1. Introduction
1.1. Some physical properties of tellurium
1.2. Relevant monographs and review articles
2-Preparation of the more important inorganic tellurium reagents
2.1. Tellurium tetrachloride
2.2. Tellurium dioxide
2.3. Alkali metal tellurides (Te 2Cat 2+ )
2.3.1. From the elements (2Na + Te - Na
2
Te)
2.3.2. From tellurium and reducing agents (Te → Te 2)
2.3.3. From tellurium and non-reducing bases
2.4. Alkali metal ditellurides (Na
2
Te
2
)
2.4.1.
From the elements (2Na+2Te→Na
2
Te
2
)
2.4.2 From tellurium and reducing agents
2.5 Hydrogen telluride (H
2
Te)
5
5
5
2.6 Sodium hydrogen telluride (NaHTe) 6
3. Preparation of the principal classes of organic tellurium compounds 7
3
4
4
4
1
1
1
3
4
5
5
3.1. Diorganyl tellurides
3.1.1. Symmetrical dialkyl tellurides
3.1.1.1. From alkali tellurides and alkylating agents
3.1.1.2. From bis(triphenylstannyl) telluride and alkylating reagents
3.1.2. Symmetrical diaryl tellurides
3.1.2.1. From alkali tellurides and non-activated aryl halides
16
16
3.1.2.2. From sodium telluride or sodium O,O-diethyl 18 phosphorotellurolate and arenediazonium fluoroborates
3.1.2.3 From potassium tellurocyanate and arenediazonium fluoroborates 19
11
11
11
15
3.1.2.4. From tellurium (IV) halides and arylmagnesium halides
3.1.2.5. From elemental tellurium and diarylmercury compounds
3.1.2.6 From diaryl ditellurides by extrusion of a tellurium atom
3.1.2.7. Bis-(phenylethynyl)telluride as Te 2+ equivalent
3.1.3. Unsymmetrical tellurides
3.1.3.1. From sodium telluride and two different alkyl halides
3.1.3.2. From organyl tellurolates and alkylating agents
3.1.3.3. By addition of aryl tellurolates to electrophilic alkenes
22
22
23
27
19
20
20
21
1

3.1.3.4. From organyl tellurolates and arylating agents 28
3.1.3.5. From diorganyl ditellurides or arenetellurenyl halides and organometallic reagents
3.1.3.6. Additional methods
28
29
3.1.4. Diorganyl tellurides by reduction of diorganyltellurium dihalides
3.2. Diorganyl ditellurides
3.2.1. From sodium ditelluride
3.2.1.1. From sodium ditelluride and alkylating agents
32
34
34
34
3.2.1.2. From sodium ditelluride and aryl halides
3.2.2. By oxidation of organotellurols or organotellurolates
3.2.3. By reduction of organotellurium trichlorides
3.2.3.1. Reduction of

-carboxyalkyltellurium trichlorides
3.2.3.2. Reduction of

-alkoxyalkyltellurium trichlorides 40
3.2.3.3. Reduction of aryltellurium trichlorides
3.2.4. Diaryl ditellurides from aryl boronic acids
3.3. Organyl tellurols
3.4. Bis-organyl telluromethanes
3.5. Organyl tellurium trihalides 44
3.5.1. Organyltellurium trichlorides from tellurium tetrachloride and organic substrates
3.5.1.1. From tellurium tetrachloride and ketones and carboxylic anhydrides
3.5.1.2. From tellurium tetrachloride and alkenes
44
44
44
3.5.1.3. From tellurium tetrachloride and arenes
3.5.1.4. From tellurium tetrachloride and arylmercury chlorides
46
47
40
41
42
43
3.5.2. By chlorinolysis of diorganyl ditellurides 48
3.5.3. Organyltellurium tribromides and triiodides by halogenolysis of the corresponding ditellurides
3.5.4. Additional method. Preparation of organyltellurium trichlorides and tribromides by the reaction of tetraorganyltin compounds with tellurium tetrachloride and tetrabromide
3.6. The products of the hydrolysis of aryl tellurium trihalides
48
49
50
3.7. Aryl tellurenyl halides
3.8. Aryl Tellurenyl pseudohalides. aryl tellurocyanates
3.9. Diorganyl tellurium dihalides
3.9.1. From elemental tellurium
3.9.2. From tellurium tetrahalides (or tellurium dioxides)
51
53
53
53
54
36
37
39
39
2

3.9.2.1. With ketones and carboxylic acid anhydrides
3.9.2.2. With alkenes
3.9.2.3. With arenes
3.9.2.4. With arylmercury chlorides
3.9.2.5. With arenediazonium salts
3.9.3. From organyltellurium trihalides
3.9.3.1. With ketones
3.9.3.2. With alkenes
3.9.3.3. With arenes
3.9.3.4. With organylmercury chlorides
3.9.4. By addition of halogens to diorganyl tellurides
3.9.5. Additional methods
3.9.5.1. Reaction of elemental tellurium with arenediazonium salts
3.9.5.2. Reaction of TeO
2
/LiCI with aryl hydrazines
3.9.5.3. Reaction of diaryl ditelluride with arenediazonium salts/CuCl
2
3.10. Diorganyl telluroxides
3.10.1.Hydrolysis of diaryltellurium dihalides
3.10.2. Oxidation of diaryl tellurides
3.11. Telluroesters
3.12. Aryl telluroformates
3.13. Telluroglucopyranosides
3.14. Water soluble diorganyl tellurides
3.15. Dihaloaryltelluro cyclopropanes
3.16. Vinylic tellurides and ditellurides
3.16.1. Starting from nucleophilic tellurium
3.16.1.1. Addition of alkali tellurides to acetylenes
3.16.1.2. From organyltellurols or tellurolates and terminal acetylenes
67
69
3.16.1.3. From organyl tellurolate (and telluride) anions and vinyl bromides
3.16.1.4. From vinylic tellurolate anions and alkyl halides
74
75
3.16.1.5. From organotellurolate anions and activated vinylic halides
3.16.1.6. From organyl tellurolates and electrophilic acetylenes
3.16.1.7. Tanden vicinal difunctionalization of alkynes
3.16.1.8. Telluroacylation of terminal alkynes
76
78
79
80
66
67
67
67
62
62
65
66
60
60
61
62
58
59
60
60
55
56
56
57
58
54
54
54
55
3

4
3.16.2. Starting from electrophilic tellurium
3.16.3. Via radical reactions
3.16.4.Reduction of acetylenic tellurides
80
3.16.2.1. By addition of tellurium tetrahalides and aryltellurium trihalides to acetylenes
3.16.2.2. From organyltellurenyl halides and vinylic Grignard reagents
80
82
3.16.2.3. From vinyltellurenyl iodides and Grignard reagents 83
83
85
3.16.5.Vinylic tellurides via olefination reactions
3.16.5.1.Horner-Emmons route
3.16.5.2. Wittig route
3.16.6. Vinyl tellurides via borane chemistry
86
86
87
89
3.16.7. Telluro (seleno)ketene acetals, 1-seleno-2-telluro-ethenes, telluro ketene acetals, telluro (stannyl)-ketene acetals and telluro(thio)ketene acetals
3.16.8. The behaviour of vinylic teIlurides toward several reagents and reaction conditions used in organic synthesis
3.17. Acetylenic tellurides
90
99
103
3.17.1. From nucleophilic tellurium reagents 103
3.17.1.1. Sodium ethynyl tellurolates
3.17.1.1.2. Lithium alkyl and ethynyl tellurolates
103
103
3.17.2. From electrophilic tellurium reagents 104
3.17.2.1. From alkynyl Grignard and lithium compounds and organyl tellurenyl halides
3.17.2.2. From tellurium tetrachloride and alkynyllithium compounds
104
106
3.17.3. Synthesis of internal acetylenes from vinylic tellurides
3.18. Allenic and propargylic tellurides
4. Tellurium in organic synthesis
4.1. Reductions
4.1.1. Reduction of carbonyl compounds
4.1.1.1. With hydrogen telluride
4.1.1.2. With phenyltellurol
4.1.1.3. With diisobutyl telluride/titanium (IV) chloride
4.1.1.4. With sodium telluride in 1-methyl-2-pyrrolidinone
4.1.2. Selective reduction of

-unsaturated carbonyl compounds
4.1.3. Reduction of conjugated arylalkenes and arylalkynes
107
107
110
110
110
110
4.1.4. Reduction of imines and enamines
110
112
112
113
114
115

5
4.1.5. Reductive desulphuration of aromatic thioketones
4.1.6. Reduction of nitro compounds
116
116
4.1.7. Reduction of other nitrogenated compounds
4.1.8 Deselenylation of

-seleno carboxylic compounds
120
122
4.1.9. Deoxygenation of oxiranes with alkali O,O-dialkyl phosphorotellurolates
4.1.10. Reductive opening of oxiranes with sodium hydrogen telluride and sodium telluride
4.1.11. Correlate reaction-tellurium-mediated resolution of racemic allyl alcohols
4.1.12. 1,2-Elimination in vicinal disubstituted substrates
123
123
125
127
4.1.12.1. Debromination of vic-dibromides with tellurium reagents
4.1.12.2. Desulfonation of vic-dimesylates and vic-ditosylates
127
131
4.1.13. Reductive fission of carbon-heteroatom bonds
4.1.13.1. Reductive removal of electronegative

substituents from ketones, acids and derivatives
4.1.13.2. Dehalogenation of polyhalogenated organic compounds
132
132
136
4.1.13.3. Reductive removal of tertiary nitro groups 136
4.1.13.4. Reductive dealkylation of quaternary ammonium salts
4.1.13.5. Reductive desulphonation of

-ketosulphones
4.1.13.6 Desulphonylative condensation of

-cyanosulphones with aldehydes
4.1.13.7. Correlate reaction - Desulphonylation of

-nitrosulphones
137
137
138
139
4.1.13.8. Monodesulphuration of diaryl thioketals and bis-sulphenylated

-dicarboxyl compounds, diorganyl trisulfides and disulfides
4.2. Tellurium-mediated formation of anionic species and their reactions with electrophiles
4.2.1. Reformatsky-type reactions
139
143
143
4.2.2. Knoevenagel-type reaction 144
4.2.3. Pinacol reaction
4.2.4. Alkylidenation of aldehydes and cyclopropanation of
 unsaturated carbonyl compounds with dibromomalonic esters
4.2.5. Telluride-assisted sulphenylation and sulphonylation reactions
145
145
146
4.2.6. Telluride-mediated aldehyde methylenation
4.2.7 Miscellaneous
4.3. Deprotection of organic functionality by tellurium reagents
4.3.1. Regeneration of carboxylic acids:cleavage of carboxylic esters
4.3.1.1. Alkyl carboxylates
148
149
150
150
151

6
4.3.1.2. Phenacyl carboxylates
4.3.1.3. Allyl carboxylates
4.3.1.4. 2-Haloethyl carboxylates
4.3.2. Regeneration of Phenols
152
152
153
154
4.3.2.1. Cleavage of aryl carboxylates and carbonates
4.3.2.2. Cleavage of aryl haloacetates
154
155
4.3.2.3. Cleavage of phenyl allyl ethers 156
4.3.3. Regeneration of amines by cleavage of trichlorot -butylcarbamates 156
4.4. Oxidation of organic substances by means of tellurium reagents
4.4.1. Bis( p -methoxyphenyl) telluroxides as a mild and selective oxidizing reagent
4.4.1.1. Conversion of thio- and selenocarbonyl compounds to their oxo analogues
4.4.1.2. Conversion of tertiary phosphines to tertiary phosphine oxides
157
157
159
4.4.1.3. Conversion of phenyl isothiocyanate to diphenylurea
4.4.1.4. Conversion of thiourea to ureas
4.4.1.5. Conversion of thiols to disulfides
4.4.1.6. Conversion of o - and p -diphenols to quinones
4.4.1.7. Conversion of acylhydrazines to acylhydrazides
4.4.1.8. Conversion of N -phenylhydroxylamine to nitrosobenzene
157
159
159
159
160
160
160
4.4.1.9. Conversion of diphenyldiazomethane benzophenone hydrazone
4.4.2. Polymer-supported bis( p -methoxyphenyl) telluroxide to 160
161
162 4.4.3. Bis(p-methoxyphenyl) telluride as a mediator in an electrolytic process
4.4.4. Bis( p -methoxyphenyl) tellurone
4.4.5. Sodium tellurite as oxidizing agent for thiols
163
164
4.4.6. TeCl
4
promoted oxidation of trialkylphosphites
4.4.7. Arenetellurinic anhydrides
165
166
4.4.8. Reaction of oxidizing tellurium reagents with the C=C bond 168
4.4.8.1. Epoxidation of olefins catalyzed by polystyrene-supported tellurinic acid
4.4.8.2. Diacetoxylation of olefins
168
169
4.4.8.3. Methoxytellurenylation and dimethoxylation of olefins
4.4.8.4. Aminotellurinylation of olefins and related reactions
4.5. Organotellurium-based ring closure reactions
4.5.1. Tellurolactonization of unsaturated carboxylic acids
173
174
178
179

7
4.5.1.1. With aryltellurium trichlorides
4.5.1.2. With benzenetellurenyl nitrobenzenesulphonate
179
180
4.5.1.3. With diaryl tellurium dihalides
4.5.1.4. Tellurolactonization of

-allenic acids with phenyltellurenyl chloride
4.5.1.5. Reductive detelluration of tellurolactones
180
181
181
4.5.2. Cyclotelluroetherification of unsaturated alcohols and allylphenols
4.5.2.1. With aryltellurinyl acetates
4.5.2. With aryltellurium trichlorides
4.5.2.3. With benzenetellurenyl nitrobenzenesulphonate
4.5.2.4. With TeO
2
/HOAc/LiCl or TeO
2
/HCl
183
183
184
185
186
4.5.2.5. With diaryl tellurium dihalides 187
4.5.2.6. Synthetic utility of the telluroetherification reactions
4.5.3. Tellurocyclofunctionalization of alkenylsubstituted

-dicarbonyl compounds
4.5.4. Tellurocyclization of olefinic carbamates
187
188
190
4.6. Conversion of organotellurium compounds into tellurium-free organic compounds
4.6.1. Detelluration of organotellurium compounds with the formation of new C-C bonds (carbodetelluration)
4.6.1.1. Synthesis of biaryls by Raney-Ni catalyzed homocoupling of diaryltellurium dichlorides and aryltellurium trichlorides
4.6.1.2. Pd(0) catalyzed homocoupling of diorganyl tellurides (and ditellurides)
4.6.1.3. Correlate reactions
191
191
191
191
192
4.6.1.4. Olefin arylation by Pd(II) catalyzed carbodetelluration of aryltellurium compounds
4.6.1.5. Pd(II) catalyzed cross-coupling reactions of aryl tellurides with alkenes
4.6.1.6. Ni(II) or Co(II) Catalyzed cross-coupling of Grignard reagents with organic tellurides
4.6.1.7. Palladium and copper catalyzed cross-coupling of organotellurium dichlorides with organostannanes and organoboronic acids.
4.6.1.8. Palladium catalyzed cross-coupling of organo-tellurium compounds with hypervalent iodonium salts
4.6.1.9. Detellurative carbonylation of organotellurium compounds: preparation of carboxylic acids
4.6.1.10. Synthesis of enones and cyclopropanes from bis(oxoalkyl)tellurium dichlorides
4.6.1.11. Conversion of telluroesters into ketones
193
194
194
194
195
196
197
198
4.6.2. Replacement of the tellurium moiety by other functionalities 198

8
4.6.2.1. By Amino Group - Allylic amine by imination of allylic tellurides
4.6.2.5. Reductive detelluration of tellurides by triphenyltin hydride
4.7. Synthesis of olefins
198
4.6.2.2. By Hydroxy Group - Hydrolysis of telluroesters to carboxylic acids and esters
4.2.2.3. By halogens
199
199
4.6.2.4. By the methoxy group 206
208
210
4.7.1. By telluroxide elimination 210
4.7.2 Correlate method: reaction of alkyl phenyl tellurides with chloramines-T
4.7.3. From telluronium ylides
214
215
4.7.3.1. Stabilized telluronium ylides
4.7.3.2. Semi-stabilized and non-stabilized telluronium ylides
215
218
4.7.3.3. Correlate reaction: the reaction of telluronium salts with carbonyl compounds mediated by organolithium reagents - formation of secondary alcohols
4.7.4. Tellurium-catalyzed decomposition of

-lithiated benzylic sulphones into 1,2-diarylethylenes
4.8. Transmetallations reactions
222
224
227
4.8.1. Lithium tellurium exchange: generation of organolithium reagents 226
4.8.1.2. Acyl- and aroyllithim compounds 233
4.8.1.3. Heterosubstituted methyllithium compounds
4.8.1.4. Ferrocenyltellurium derivatives
4.9. Reactivity and synthetic applications of vinylic tellurides
4.9.1. Vinylcuprates by copper-tellurium exchange
234
236
237
237
4.9.1.1. Conjugate addition to enones 237
4.9.1.2. Conjugate addition of higher order cyanocuprates to enone, followed by O-functionalization
4.9.1.3. Reaction with epoxides
240
243
4.9.1.4. Reaction with bromoalkynes
4.9.1.5. Synthesis of (-)-Macrolactin A
244
245
4.9.2. Tellurium-zinc and tellurium-alumminum exchange
4.9.3. Coupling reactions
245
248
4.9.3.1 Pd(II) catalyzed homocoupling of vinyl tellurides 248
4.9.3.2. Pd(II) catalyzed cross-coupling of vinylic tellurides with alkenes 249
4.9.3.3. Ni(II) or Cu(I) catalyzed cross-coupling of vinyl tellurides with
Grignard reagents
250

9
4.9.3.4. Pd(II) and Ni(II) catalyzed Sonogashira type cross-coupling of vinyl tellurides and vinyl tellurium dichlorides with terminal alkynes
4.9.3.5. Pd/Cu catalyzed cross-coupling of vinylic tellurides with organyl zinc reagents
4.9.3.5. Detellurative carbonylation of vinylic tellurides
252
254
256
4.10. Free radical chemistry
4.10.1. Telluride ion-promoted coupling of allylic halides
258
258
4.10.2. Organyl tellurides as exchangers of carbon radicals
4.10.2.1. Tellurium-mediated addition of carbohydrates to olefins
4.10.2.2. Intramolecular radical cyclization
4.10.3. Reactions of tetraorganyl tellurium with acetylenes
259
259
260
262
4.10.4. Telluroesters as source of acyl radicals
4.10.5. Aryl telluroformates as precursors of oxyacyl and alkyl radicals
263
268
4.10.6. Aryltelluroformates as precursors of selenium containing heterocycles
4.10.7. Allyloxy and 2-propargyloxy alkyl tellurides as precursors of tetrahydrofuran derivatives
4.10.8. Telluroglycosides as source of glycosyl radicals
268
269
270
4.10.9. Radical mediated group transfer imidoylation with isonitriles 271
4.10.10. Three component coupling of silyltellurides, carbonyl compounds and isocyanides
4.10.11. Synthesis of substituted quinones via organotellurium compounds
4.10.12. Thiotelluration of vinyl cyclopropanes. Thio and selenotelluration of acetylenes
4.10.13. Perfluoroalkyltelluration of terminal olefins and alkynes
273
275
277
279
4.10.14. Synthesis of indole derivatives via radical cyclization of N -(ortho ethynylbenzene)-phenyltelluro trifluoro acetimidates
4.10.15. Organotellurium compounds as initiators for controlled living radical polymerization
5. Telluroheterocycles
280
281
283
5.1. Tellura-3,5-cyclohexanedione dichlorides (3,5-dioxotellurane-1,1dichlorides
5.2. Oxa and 1-thia-4-telluranes
5.3. Tellurophenes
5.3.1. Preparation
5.3.1.1. From alkali metal tellurides
5.3.1.2. From tellurium tetrachloride
5.3.1.3. From 1,4-dibutyltellurobutadiene
283
283
283
284
284
285
285

10
5.3.1.4. From butyltellurobutenines
5.3.2. Reactions of tellurophene
5.3.2.1. Via 2-lithiotellurophene-2-substituted derivatives
5.3.2.2. Formylation
286
287
287
287
5.3.2.3. Acetylation
5.3.2.4. Chloromethylation
5.3.2.5. Acetoxymercuriation
5.3.2.6. Modifications of the functionalized tellurophenes
5.3.2.7. Formation of complexes
5.3.2.8. Removal of tellurium from the ring
5.4. 1-Benzotellurophenes
5.4.1. Preparation
5.4.1.1. From tellurium
289
289
289
289
5.4.1.2. From TeO
2
290
5.4.1.3. Via cyclization of ortho acetyl or formyl substituted phenyl telluro compounds
5.4.1.4. From o -phenylethenyl tellurium trichloride
291
292
5.4.2. Reactions of 1-benzotellurophene and 3-oxo-2,3dihydrobenzotellurophene
5.4.3. Ring cleavage of the tellurophene ring
5.5. Benzotellurepines
5.5.1. Preparation
5.5.2. Reactions
5.6. 2-Benzotellurophenes
5.6.1. Preparation
5.7. Telluro[3,4-c]thiphene
5.7.1. Preparation
5.8. Dibenzotellurophenes
5.8.1. Preparation
5.8.1.1. From tellurium
292
294
295
295
297
297
297
298
298
299
299
299
300 5.8.1.2. From tellurium dichloride
5.8.1.3. From tellurium IV halides
5.8.1.4. From bis[2,2´-biphenyldiyl]tellurium
300
301
5.8.2. Reactions
5.8.2.1. Halogenation
301
301
287
288
288
288
289

11
5.8.2.2. Cleavage of Te-C bond
5.9. Naphtothiatellurole, Naphtoselenatellurole, Naphtoditellurole
5.9.1. Preparation
5.10. 2H-1,3-Ditelluroles
302
302
302
303
5.10.1. Preparation
5.10.2. Reactions
5.11. Tetratellurafulvalenes
5.11.1. Preparation
303
304
305
305
5.12. Tellurin and derivatives 4-H-tellurins and 4-oxo-4-H-tellurins
(telluropyran-4-ones)
5.12.1. Preparation
306
306
5.12.2. Reactions
5.13. 2H-1-Benzotellurin
5.13.1. Preparation
5.14. 4H-1-Benzotellurins and 4-oxo-4H-benzotellurins
5.14.1. Preparation
5.15. Telluroxanthenes/Telluroxanthones and derivatives
5.15.1. Preparation
5.15.2. Reactions
5.16. Phenoxatellurins
5.16.1. Preparation
5.17. Phenothiatellurins/Phenoselenotellurins
5.17.1. Preparation
5.18. Telluranthrenes
5.18.1. Preparation
5.18.1.1. From tellurium
5.18.1.2. From sodium telluride
5.19. Bis-thieno-1,4-ditellurins
5.19.1. Preparation
5.20. 1,4-Tellurino-1,4-tellurins
5.20.1. Preparation
317
317
5.21. Benzene fused heterocycles containing tellurium, selenium and sulfur
5.21.1. Preparation
318
318
5.22. 1,5-Ditelluracyclooctane and 5H,7H-dibenzo[b,g][1,5]tellurothiocin 319
314
314
315
315
315
316
317
317
308
309
309
309
309
310
311
311
313
313

12
5.22.1. Preparation
5.23. Ditellurane derivatives
5.23.1. Preparation
5.24. Reductive dimerization of telluro- and selenoxanthone
5.25. Tellurosteroids
5.26. 21,21-Dihalo-21-telluroporphyrin
6. Toxicology of organotellurium compounds
7. Pharmacology of organotellurium compounds
7.1. Chemopreventive activity
8. Miscellaneous
8.1. Some additional applications of TeCl
4
8.1.1. Preparation of

-methylene ketones
8.1.2. Olefin inversion by syn-chlorotelluration/anti-dechlorotelluration
8.1.3. TeCl
4
as a catalyst for dithioacetalization and ketalization
8.1.4. TeCl
4
as reagent for the conversion of alcohols to alkyl chlorides and as a Lewis acid catalyst for aromatic alkylation
8.1.5. TeCl
4
-promoted rearrangement of cycloheptatrienes to benzylic alcohols
8.1.6. TeCl
4
as catalyst for cationic oligo- and polymerization reactions
8.2.

-Hydroxyalkylation of

-unsaturated compounds
8.3. Conversion of allylsilane into allylamines via phenyltellurinylation
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