Comprehensive Organic Functional Group Transformations 2 in 7 v. Volume 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 This new seven volume work builds on Elsevier's impressive and established organic chemistry MRW portfolio. Comprehensive Organic Functional Group Transformations II (COFGT-II) will provide the first point of entry to the literature for all scientists interested in chemical transformations. Presenting the vast subject of organic synthesis in terms of the introduction and interconversion of all known functional groups, COFGT-II will provide a unique information source documenting all methods of efficiently performing a particular transformation. Organised by the functional group formed, COFGT-II will consist of 144 specialist reviews, written by leading scientists who will evaluate and summarise the methods available for each functional group transformation. This work will be published both as a traditional 7 volume printed set and on-line via ScienceDirect, the world's best internet resource for scientific, technical and medical information COFGT-II provides the first point of entry to the literature for all scientists interested in chemical transformations. Presenting the vast subject of organic synthesis in terms of the introduction and interconversion of all known functional groups, COFGT-II provides a unique information source documenting all methods of efficiently performing a particular transformation. Organized by the functional group formed, COFGT-II consists of 144 specialist reviews, written by leading scientists who evaluate and summarize the methods available for each functional group transformation