Comprehensive Organic Functional Group Transformations II: v. 5(Carbon with Two Attached Heteroatoms with at Least One Carbon-to-Heteroatom Multiple Link )

Cover Page......Page 1
Book Info......Page 2
Editors-in-Chief......Page 3
Editor of Volume 2......Page 5
Editor of Volume 4......Page 6
Editor of Volume 6......Page 7
Preface......Page 8
Introduction to Volume 5......Page 9
Explanation of the reference system......Page 10
Journal Abbreviations......Page 11
Techniques/Conditions......Page 13
Reagents, Solvents, etc.......Page 14
Part I: Tricoordinate Carbon Functions with One DoublyBonded and One Singly Bonded Heteroatoms, RC=YX......Page 17
Part II: Dicoordinate Carbon Functions with Two DoublyBonded Heteroatoms, Y1=C=Y2......Page 18
General Methods for Acid Halides......Page 19
Acid halides from acid chlorides......Page 20
Acid Fluorides......Page 21
Acid fluorides from acid chlorides......Page 22
Acid fluorides from carboxylic acids......Page 24
Acid fluorides from alcohols and aldehydes......Page 25
Using thionyl chloride......Page 26
Using oxalyl chloride......Page 28
Using phosphorus chlorides......Page 29
Acid Bromides......Page 30
Acid bromides from carboxylic acids......Page 31
Acid Iodides......Page 32
References......Page 33
Biographical sketch......Page 35
5.02 Carboxylic Acids......Page 37
Hydrolysis of esters......Page 38
Hydrolysis of nitriles......Page 39
Hydrolysis of amides......Page 40
By Carbonation of Organometallic Reagents......Page 41
By Oxidation Reactions......Page 42
By Miscellaneous Reactions......Page 45
By hydrolysis reactions......Page 47
By carbonylation of organometallic reagents......Page 55
By oxidation reactions......Page 59
By hydrolysis reactions......Page 62
By oxidation reactions......Page 67
By miscellaneous reactions......Page 68
By hydrolysis reactions......Page 73
By carbonation of organometallic reagents......Page 75
By oxidation reactions......Page 76
By miscellaneous reactions......Page 78
By hydrolysis reactions......Page 80
By carbonation of organometallic reagents......Page 83
By miscellaneous reactions......Page 85
By hydrolysis reactions......Page 86
By carbonation of organometallic reactions......Page 93
By miscellaneous reactions......Page 96
By hydrolysis reactions......Page 100
By carbonation of organometallic reagents......Page 104
By oxidation reactions......Page 106
By miscellaneous reactions......Page 107
By hydrolysis reactions......Page 108
By carbonation of organometallic reagents......Page 109
By hydrolysis reactions......Page 110
By Carbonation of Organometallic Reagents......Page 113
By Miscellaneous Reactions......Page 115
By Hydrolysis Reactions......Page 116
By Carbonation of Organometallic Reagents......Page 118
By Oxidation Reactions......Page 121
By Miscellaneous Reactions......Page 123
Carboxylic Acids via Biotransformations......Page 124
References......Page 134
Biographical sketch......Page 143
5.03 Carboxylic Esters and Lactones......Page 145
Direct Esterification Using Carboxylic Acids and Alcohols......Page 146
Esterification by Carboxylic Group-activated Intermediates (Mixed Anhydrides or Activated Esters)......Page 148
Esterification of Alcohols with Acid Halides and Anhydrides......Page 149
Esterification via Hydroxyl Group Activation......Page 152
Transesterification......Page 154
Enzymatic Transesterification......Page 156
Monoacylation of Polyols......Page 157
Nitrogen-substituted Alcohol Components......Page 158
Without Changing the Number of Carbons......Page 159
Esters via Baeyer-Villiger Oxidation......Page 162
Alkoxycarbonylation......Page 163
Arndt-Eistert Homologation......Page 164
Esters of Cycloalkanoic Acids......Page 166
Enolate alkylation......Page 168
Conjugate addition to alpha,beta-enoates......Page 169
alpha,beta-Unsaturated esters via redox reactions......Page 172
alpha,beta-Unsaturated esters via alkenation......Page 173
alpha,beta-Unsaturated esters via Heck coupling or alkoxycarbonylation......Page 174
gamma,delta-Unsaturated esters via Claisen-Johnson rearrangement......Page 175
Lactones......Page 176
beta-Lactones......Page 177
gamma-Lactones by direct cyclodehydration of gamma-hydroxycarboxylates......Page 179
gamma-Lactones by enolate additions......Page 180
gamma-Lactones from beta-,gamma-, and gamma-delta-ene-carboxylates......Page 181
gamma-Lactones via redox reactions......Page 182
delta-Lactones......Page 183
Carboxylic group-activated methods......Page 184
Hydroxyl group-activation methods......Page 186
References......Page 187
Biographical sketch......Page 192
5.04 Other Acyloxy Compounds......Page 193
5.05 Acylsulfur, -selenium, or -tellurium Functions......Page 195
Selenocarboxylic Acids......Page 196
From acyl halides......Page 197
From carboxylic acids......Page 198
From thiocarboxylic esters......Page 199
From thiocarboxylic acids......Page 201
Miscellaneous......Page 202
From acyl halides......Page 204
Miscellaneous......Page 205
Bis(acyl) Sulfides......Page 206
Acylsulfenyl Bromides......Page 207
Monoacyl-substituted disulfides......Page 208
Acylsulfenyl selenides......Page 209
Bis(acyl) disulfides......Page 210
Bis(acyl) diselenides......Page 211
Acylthiosilanes and their Selenium and Tellurium Analogs......Page 212
References......Page 213
Biographical sketch......Page 217
5.06 Amides......Page 219
Introduction......Page 220
Unhindered amides......Page 222
Stereocontrolled formation of amides......Page 223
Overview of major recent developments......Page 224
Acylation of Amines......Page 225
Directly from carboxylic acids......Page 226
From simple esters......Page 227
From active esters......Page 230
From acid anhydrides......Page 235
From acyl halides......Page 237
Using in situ coupling reagents......Page 239
Uronium salts......Page 241
Other methods......Page 242
Triazenes......Page 243
N-Heterocyclic leaving groups......Page 244
Other N-leaving groups......Page 245
Other acylating systems......Page 246
Hydrolysis of Nitriles......Page 247
Amino acids......Page 248
2-Arylacetonitriles......Page 249
Other nitrile hydratase substrates......Page 250
Lewis acid-catalyzed selective hydrolysis of nitriles......Page 251
Beckmann rearrangement......Page 252
Claisen rearrangement......Page 253
Wolff rearrangement......Page 254
Willgerodt rearrangement......Page 255
Other rearrangement processes......Page 256
Special routes to beta-lactams......Page 257
Other routes to "normal" amides......Page 258
Methods from simple esters......Page 259
Hydrolysis of nitriles......Page 260
Methods from simple esters......Page 264
Methods from active esters......Page 265
Methods using diimides......Page 267
Methods using phosphorus reagents......Page 268
Methods using uronium salts......Page 269
Methods using iminium salts......Page 272
Other acylation methods......Page 275
Beckmann rearrangement......Page 278
Willgerodt rearrangement......Page 279
Other methods......Page 280
Claisen rearrangement......Page 281
Methods from carboxylic acids......Page 282
Methods from active esters......Page 283
Methods from acyl halides......Page 284
Beckmann rearrangement reactions......Page 285
Hydrolysis of nitriles......Page 286
Methods from active esters......Page 287
Claisen rearrangement......Page 288
Other methods......Page 290
Hydrolysis of nitriles......Page 291
Methods from active esters......Page 293
Methods using uronium salts......Page 295
Methods using iminium salts......Page 296
Other acylation methods......Page 297
Beckmann rearrangement......Page 298
Claisen rearrangement......Page 299
Other rearrangements......Page 300
Methods using diimides......Page 301
Methods using iminium salts......Page 302
Other acylation methods......Page 303
Schmidt rearrangement......Page 304
References......Page 305
Biographical sketch......Page 311
5.07 N-Heterosubstituted Amides......Page 313
N-Chloroamides......Page 315
N-Hetero-N-chloroamides......Page 316
From amides......Page 317
N,N-Dibromoamides......Page 318
From acylation of hydroxylamines......Page 319
From the ring opening of cyclic acid anhydrides......Page 323
From oximes......Page 324
From solid-phase synthesis......Page 325
From oxidation of O-alkylhydroxamates......Page 326
From the formylation of hydroxylamines......Page 327
From the reaction of hydroxylamines with succinic anhydride......Page 328
From ozonolysis of O-alkyloximes......Page 329
From reactions with isatoic anhydride......Page 330
From N-methoxy-N-methylurea......Page 331
From amides......Page 332
From sulfenyl chlorides......Page 333
From sulfinamides......Page 334
From acylation of sulfonamides......Page 335
From sulfonylation of amides......Page 338
From sulfonyl azides......Page 339
From 1-acyl-2-(alkylsulfonyl)hydrazines......Page 340
From acylation of hydrazine and its derivatives......Page 341
From reaction of alcohols, ethers, and thioethers......Page 350
From alkyl and aryl halide compounds......Page 352
From ring opening of aziridinium ion species......Page 353
From 1-amino-5-hydroxytriazole derivatives......Page 355
From acylation of hydrazones......Page 356
From acylhydrazines......Page 357
From thiosemicarbazides......Page 358
N-Acyl Triazenes......Page 359
From amides......Page 360
From silylamides......Page 361
From acylation of phosphoramines......Page 362
From acyl azides......Page 364
From silylation of amides......Page 365
From acylation of N-silylamines......Page 366
From ring opening of oxazolines......Page 367
References......Page 368
Biographical sketch......Page 374
Introduction......Page 375
Functions with P-H or P-C Bond Only......Page 376
P-other heteroatom-bonded systems......Page 379
Functions with Two P-Heteroatom Bonds......Page 381
Functions with Single P-C Bonds......Page 382
Functions with Single P-Heteroatom or P-Metal Bonds Only......Page 383
With at least one oxygen substituent (but no halogen substituent)......Page 384
P=other heteroatom bonded systems......Page 388
References......Page 389
Biographical sketch......Page 392
AcylSilicon Derivatives, R1COSiR23......Page 393
Oxidation of alpha-silyl alcohols......Page 394
alpha-Silyl alcohols by silyl addition to aldehydes......Page 395
alpha-Silyl alcohols by regioselective ring-opening reactions of silyl oxiranes......Page 397
Reactions with acid chlorides......Page 398
Reactions with carboxylic acid esters......Page 399
Transition metal-catalyzed synthesis......Page 400
Silyl oxirane rearrangement......Page 401
gem-bis(Trialkylsilyl) compounds......Page 402
Acetylenic acyl silanes from reverse Brook rearrangement then oxidation......Page 404
alpha,beta-Unsaturated acyl silanes via reverse Brook rearrangement of allenes......Page 405
Acetylenic acyl silanes from silylation of propargylic ethers then oxidation......Page 406
alpha,beta-Unsaturated acyl silanes via 1,4-addition......Page 407
Annulation reactions of alkenoyl silanes......Page 408
Acylgermanium Derivatives, R1COGeR23......Page 411
Coupling of Germyl Metallic Species and Carboxylic Acid Derivatives......Page 412
Chemistry of Acyl Germanes......Page 413
References......Page 414
Biographical sketch......Page 416
General Introduction......Page 417
Introduction......Page 418
Acylzirconium Compounds......Page 419
Acylchromium Compounds......Page 421
Acylmolybdenum Compounds......Page 422
Acylmanganese Compounds......Page 423
Acylrhenium Compounds......Page 425
Acyliron Compounds......Page 426
Acylruthenium Compounds......Page 430
Acylosmium Compounds......Page 431
Acylcobalt Compounds......Page 432
Acylrhodium Compounds......Page 434
Acyliridium Compounds......Page 437
Acylnickel Compounds......Page 438
Acylpalladium Compounds......Page 440
Acylplatinum Compounds......Page 446
Acylgold Compounds......Page 447
Acyltin Compounds......Page 448
References......Page 449
Biographical sketch......Page 452
5.11 Thio-, Seleno-, and Telluroacyl Halides......Page 453
Thioacyl Fluorides via Dechlorination of 1-Chlorosulfenyl Chlorides......Page 454
Thioacyl Chlorides from Dithiocarboxylic Acids......Page 455
Thioacyl Chlorides via Sulfurization of Polyhaloalkenes, -alkanes, and -alkyl Derivatives......Page 456
Thioacyl Chlorides from Reaction between Thiophosgene and Aryllithium Salts......Page 457
Miscellaneous Reactions......Page 458
Halosulfines via dehydrohalogenation of sulfonyl halides......Page 459
Halosulfines via dichlorosulfenyl chlorides......Page 461
Halosulfinimides by dehydrohalogenation of 1,2-dihalosulfenamides......Page 462
Selenoacyl Fluorides from Mercuric Perfluoroalkylselenols......Page 466
Selenoacyl Iodides......Page 468
Telluroacyl Halides......Page 469
Telluroacyl Fluorides via Pyrolysis of Perfluoroalkyltrimethylstannyl Tellurides......Page 470
Telluroacyl chlorides......Page 473
References......Page 474
Biographical sketch......Page 476
5.12 Thio-, Seleno-, and Telluroacyloxy Functions, R1C(S)OR2, R1C(Se)OR2, R1C(Te)OR2, etc.......Page 477
Spectroscopic methods......Page 478
Theoretical methods......Page 479
Spectroscopic methods......Page 480
Carbotelluroic O-Acids......Page 481
Higher Oxidation States of the Chalcogen......Page 482
Class A: from RC(S)X......Page 483
Class B: from RC(Z)OR......Page 484
Miscellaneous......Page 485
Properties and reactions......Page 487
Reaction of alkyneselenolate salts or alkyneselenols with alcohols......Page 491
Miscellaneous......Page 492
Reactions......Page 494
Higher Oxidation States of the Chalcogen......Page 496
Introduction......Page 497
Carbothioic Anhydrides......Page 498
B-Thioacyloxy compounds......Page 499
Si-Thioacyloxy compounds......Page 500
Si-Selenoacyloxy compounds......Page 501
X=Group 15 Elements......Page 502
O-(Thioacyl)hydroxylamines and -oximes......Page 503
P-Thioacyloxy compounds and their selenium analogs......Page 504
X=Group 16 Elements......Page 505
References......Page 506
Biographical sketch......Page 509
Introduction......Page 511
Dithioic Acid Alkali Metal and Mg Salts......Page 512
Inner Salts of Dithioic Acids......Page 513
Dithioic Acid Esters......Page 514
Dithioalkanoic acid esters and aromatic and heteroaromatic acid esters......Page 515
alpha,beta-Unsaturated dithioic acid esters......Page 520
Dithioic acid esters having sulfur in higher oxidation states......Page 523
Dithioic acid Si, Ge, Sn, Pb esters......Page 524
Dithiocarbamyl-azo Dyes, Thioacylsulfanylphosphines and -arsines......Page 526
Trithioperesters......Page 527
Selenothioic and Diselenoic Acid Esters......Page 528
Selenothioic and Diselenoic Acid Salts......Page 531
References......Page 533
Biographical sketch......Page 536
Thionoamides from Carboxamides......Page 537
Use of phosphorus pentasulfide......Page 538
Use of Lawesson’s reagent......Page 540
Use of reagents related to Lawesson’s......Page 544
Miscellaneous reagents......Page 545
Thionoamides From Nitriles......Page 547
Thioacylation of Amines......Page 551
Thiocarbamoylation......Page 557
Aminosulfuration/Sulfuration......Page 561
Manipulation of an Existing Thionoamide......Page 562
Miscellaneous Methods......Page 567
Selenoamides......Page 569
Selenoamides from Carboxamides......Page 570
Selenoamides from Nitriles......Page 571
Manipulation of an Existing Selenoamide......Page 573
Miscellaneous Methods......Page 575
Telluroamides......Page 578
References......Page 579
Biographical sketch......Page 588
N-Acylthionoamides, N-Acylselenoamides, and N-Acyltelluroamides-R1C(S)NR2COR3......Page 589
N-Thionoacyl, N-Selenoacyl, and N-Telluroacylthionoamides (and Their Se and Te Analogs)-R1C(S)NR2C(S)R3......Page 591
Singly Bonded Nitrogen Functions other than Amides-Rc(S)N=Y, Rc(S)N=Z......Page 592
N-Thionoacylhydroxylamines and their Se and Te Analogs-R1C(S)NHOR2......Page 593
N-Thionoacylhydrazines and N-Thionoacylhydrazones and their Derivatives (and their Se and Te Analogs)-RC(S)NHNH2, R1C(S)NHN=Cr22......Page 595
N-Phosphonothionoamides, N-Phosphonoselenoamides, and N-Phosphonotelluroamides-R1C(S)NHPR22......Page 597
References......Page 598
Biographical sketch......Page 599
Singly Bonded Silicon Derivatives-R1C(S)SiR23, R1C(Se)SiR23, etc.......Page 601
General Comments and Methods......Page 604
References......Page 605
Biographical sketch......Page 607
5.17 Iminoacyl Halides and Oxy Functions......Page 609
Reactions with phosphorus tri- and pentahalides......Page 610
From Nitriles and Isonitriles......Page 613
From Amines......Page 614
From Imidoyl Halides......Page 615
Miscellaneous Methods......Page 616
By halogenation of aldoximes......Page 617
By halogenation of nitroalkanes and nitroalkenes......Page 620
By nitrosation of amidoximes......Page 622
General Remarks......Page 623
From diazonium halides......Page 624
By halogenation of hydrazones and azines......Page 625
From hydrazidoyl halides......Page 626
N-Phosphorylated Imidoyl Halides......Page 627
From carboxylic acid orthoesters or orthoamides......Page 628
From nitriles and isonitriles......Page 629
From heterocyclic compounds (ring-opening reactions)......Page 630
From imidates and amidines......Page 631
From metal complexes......Page 632
Miscellaneous methods......Page 633
From hydroxylamine and thioesters......Page 634
From ethyl hydroxyacetimidate......Page 635
By alkylation of an N-hydroxyamide or its ester......Page 636
N-Sulfonylimidates......Page 637
N-Sulfinylimidates......Page 638
From hydrazonoyl halides (hydrazidoyl halides)......Page 639
Miscellaneous methods......Page 640
N-Phosphorylated Imino-esters......Page 641
Mixed Anhydrides from Carboximidic Acids and Inorganic or Organic Acids......Page 642
From carboxylic acid amides and their salts and silylating agents......Page 644
References......Page 646
Biographical sketch......Page 654
Thiolimidic Acids, R1C(NR2)SH......Page 657
Thioimidic esters and anhydrides from thioamides, thiolactams, and related compounds......Page 658
Thioimidic esters and thioiminium salts from nitriles, nitrilium salts, isonitriles, and thiocyanates......Page 659
Thioimidic esters from imidoyl halides, thioimidoyl chlorides, and imidoyl derivatives......Page 660
Thioimidic esters from thioimidic esters......Page 661
Selenoimidic esters from selenoamides, imidoyl derivatives, and isoselenocyanates......Page 662
Telluroimidic esters, R1C(NR2)TeR3......Page 664
Imidoyl disulfides......Page 665
S-Imidoyl Sulfenamides and Related Structures, R1C(NR2)SNR3R4 and R1C(NR2)SN=CR3......Page 666
S-Imidoyl tin and mercury derivatives, R1C(NR2)SSnR3 and R1C(NR2)SHgSC(NR2)CR1......Page 667
References......Page 668
Biographical sketch......Page 672
5.19 Amidines and N-Substituted Amidines......Page 673
General methods......Page 674
Formamidines from disubstituted formamides, Vilsmeier reagents, and disubstituted thioformamides......Page 676
Formamidines from orthoformates, acetals, and aminals......Page 677
Formamidines from 1,3,5-triazine......Page 678
Formamidines, prepared by miscellaneous methods......Page 679
Aliphatic amidines from nitriles......Page 680
Aliphatic amidines from amides......Page 683
Aliphatic amidines from thioamides and thioimidic esters......Page 684
Aliphatic amidines, prepared by N-alkylation of simpler amidines......Page 685
Aromatic amidines from nitriles......Page 686
Aromatic amidines from thioamides and thioimidic esters......Page 689
Aromatic amidines from compounds with cumulated double bonds......Page 690
N-Thioacylamidines......Page 691
N-Selenoacylamidines......Page 692
N-Chloroamidines......Page 693
N-Imidoylhydroxylamines from hydroxylamine......Page 694
N-Imidoylhydroxylamines from amines and ammonia......Page 695
N-Imidoylsulfenamides R1C(NR2)NR3SR4......Page 696
N-Imidoylsulfimides......Page 697
N-Imidoylsulfonamides......Page 698
Amidine derivatives with an N-selenium bond......Page 700
Primary amidrazones, RC(NH)NHNH2......Page 701
N-Substituted amidrazones from hydrazines......Page 702
N1-Acylamidrazones......Page 703
N3-Acylamidrazones......Page 704
N-Phosphorylamidine derivatives......Page 705
Amidines with an N-antimony bond......Page 706
Monosilylamidines......Page 707
N-Borylamidines......Page 708
Amidines with an N-metal bond where M is a group 14 metal......Page 709
Amidines with an N-metal bond, where M is a lanthanide or actinide metal......Page 710
References......Page 711
Biographical sketch......Page 717
5.20 Iminoacyl Functions Linked to Any Heteroatom Other Than Halogen, Chalcogen, or Nitrogen......Page 719
From cyanophosphanes......Page 720
From imidoyl halides......Page 721
From alpha-aminophosphorus derivatives......Page 722
From phosphorus-substituted oxime and hydrazone derivatives......Page 723
From acylphosphorus derivatives......Page 724
From isocyanides......Page 725
From cyanohydrins......Page 726
Tetracoordinate Germanium Derivatives......Page 727
From isocyanides......Page 728
Imidoyl Derivatives of Transition Metals......Page 729
Imidoyl transition metal derivatives from isocyanide insertion reactions......Page 730
Imidoyl-Ti, -Zr, and -Hf derivatives......Page 732
Imidoyl-Cr, -Mo, and -W derivatives......Page 733
Imidoyl-Mn and -Re derivatives......Page 734
Imidoyl-Ni, -Pd, and -Pt derivatives......Page 735
Imidoyl-Sn derivatives......Page 736
References......Page 737
Biographical sketch......Page 741
5.21 N-Heterosubstituted Iminoacyl Functions......Page 743
Haloimidic Derivatives......Page 744
N-Haloimidic acids and salts......Page 745
N-Haloamidines......Page 746
From aci-nitro compounds and nitro alkenes......Page 747
From aldoximes......Page 751
From alpha-amino acid derivatives......Page 753
From carbonyl compounds......Page 754
From N-alkoxyamides......Page 755
Other methods......Page 756
Isomerization......Page 757
From oxyimidic halides......Page 758
From nitrile oxides......Page 759
From carboxylic acid alkoxy amides and acyloxy amides......Page 760
Oxyimidic Sulfur Derivatives......Page 763
From nitro compounds......Page 764
From oxyimidic thioacids and esters......Page 765
Oxyimidic Selenium, Silicon, and Tellurium Derivatives......Page 766
From nitriles......Page 767
From oxyimidic halides......Page 768
From amidines and hydroxyamidines......Page 769
Other methods......Page 770
From phosphonic acid esters......Page 771
From phosphites......Page 772
Thioimidic Halides and Related Structures......Page 773
Thioimidic Esters and Related Structures......Page 774
Thioimidic Amides and Related Structures......Page 776
Thioimidic Silicon and Selenium Derivatives......Page 777
From hydrazones......Page 778
From 2-halo-1,3-dicarbonyl compounds......Page 780
From diazonium salts and related compounds......Page 781
Transhalogenation......Page 782
From hydrazides......Page 783
From thioamides, thioureas, thiocarbonyl hydrazides, and derivatives......Page 785
Other methods......Page 787
Hydrazonic Derivatives of Phosphorus and Silicon......Page 789
From nitriles......Page 791
From amines and hydrazine derivatives......Page 792
From imidic esters......Page 793
From amidines......Page 794
From amides and related structures......Page 795
From thiocarbazides and related structures......Page 796
From hydrazones......Page 797
From 1-nitroaldehyde hydrazones......Page 798
From hydrazonamides......Page 799
Imidophosphorane Esters......Page 800
Imidophosphorane Thioesters......Page 801
Other Imidoyl Derivatives of Phosphorus......Page 802
N-Silylimidoyl Derivatives......Page 803
N-Selenylimidoyl Derivatives......Page 804
N-Borylimidoyl Derivatives......Page 805
References......Page 806
Diazo Functions with an alpha-Heteroatom......Page 817
alpha-Diazo oxygen and Sulfur Compounds......Page 818
alpha-Diazo nitrogen Compounds......Page 820
alpha-Diazo Phosphorus(V) Compounds......Page 821
alpha-Diazo Phosphorus(III) Compounds......Page 822
alpha-Diazo Boron Compounds......Page 824
alpha-Diazo Silicon Compounds......Page 825
alpha-Diazo metal Compounds......Page 827
References......Page 828
Biographical sketch......Page 830
5.23 Phosphoacyl Functions and Their As, Sb, and Bi Analogs......Page 831
From phosphaalkynes......Page 832
From chloromethylene phosphanes......Page 833
Bromine derivatives-R1C(PR2)Br......Page 835
From silylphosphanes and acid chlorides......Page 836
From peripheral reactions......Page 838
From 2,5-(chlorophosphanyl)phosphanylthiophenes by dehydrochlorination......Page 840
From phosphaalkynes......Page 841
From nitriles......Page 842
From phosphavinylidene carbenoids and isocyanates......Page 843
Peripheral reaction at phosphaalkenes......Page 845
From phosphavinylidene carbenoids......Page 846
From phosphaalkynes......Page 847
From 1,2,4-triphospholides......Page 848
The availability of phosphavinyl......Page 849
From phosphaalkynes......Page 850
From 1,3,5-Dewar-triphosphinines......Page 858
From 1,3,5-triphosphinines......Page 859
From 1,2,5-triphosphabenzvalenes......Page 864
From 1,2,4-triphospholes......Page 865
From ylides......Page 866
By miscellaneous methods......Page 868
From C-halo-(C-silyl)phosphaalkenes......Page 869
From phosphaalkynes......Page 870
From phosphaalkynes......Page 871
From iodomethylene phosphanes......Page 872
From phosphavinyl Grignard reagents......Page 873
Derivatives with group 14 metals......Page 874
Derivatives with group 13 metals......Page 875
Transition metal derivatives......Page 876
Oxygen derivatives......Page 878
From lithium (silyl)arsenides and carbenium salts......Page 879
Oxygen derivatives-R1C(SbR2)OR3......Page 880
lambda3,sigma2-Methylene phosphoranes......Page 881
eta1-Phosphaalkene complexes-RC[PX1(M)]X2......Page 883
Introduction......Page 887
Bromine derivatives-R1C(PR23)Br......Page 888
Iodine derivatives-R1C(PR23)I......Page 889
From ylides......Page 890
Derivatives with tricoordinate sulfur-R1C(PR23)SR3R4......Page 891
Derivatives with dicoordinate selenium-R1C(PR23)SeR3......Page 892
Derivatives with dicoordinate nitrogen-R1C(PR23)NR3......Page 893
Derivatives with tricoordinate nitrogen-R1C(PR23)NR32......Page 894
Derivatives with dicoordinate phosphorus-R1C(PR32)PR3......Page 896
From ylides......Page 897
From phosphaalkenes......Page 901
From carbenes......Page 902
From bis(iminophosphoranyl)methanide complexes......Page 903
From ylides......Page 905
Arsenic derivatives-R1C(PR23)AsR32......Page 910
Antimony derivatives-R1C(PR23)SbR32......Page 911
From ylides......Page 912
Transition metal derivatives-R1C(PR23)MLn......Page 913
Chalcogen derivatives-R1C(AsR23)ER3n (E=O, S, Se, Te)......Page 914
Tetracoordinate Bismuth Functions-R1C(BiR23)X......Page 915
References......Page 916
Biographical sketch......Page 920
From acyl silanes......Page 921
Boron Derivatives, R1C(X)=BR22......Page 925
References......Page 926
Biographical sketch......Page 927
Structure and Bonding......Page 929
From lithium salts......Page 930
From "ate" complexes......Page 935
From acyl complexes......Page 936
Formation of the M=C Double Bond from Acid Derivatives......Page 937
Alkyne-Vinylidene and Related Rearrangements......Page 939
Miscellaneous Methods......Page 941
alpha-Carbanion Reactions......Page 943
Alkylation and acylation......Page 944
Aldol condensations and related processes......Page 946
Carbene as a Michael acceptor......Page 948
Carbene as a Michael donor......Page 952
Cycloaddition Reactions......Page 953
Miscellaneous Reactions......Page 956
References......Page 959
Biographical sketch......Page 965
Introduction......Page 967
Reaction with phosgene, diphosgene, and triphosgene......Page 968
Reaction with carbon monoxide......Page 971
Reaction with activated carbonates......Page 973
Reaction with carbon dioxide......Page 975
Reaction of iminophosphoranes with carbon dioxide......Page 976
From carbamates and boron halides......Page 977
From Ureas......Page 978
From arylpalladium(II) azido complexes......Page 979
From acyl azides (Curtius rearrangement)......Page 980
From rhenium hydrazide complexes......Page 983
From Other Isocyanates......Page 984
From four-membered nitrogen heterocycles......Page 985
Blocked Isocyanates......Page 986
References......Page 988
Biographical sketch......Page 991
Chalcogen Functions......Page 993
Carbon disulfide......Page 994
From amine derivatives......Page 995
Isothiocyanates from halides......Page 997
Isothiocyanates from thiocyanates......Page 998
Isothiocyanates from alkenes......Page 1000
Isothiocyanates by cleavage of nitrogen-sulfur-containing heterocycles......Page 1001
Isothiocyanates from allylsilanes and allylstannanes......Page 1003
Isoselenocyanates from amines and their derivatives......Page 1004
Acyl and imidoyl isoselenocyanates......Page 1005
References......Page 1006
Biographical sketch......Page 1008
Introduction......Page 1009
Via metal salts......Page 1010
Via acid chlorides and related reagents......Page 1011
Via isocyanates and isothiocyanates......Page 1013
Via oxidation of selenoureas......Page 1018
Via metathesis......Page 1019
Via rearrangement......Page 1021
Carbodiimides of the type RN=C=NR, where R=SiR13......Page 1022
Carbodiimides of the type MN=C=NM, where M=metal......Page 1023
Metalloid Derivatives, R1-M=C=N-R2 (M=Si, Sn)......Page 1024
References......Page 1025
Biographical sketch......Page 1027
Dicoordinated phosphorus and arsenic functions......Page 1029
Higher-coordinated phosphorus functions......Page 1030
Functions with one tetracoordinated and one tricoordinated phosphorus atom......Page 1031
Functions with two tetracoordinated phosphorus atoms......Page 1032
Metalloid Functions......Page 1034
Metal Functions......Page 1035
Derivatives with Two Metalloid Functions......Page 1036
Compounds Bearing Two Metal Functions......Page 1037
References......Page 1038
Biographical sketch......Page 1040
5.30 Nitriles with a Heteroatom Attached to the Cyanocarbon......Page 1041
Cyanate Formation via Thermolysis of Thiatriazoles......Page 1042
Cyanate Formation via the Reaction of Alcohols or Phenols with Cyanogen Halides......Page 1043
Cyanate Formation from O-Alkyl Thiocarbamates and Thiocyanates......Page 1044
Thiocyanates-RSC=N......Page 1045
Formation of the R-SCN bond via displacement of X from R-X......Page 1046
Formation of the R-SCN bond by attack of nucleophilic thiocyanate on other carbon electrophiles......Page 1048
Formation of the R-SCN bond by reaction of an alkene with an electrophile and -SCN......Page 1049
Formation of the R-SCN bond by reactions with electrophilic sulfur......Page 1050
Formation of the R-SCN bond by homolytic reactions......Page 1051
Nucleophilic cyanation of sulfur......Page 1052
Electrophilic cyanation of sulfur......Page 1053
Formation of RSCN by Fragmentation/Rearrangement Reactions......Page 1054
Formation of the R-SeCN bond by nucleophilic substitution reactions......Page 1055
Additions to double bonds......Page 1058
Formation of the RSe-CN bond......Page 1059
Formation of the RTe-CN bond......Page 1060
Formation of an R-NCN bond leading to alkylcyanamides......Page 1061
Formation of an R-NCN bond leading to arylcyanamides......Page 1062
Preparations of acylcyanamides......Page 1063
Preparations of iminocyanamides......Page 1064
Formation of the RN-CN bond by reaction with nucleophilic cyanide......Page 1065
Reaction of primary and secondary nitrogen with electrophilic cyanide......Page 1066
Reaction of tertiary nitrogen with electrophilic cyanide......Page 1067
Dehydration and equivalent reactions leading to cyanamides......Page 1068
Rearrangement and fragmentation reactions leading to cyanamides......Page 1069
Singly Bonded Phosphorus, Antimony, Arsenic, and Bismuth Derivatives-R2P-C=N, R2Sb-C=N, R2As-C=N, R2Bi-C......Page 1071
Modification of the substitution pattern at phosphorus(III)......Page 1072
Formation of the P-CN bond......Page 1073
Modification of the substitution pattern at phosphorus(V)......Page 1074
Bismuth Derivatives......Page 1075
R3SiCN Compounds......Page 1076
R2BCN Compounds......Page 1077
Singly Bonded Metal Derivatives......Page 1079
Palladium derivatives......Page 1080
Platinum derivatives......Page 1081
Gold derivatives......Page 1082
Derivatives of other transition metals......Page 1083
Gallium derivatives......Page 1084
Tin derivatives......Page 1085
Heteronitrilium Compounds with the General Formula RXC=N+-Y......Page 1086
Nitriliumborates-R3B--CN+-CR3......Page 1087
Silylnitrilimines-R3Si-CN+-N--R and phosphoranylnitrilimines-R2P(X)-CN+-N--R......Page 1088
Cyanamidiummetallates-R2N-CN+-MXn-......Page 1089
References......Page 1090
Biographical sketch......Page 1097
Triply Bonded Phosphorus Attached to the sp-Carbon Atom......Page 1099
At room temperature and low temperatures......Page 1101
Intermolecular......Page 1102
In the presence of sodium hydroxide......Page 1103
Amino-substituted phosphaalkynes......Page 1104
Isomerization under flash vacuum pyrolysis conditions......Page 1105
Transition metal-catalyzed rearrangements......Page 1106
From Phosphinodiazoalkanes......Page 1107
Triply Bonded Arsenic Attached to the sp-Carbon Atom......Page 1108
References......Page 1109
Biographical sketch......Page 1111