Modem Acetylene Chemistry

✍ Scribed by Peter Stang, François Diederich

• Publisher: Wiley-VCH
• Year: 1995
• Tongue: English
• Leaves: 531
• Edition: 1
• Category: Library

✦ Synopsis

This comprehensive handbook presents the full potential of modern acetylene chemistry, from organic synthesis through materials science to bioorganic chemistry. K. Houk, H. Hopf, P. Stang, K. M. Nicholas, N. Schore, M. Regitz, K. C. Nicolaou, R. Gleiter, L. Scott, R. Grubbs, H. Iwamura, J. Moore, and F. Diederich - internationally renowned authors introduce the reader, in a didactically skilful manner, to the state-of-the-art in alkyne chemistry. Emphasis is placed on presenting carefully selected and instructive examples as well as essential references to the original literature. Special benefits: Each chapter is rounded off by useful experimental procedures.

✦ Table of Contents

Modern Acetylene Chemistry......Page 7
Contents......Page 11
Foreword......Page 9
List of Contributors......Page 23
1.2 Electronic structures of acetylene and monoacetylenes......Page 26
1.2.1 Ground-state potential energy surfaces......Page 28
1.2.2 Excited-state potential energy surfaces......Page 30
1.2.3 Radical Ions......Page 31
1.3.1 Pericyclic reactions......Page 32
1.3.2 Electrophilic reactions......Page 35
1.3.4 Radical additions......Page 36
1.3.5 Molecular complexes......Page 37
1.4.1 Diacetylene......Page 38
1.4.2 Cn and cyclic Cn......Page 40
1.4.2.2 C3......Page 43
1.4.2.4 C5, C7, and C9......Page 44
1.4.2.5 C6, C8 and C10......Page 45
1.4.2.7 C18......Page 47
1.5 Conclusion......Page 50
References......Page 51
2.1 Introduction......Page 58
2.2.1 Synthesis......Page 59
2.2.2.1 A short summary of the older literature......Page 63
2.2.2.2 Novel cycloadditions with cyanoacetylenes — simple and efficient methods for the construction of complex carbon frame......Page 64
2.2.2.3 Cyanoacetylenes as precursors for reactive and interstellar intermediates......Page 71
2.3.2.1 The preparation of the 1-Halogeno- and 1,2-Dihalogenoethynes......Page 73
2.3.2.2 More highly unsaturated halogenoacetylenes......Page 75
2.3.2.3 Derivatives of 1-halogenoacetylenes......Page 77
2.3.3 Novel preparative uses of 1-Halogeno- and 1,2-Dihalogenoacetylenes......Page 78
2.4.2 Dicyanoacetylene (2)......Page 85
2.4.4 Chloroacetylene (93)......Page 86
References......Page 87
3.1 Introduction......Page 92
3.2.1 Alkynyliodonium sulfonates......Page 93
3.2.2 Alkynyliodonium tetrafluoroborates......Page 94
3.2.3 Heterocyclic alkynyliodonium species......Page 95
3.2.4 Mechanism of formation......Page 96
3.2.6 Bis-iodonium species......Page 97
3.2.7 Properties of alkynyliodonium salts......Page 98
3.3.1 Spectroscopic properties......Page 99
3.3.2 X-ray and molecular structure......Page 100
3.4 Reactions and uses of alkynyliodonium salts......Page 101
3.4.1 Reaction with nucleophiles......Page 102
3.4.1.1 Carbon nucleophiles......Page 103
3.4.1.2 Nitrogen nucleophiles......Page 105
3.4.1.3 Oxygen nucleophiles......Page 106
3.4.1.4 Sulfur nucleophiles......Page 108
3.4.1.5 Phosphorus nucleophiles......Page 111
3.4.1.6 Halogen nucleophiles......Page 112
3.4.2 Reaction with organometallic species......Page 113
3.4.3.1 [2 + 4]-Diels–Alder cycloadditions......Page 115
3.4.3.2 1,3-Dipolar cycloadditions......Page 116
3.6.1 (Cyano{[(trifluoromethyl)sulfonyl]oxy)iodo}benzene, 7......Page 117
3.6.4 General procedure for the preparation of bis-iodonium diyne bis-triflates, 34 and 35......Page 118
3.6.7 General procedure for the preparation of cyclopentenones and γ-lactams......Page 119
References......Page 120
4.2.1 Alkyne complexes......Page 124
4.2.2 Propargylium–metal complexes......Page 126
4.3 Complexes of novel alkynes......Page 129
4.4.1.1 Nucleophilic addition......Page 132
4.4.1.2 Electrophilic addition......Page 133
4.4.1.3 M – H addition/hydrogenation......Page 134
4.4.1.5 Coupling reactions with unsaturated substrates......Page 135
4.4.1.6 Alkyne scission/metathesis/polymerization......Page 139
4.4.1.8 Demetalation......Page 140
4.4.2.1 Alkyne–vinylidene isomerization......Page 141
4.4.2.2 Reactions of complexed terminal alkynes with base......Page 142
4.4.3.2.1 General reaction features......Page 143
4.4.3.2.2 Proton loss/elimination......Page 145
4.4.3.2.3 Coupling with noncarbon nucleophiles......Page 146
4.4.3.2.4 Coupling with carbon nucleophiles......Page 147
4.5 Special applications of metal–alkyne complexes......Page 153
4.6.1 μ-[(η2, η2-1-Methyl-2-propynylium)dicobalthexacarbonyl] tetrafluoroborate(126)......Page 155
4.6.3 μ-[η2,η2-dl-3,4–Diphenyl-1,5-cyclooctadiyne]-bis-hexacarbonyldicobalt (128)......Page 156
References......Page 157
5.2 Cycloadditions of acetylenes with Fischer carbenes......Page 164
5.2.1 Naphthols – the Dötz reaction......Page 165
5.2.2 Indenes......Page 172
5.2.3 Cyclobutenones......Page 174
5.2.4 Cyclopentenones......Page 175
5.2.6 Cyclopropanes......Page 176
5.2.7 Heterocyclic ring systems......Page 178
5.3 The Pauson–Khand reaction: cycloadditions of olefins, acetylenes, and CO......Page 179
5.3.1 Background and mechanism......Page 180
5.3.2 Intermolecular Pauson–Khand reaction......Page 182
5.3.3 Intramolecular Pauson–Khand reaction......Page 186
References......Page 192
6.1 Introduction......Page 198
6.2 Syntheses of phosphaalkynes......Page 199
6.3 Reactivity of phosphaalkynes......Page 200
6.4 The history of phosphorus-carbon cage compounds from phosphaalkynes......Page 201
6.5.1.1 Diphosphatetracyclodecenes......Page 202
6.5.1.2 Phosphaprismanes and phosphabenzvalenes......Page 203
6.5.1.3 Diphosphatricyclooctenes......Page 205
6.5.1.4 Diphosphatetracycloundecadienones and oxadiphosphapentacyclononade- capentaenones (the tropone reaction of phosphaalkynes)......Page 207
6.5.1.5 Diphosphirenes as intermediates for phosphorus-carbon cage compounds......Page 208
6.5.1.6 Thermal cyclotetramerization......Page 209
6.5.2 Construction by extrusion of Cp2Zr from phosphaalkyne dimer complexes......Page 210
6.5.2.2 Tetraphosphacubanes and isomeric cage compounds......Page 211
6.5.2.3 P-functionalization of the tetraphosphacubane system......Page 213
6.5.3.1 Spirocyclotrimerization......Page 214
6.5.3.2 Phosphaalkyne tetramers from the spirocyclotrimer 71a......Page 215
6.5.3.3 Hexaphosphapentaprismane from the spirocyclotrimer 71a......Page 217
6.5.3.4 Phosphorus-carbon-aluminum cage compounds......Page 219
6.6 Outlook......Page 220
6.7.2 (2,2-Dimethylpropylidyne)phosphane (9a)......Page 221
6.7.5 2,4,6-Tri-tert-butyl-1,5-diphospha-3-phosphoniaspiro[3.4]hexa-1,4-diene-6-t- richloroaluminate (71a)......Page 222
6.7.8 2,5,7,9-Tetra-tert-butyl-3,3,4-triethyl-4-aluminato-3,6,8.triphospha-1-phosphoniatetracyclo[4.2.1.01,5.04,9]nona-2,7-diene (81)......Page 223
References......Page 224
7.1 Introduction......Page 228
7.2.1 The cycloaromatization of conjugated polyenyne systems......Page 230
7.2.2 Application to the synthesis of aromatic systems......Page 231
7.3 The discovery of the enediyne antibiotics......Page 232
7.3.1 Neocarzinostatin......Page 233
7.3.2 The calicheamicins......Page 237
7.3.3 The esperamicins......Page 241
7.3.4 The dynemicins......Page 242
7.3.5.1 Kedarcidin......Page 246
7.3.5.2 C-1027......Page 248
7.4.1.1 Theoretical considerations......Page 249
7.4.1.2 Synthetic studies......Page 251
7.4.2.1 Synthetic and theoretical studies on the Bergman cycloaromatization of cyclic enediynes......Page 263
7.4.2.2 Synthetic approaches to the calicheamicin aglycone......Page 266
7.4.2.3 Synthetic approaches to the calicheamicin/esperamicin carbohydrate fragments......Page 274
7.4.2.4 Total synthesis of calicheamicin γI1......Page 283
7.4.3 Dynemicin synthetic studies......Page 286
7.5 Medical applications of the enediyne antibiotics......Page 298
7.6 Concluding remarks......Page 299
References......Page 301
8.1 Introduction......Page 310
8.2.1.1 Using acetylenic reactivity: nucleophilic substitution with metal acetylides and related reactions......Page 311
8.2.1.2 Employing propargylic cations, anions, and radicals......Page 313
8.2.2.1 1,2-Elimination......Page 317
8.2.2.2 Cycloelimination reactions......Page 318
8.2.2.3 Ring contraction......Page 319
8.2.3 Ring-enlargement reactions......Page 320
8.3.1 Structures of cyclic mono- and dialkynes......Page 321
8.3.2 Photoelectron spectra of cyclic diacetylenes......Page 326
8.4.1 Rearrangement of cyclic alkynes......Page 328
8.4.2 Transannular reactions......Page 330
8.4.3.1 Homonuclear addition reactions......Page 333
8.4.3.3 Cycloaddition reactions......Page 334
8.5 Reactions of cyclic alkynes with metal compounds......Page 336
8.7.1.3 1,8-Cyclotetradecadiyne (120)......Page 339
8.7.3 Cyclonon-2-ynone (91) and bicyclo[6.1.0]non-1(8)-en-9-one (92)......Page 340
References......Page 341
9.1 Introduction......Page 346
9.2 Pericyclynes......Page 347
9.3 “Exploded” pericyclynes......Page 355
9.4 Homoconjugated mixed polyalkyne/diyne macrocycles......Page 362
9.5 Heterocyclic cognates of pericyclynes......Page 365
9.6.1 Conversion of a methyl ketone to a terminal acetylene (28 → 30, Fig. 9-8)
......Page 370
9.6.3 Preparation of a 1,2-diyne by cross-coupling of a preformed copper acetylide with a bromoalkyne - 2:1 example (49 + 50 → 51, Fig. 9-14)
......Page 372
9.6.5 Coupling of a terminal acetylene with a tertiary propargylic chloride - 2:1 example (47 → 69, Fig. 9-20)
......Page 373
References......Page 374
10.1 Introduction......Page 378
10.2.1.1 Acetylene polymerization......Page 383
10.2.1.2 Polymerization of substituted alkynes......Page 384
10.2.2.1 Nonmetathetic routes......Page 388
10.2.2.2 Routes using olefin metathesis......Page 391
10.2.3 Ring-opening of cyclooctatetraene......Page 393
10.4.1 Synthesis of substituted polycyclooctatetraenes......Page 401
10.4.3.1 Synthesis of poly(diethyl 7-oxabicyclo[2.2.1]hepta-2,5-diene-2,3-dicarboxylate)......Page 402
10.4.3.3 Solution production of polyacetylene from poly(diethyl 7-oxabicyclo[2.2.1] hepta-2;5-diene-2,3-dicarboxylate)......Page 403
References......Page 404
11.2.1 Alkynyl compounds carrying unpaired electrons in remote substituents......Page 410
11.2.2 Alkynes bonded to paramagnetic transition metals......Page 412
11.2.3 2-Propynylidenes......Page 414
11.3.1 What makes acetylenic compounds unique in assembling their molecules?......Page 416
11.3.2 Guiding principles on aligning electron spins in parallel between two neighboring molecules......Page 417
11.3.3 Crystals of antiferromagnetic 1,3-butadiyne and ferromagnetic 1,3,5-hexatriyne both carrying 4-chloro-3-(N-tert-butyl-N-oxyamino)phenyl as a stable free-radical substituent......Page 418
11.4.1 Natural spins detected during the solid-state polymerization of 1,3-butadiynes......Page 420
11.4.2 Topological control of the high-spin vs. low-spin ground states of π-Conjugated diradicals and dicarbenes......Page 423
11.4.3.1 Poly(phenylacetylenes)......Page 425
11.4.3.2 Poly(phenyldiacetylenes)......Page 427
11.5 Cyclotrimerization reaction of benzoylacetylenes in the presence of a secondary amine......Page 428
11.7.1 Characterization of magnetic properties......Page 434
11.7.2.3 1,3,5-Tris[3-(3,5-dibenzoylbenzoyl)benzoyl]benzene (49)......Page 435
References......Page 436
12.1 Introduction......Page 440
12.1.1 Structural parameters of phenylacetylenes......Page 441
12.2 Phenylacetylene dendrimers......Page 443
12.2.1 Synthetic considerations for phenylacetylene dendrimer construction......Page 444
12.2.1.1 The divergent and convergent synthetic approaches......Page 445
12.2.1.2 Convergent synthesis of phenylacetylene dendrimers......Page 446
12.2.1.4 Synthesis of dendrimers by repetition of monomer enlargement (SYNDROME method)......Page 448
12.2.1.5 “Double exponential” dendrimer growth......Page 449
12.3 Phenylacetylene macrocycles......Page 451
12.3.1 Phenylacetylene macrocyclic framework......Page 453
12.3.2.1 The double cyclization of branched phenylacetylene oligomers......Page 455
12.3.2.2 Tandem bimolecular coupling followed by intramolecular cyclization to form a foldable phenylacetylene macrotetracycle......Page 456
12.4 Synthesis of sequence-specific phenylacetylene oligomers and dendrimers on an insoluble solid support......Page 458
12.5 Conclusions......Page 461
12.6.3 Sample preparation for mass spectrometry......Page 462
12.6.4.3 General procedure C: trimethylsilyl deprotection......Page 463
12.6.7 Propylaminomethylated polystyrene (29)......Page 464
12.6.8 Direct triazene linkage to propylaminomethylated polystyrene (31)......Page 465
References......Page 466
13.2 Synthetic approaches to the cyclocarbons......Page 468
13.2.1 The retro-Diels-Alder route to cyclo-C18......Page 470
13.2.2 The 3-cyclobutene-1,2-dione route to the cyclocarbons......Page 471
13.2.3 The transition metal complex route to cyclo-C18......Page 473
13.3.1 Synthesis of tetraethynylethene (20) and geminally bisdeprotected derivatives......Page 474
13.3.3 Synthesis of trans-bis(triisopropylsilyl)-protected and trans-bisdeprotected tetraethynylethenes......Page 476
13.3.4 Synthesis of cis-bisdeprotected tetraethynylethenes......Page 477
13.3.5 Other perethynylated compounds as potential monomers for carbon networks......Page 478
13.4.1 Perethynylated dehydroannulenes......Page 481
13.4.2 Perethynylated expanded radialenes......Page 484
13.5.1 Linear polyynes: short oligomers of elusive carbyne......Page 486
13.5.2 Stable soluble conjugated carbon rods with a polytriacetylene backbone......Page 488
13.7.1 3,4-Bis[triisopropylsilyl)ethynyl]-3-cyclobutene-1,2-dione (12f)......Page 489
13.7.3 3-Dibromomethylene-1,5-bis(trimethylsilyl)-1,4-pentadiyne (23)......Page 490
13.7.6 General procedure for solution-spray flash vacuum pyrolysis (SS-FVP)......Page 491
References......Page 494
Index
......Page 498