.
Figure 39 PIDA-mediated homogeneous azidization and selenylation of glycals.

Figure 40 HTIB-mediated synthesis of trifluoromethyl-2-isoxazoline-N-oxides.

Abbreviation: HTIB, [hydroxy(tosyloxy)iodo]benzene.
Figure 40 HTIB-mediated synthesis of trifluoromethyl-2-isoxazoline-N-oxides.

Figure 41 HTIB-mediated synthesis of 4-methoxy-2H-chromene.

Abbreviation: HTIB, [hydroxy(tosyloxy)iodo]benzene.
Figure 41 HTIB-mediated synthesis of 4-methoxy-2H-chromene.

Figure 42 Intramolecular carbotrifluoromethylation of alkynes with Togni’s reagent and Cu(I).

Abbreviations: h, hours; DCM, dichloromethane.
Figure 42 Intramolecular carbotrifluoromethylation of alkynes with Togni’s reagent and Cu(I).

Figure 43 Trifluoromethylation of indole derivatives with Togni’s reagent.

Abbreviations: rt, room temperature; h, hours.
Figure 43 Trifluoromethylation of indole derivatives with Togni’s reagent.

Figure 44 (A) Synthesis of biologically important 1-trifluoromethylated isoquinolines with Togni’s reagent. (B) Proposed mechanism.

Abbreviation: h, hours.
Figure 44 (A) Synthesis of biologically important 1-trifluoromethylated isoquinolines with Togni’s reagent. (B) Proposed mechanism.

Figure 45 Aryltrifluoromethylation of N-phenylcinnamamides by using Togni’s reagent and copper catalyst.

Abbreviation: h, hours.
Figure 45 Aryltrifluoromethylation of N-phenylcinnamamides by using Togni’s reagent and copper catalyst.

Figure 46 Direct alkynylation of indole and pyrrole heterocycles by using TIPS-EBX.

Abbreviation: TIPS-EBX, [(triisopropylsilyl)ethynyl]benziodoxolone.
Figure 46 Direct alkynylation of indole and pyrrole heterocycles by using TIPS-EBX.

Figure 47 Selective cobalt(III)-catalyzed alkynylation of indoles using hypervalent iodine-alkyne reagents.

Abbreviations: TFE, 2,2,2-Trifluoroethanol; h, hours; Cp*, cyclopentadienyl.
Figure 47 Selective cobalt(III)-catalyzed alkynylation of indoles using hypervalent iodine-alkyne reagents.

Figure 48 Metal-free alkynylation of various heterocyclic compounds with TMS-EBX.

Figure 48 Metal-free alkynylation of various heterocyclic compounds with TMS-EBX.

Figure 49 (A) Cycloaddition of ortho-silyl aryltriflates and iodonium ylides. (B) Proposed mechanism.

Abbreviation: rt, room temperature.
Figure 49 (A) Cycloaddition of ortho-silyl aryltriflates and iodonium ylides. (B) Proposed mechanism.

Figure 50 Ru-catalyzed nitrogen atom transfer.

Abbreviations: h, hours; DCM, dichloromethane.
Figure 50 Ru-catalyzed nitrogen atom transfer.

Figure 51 Diaryliodonium salts-mediated arylation of indoles at C2.

Abbreviations: rt, room temperature; h, hours.
Figure 51 Diaryliodonium salts-mediated arylation of indoles at C2.

Figure 52 Cu-catalyzed tandem C–H/N–H arylation of indoles with diaryliodonium salts.

Abbreviations: eq., equivalent; DMEDA, N,N’-Dimethyl-1,2-ethanediamine.
Figure 52 Cu-catalyzed tandem C–H/N–H arylation of indoles with diaryliodonium salts.

Figure 53 Arylation of N-containing heterocycles with diaryliodonium salts.

Abbreviations: rt, room temperature; h, hours.
Figure 53 Arylation of N-containing heterocycles with diaryliodonium salts.

Figure 54 A Cu(OTf)2-catalyzed, three-component regioselective synthesis of polysubstituted quinolones.

Abbreviations: eq., equivalent; DCE, 1,2-dochloroethane.
Figure 54 A Cu(OTf)2-catalyzed, three-component regioselective synthesis of polysubstituted quinolones.

Figure 55 Oxidative cleavage of the glycol C–C bond with DMP.

Abbreviations: DMP, Dess–Martin periodinane; rt, room temperature; h, hours.
Figure 55 Oxidative cleavage of the glycol C–C bond with DMP.

Figure 56 Synthesis of 2-substituted benzothiazoles with DMP.

Abbreviations: DMP, Dess–Martin periodinane; rt, room temperature; min, minutes.
Figure 56 Synthesis of 2-substituted benzothiazoles with DMP.

Figure 57 IBX-mediated stereoselective 5-exo and 6-exo formations of isoxazolidines and [1,2]oxazinanes.

Abbreviations: IBX, 2-iodoxybenzoic acid; DMSO, dimethyl sulfoxide; min, minutes.
Figure 57 IBX-mediated stereoselective 5-exo and 6-exo formations of isoxazolidines and [1,2]oxazinanes.

Figure 58 IBX-mediated SET synthesis of isoxazolines involving multiple components.

Abbreviations: IBX, 2-iodoxybenzoic acid; SET, single-electron transfer; DCM, dichloromethane.
Figure 58 IBX-mediated SET synthesis of isoxazolines involving multiple components.

Figure 59 Direct functionalization of indoles to isatins by NaI/IBX-SO3K.

Abbreviation: DMSO, dimethyl sulfoxide.
Figure 59 Direct functionalization of indoles to isatins by NaI/IBX-SO3K.

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