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[INDEX [ A Acid-catalyzed dehydration, of alcohols, Addition reactions, 337–390 303–308 Absolute configuration, 229–231 of alkenes, 338–373 Acid-catalyzed esterification, 778–780 Absorption spectrum, 590 Adduct, 599 Acid-catalyzed halogenation, of aldehydes Acetals, 728–730 Adenosine diphosphate (ADP), 423 and ketones, 818 Adenosine triphosphate (ATP), 274, 423, Acetaldehyde, 10, 72, 76, 78, 372, 714 Acid-catalyzed hemiacetal formation, 967–968 Acetaldehyde enolate, 53 726–727 Adenylate cyclase, 1095 physical properties, 10 Acid-catalyzed hydration, of alkenes, 354, Adipic acid, 765 Acetic acid, 73–74, 76, 78, 113, 118–119, 496–497 Adipocytes, 1016 126–128, 147, 762 Acid chlorides, see Acyl chlorides Adrenaline, 273, 899 physical properties, 78 Acid derivatives, synthesis of, 775 Adrenocortical hormones, 1032 and pK , 114 a Acidic hydrolysis of a nitrile, 790–791 Adriamycin, see Doxorubicin Acetoacetic ester synthesis, 825–830 Acidity: Agent Orange, 643–644 acylation, 829–830 carboxylic acids vs. alcohols, 126–132 Aggregation compounds, 163 dialkylation, 826 effect of solvent on, 132 Aglycone, 974–975 substituted methyl ketones, 826–827 hybridization, 122–123 Alanine, 909, 1048, 1051 Acetone, 14, 57, 72, 79, 711 inductive effects, 123 isoelectric point of, 1051 Acetonides, 979, 1007–1008 relationships between structure and, titration curve for, 1052 Acetonitrile, 75 120–123 Albrecht, Walther, 608–609 Acetylcholine, 890–891, 900–901 Acidity constant (Ka), 113–114 Albuterol, 492 Acetylcholinesterase, 900, 1081 Acid strength, 113 Alcohols, 55, 67–68, 132. See also Primary Acetyl-coenzyme A, 773 Acne medications, chemistry of, 450 alcohols; Secondary alcohols; Tertiary Acetylenes, 7, 57, 161, 283, 325 Acrylonitrile, anionic polymerization of, 477 alcohols structure of, 40–42 Actin, 168 acid-catalyzed dehydration of, 303–308 Acetylenic hydrogen atom, 161, 312 Activating groups, 677–678, 685, 690 acidity of, 126–128 of terminal alkynes, substitution of, Activation energies, 462 as acids, 500 312–313 Active hydrogen compounds, 833–834 addition of: Acetyl group, 713 Active methylene compounds, 833–834 acetals, 728–730 Achiral molecules, 194, 197, 200, 462 Active site, 1076 hemiacetals, 726–727 Acids: of enzyme, 1055 thioacetals, 731 alcohols as, 500 Acyclovir, 1098 alcohol carbon atom, 490 Brønsted–Lowry, 105–106, 139 Acylation, 829–830 from alkenes: Lewis, 109–111 Acylation reaction, 669 through hydroboration–oxidation, in nonaqueous solutions, 135–136 Acyl chlorides (acid chlorides), 670, 349–352 phenols as, 130–131 716–717, 766–767, 774–777 through oxymercuration– relative strength of, 115 aldehydes by reduction of, 716–718 demercuration, 349–350 in water, 106 esters from, 780 boiling points, 492 Acid anhydrides, reactions of, 800 reactions of, 776–777, 799–800 conversion of: Acid–base reactions, 105–109, 120–123COPYRIGHTEDsynthesis of, 775–776 MATERIAL into alkyl halides, 501 acids and bases in water, 106–107 using thionyl chloride, 776 into a mesylate, 507 of amines, 909 Acyl compounds: dehydration of, 303–305 Brønsted–Lowry acids and bases, 105–106 relative reactivity of, 774–775 acid-catalyzed, 303–308 curved arrows, 107 spectroscopic properties of, 768–770 carbocation stability and the transition mechanism for, 107–108 Acyl groups, 669–670 state, 308–312 opposite charges attract, 137 as ortho–para directors, 679–680 ethanol, 490, 493–495 predicting the outcome of, 118–120 Acyl halide, 670 as a biofuel, 495 and the synthesis of deuterium and as insecticide, 676 ethylene, 495 tritium-labeled compounds, Acylium ions, 429 polymerization of, 475 136–137 Acyl substitution, 761, 773–775, 812 from Grignard reagents, 552–560 water solubility as the result of salt by nucleophilic addition–elimination, hydrogen bonding, 493 formation, 119–120 773–774 infrared (IR) spectra of, 93–94 Acid-catalyzed acetal formation, 728–729 Acyl transfer reactions, 773 intermolecular dehydration, ethers by, Acid-catalyzed aldol condensations, 858–859 Adamantane, 182 508–509 Acid-catalyzed aldol enolization, 816 Addition polymers, 474, 797 mesylates, 505–507 I-1 I-2 INDEX methanol, 493, 494, 500 Aldol reactions, synthetic applications of, ketones from, 720–721 nomenclature, 154–155, 490–491 859–860 Markovnikov additions, 341 oxidation of, 542–547 Aldonic acids, synthesis of, 980–981 regioselective reactions, 344 physical properties of, 492–494 Aldose, 968, 979, 980, 984, 986–987 Markovnikov’s rule, 340–345 primary, 67 Aldose, d-family of, 988 defined, 341 propylene glycols, 493, 495 Aldotetrose, 968–970, 987 theoretical explanation of, 342–343 reactions of, 498–499 Aliphatic aldehydes, 712 mechanism for syn dihydroxylation of, with hydrogen halides, alkyl halides nomenclature of, 712 368–369 from, 501–504 Aliphatic amines, reactions with nitrous in natural chemical syntheses, 381–382 with PBr3 or SOCI2, alkyl halides from, acid, 911 oxidation of, 369, 770 504–505 Aliphatic compounds, 618. See also Aromatic environmentally friendly by reduction of carbonyl compounds, compounds methods, 521 537–541 Aliphatic ketones, nomenclature of, 713 oxidative cleavage of, 371–373 spectroscopic evidence for, 547 Alkadienes, 582 physical properties of, 283 structure, 490–491 Alkaloids, 839, 887, 899 preparation of carboxylic acids by synthesis/reactions, 489–532 Alkanedioic acids, 765 oxidation of, 770 tert-butyl ethers by alkylation of, 511 Alkanes, 56–57, 145 properties/synthesis, 282–336 tosylates, 505–506 bicyclic, 181–182 radical addition to, 472–474 triflates, 505–506 branched-chain, 149 radical polymerization of, 474–478 Alcohol dehydrogenase, 539 nomenclature of, 147–149 rearrangements, 348–349 Aldaric acids, 981–982 chemical reactions of, 182 relative stabilities of, 284–287 Aldehydes, 55, 71–72, 711–760 chlorination of, 455–456 stereochemistry of the ionic addition to, acid-catalyzed halogenation of, 818 combustion of, 479, 481 326–327 α,β -unsaturated, additions to, 869–871 cycloalkanes, 145 stereospecific reactions, 363–364 Baeyer-Villiger oxidation, 741–743 defined, 145 synthesis of alcohols from, 496–499 base-promoted halogenation of, 817 halogenation of, 454–455, 466–467 use in synthesis, 524–525 carbonyl group, 535, 712 IUPAC nomenclature of, 147–149 Alkene diastereomers, (E )-(Z ) system for designating, 283–284 chemical analyses for, 743 multiple halogen substitution, 454–455 Alkenyl, 242, 274–275 from esters and nitriles, 718–720 no functional group, cause of, 64 Alkenylbenzenes, 686–687 IR spectra of, 743–744 nomenclature and conformations of, additions to the double bond of, 687 mass spectra of, 745–746 148–155 petroleum as source of, 145 formation of, by elimination NMR spectra of, 744–745 reactions, 687 physical properties of, 161–163 nomenclature of, 712–714 oxidation of the benzene ring, 688 polycyclic, 181–182 nucleophilic addition to the carbon– oxidation of the side chain, 688 oxygen double bond, 723–726 reactions of, with halogens, 454–456 Alkenyne, 582 oxidation of, 741 shapes of, 146–148 Alkoxides, 289, 500 by oxidation of 1° alcohols, 715–716 sources of, 145–146 Alkoxide ions, 136 oxidation of primary alcohols to, 542 “straight-chain,” 146 Alkoxyl group, 74 by ozonolysis of alkenes, 716 synthesis of, 182–184 Alkoxyl radicals, 449 unbranched, 148–149 in perfumes, 715 Alkoxymercuration–demercuration, synthesis physical properties of, 714–715 Alkanide shift, 310 of ethers by, 511 preparation of carboxylic acids by Alkatrienes, 582 Alkyl alcohols, 491 oxidation of, 770–773 Alkenes, 56, 57 Alkylation, of alkynide anions, 316–317, reduction by hydride transfer, 539 addition of sulfuric acid to, 338, 346 322–323, 336 by reduction of acyl chlorides, esters, and addition of water to, 346–349 Alkylbenzenes: nitriles, 716–718 mechanism, 338 conjugated, stability of, 687 relative reactivity, 725 addition reactions, 338–373 preparation of carboxylic acids by spectroscopic properties of, 743–746 alcohols from, through oxymercuration– oxidation of, 771 summary of addition reactions, 746–747 demercuration, 349–350 reactions of the side chain of, 686 synthesis of, 715–720 aldehydes by ozonolysis of, 716 Alkylboranes: Tollens’ test (silver mirror test), 743 anti 1,2-dihydroxylation of, 519–521 oxidation/hydrolysis of, 353–355 UV spectra, 746 defined, 145, 283 regiochemistry and stereochemistry, Aldehyde hydrates, 542 dipole moments in, 63–64 356–357 Alder, Kurt, 599, 608–609 electrophilic addition, 339–340 protonolysis of, 359 Alditols, 984 of bromine and chlorine, 359–363 Alkyl chlorides, 273 Aldol additions, 857–858 defined, 339 Alkyl chloroformates, 793–794 Aldol addition product, dehydration of, 858 of hydrogen halides, 340–345 Alkyl groups, 257 Aldol addition reactions, 856–857 functional group, 64 branched, nomenclature of, 151–152 Aldol condensations, 856, 858 halohydrin formation from, 364–366 and the symbol R, 64–65 acid-catalyzed, 858–859 heat of reaction, 285 unbranched, 149 crossed, 861–866 how to name, 158–160 nomenclature of, 149 cyclizations via, 867–868 hydrogenation of, 183–184, 317–318 Alkyl halides, 65–66, 240–243 Aldol condensation reactions, 850 ionic addition to, 343 alcohol reactions: INDEX I-3 with hydrogen halides, 501–504 stabilization of, by electron delocalization, heterocyclic, 892 with PBr3 or SOCI2, 504–505 468–469 basicity of, 895–896 conversion of alcohols into, 501 Allylic substitution, 466–469 infrared (IR) spectra of, 94–95 dehydrohalogenation of, 287–289 defined, 466 monoalkylation of, 906 bases used in, 289 Allyl radical, 573 nomenclature, 891–892 defined, 288–291 molecular orbital description of, 573 oxidation
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  • Organocuprate Aggregation and Reactivity: Decoding the 'Black Box'

    Organocuprate Aggregation and Reactivity: Decoding the 'Black Box'

    Dissertation zur Erlangung des Doktorgrades der Fakultät für Chemie und Pharmazie der Ludwig-Maximilians-Universität München Organocuprate Aggregation and Reactivity: Decoding the ‘Black Box’ Aliaksei Putau aus Vitebsk, Weißrussland 2012 Erklärung Diese Dissertation wurde im Sinne von § 7 der Promotionsordnung vom 28. November 2011 von Herrn Prof. Dr. Konrad Koszinowski betreut, und von Herrn Prof. Dr. Mayr von der Fakultät für Chemie und Pharmazie vertreten. Eidesstattliche Versicherung Diese Dissertation wurde selbständig, ohne unerlaubte Hilfe erarbeitet. München, 11.06.2012 _______________________ Aliaksei Putau Dissertation eingereicht am: 12.06.2012 1. Gutachter Prof. Dr. Herbert Mayr 2. Gutachter Prof. Dr. Konrad Koszinowski Mündliche Prüfung am: 20.07.2012 Acknowledgements It is a pleasure to thank the many people who made this project possible. My gratitude to my PhD supervisor, Prof. Dr. Konrad Koszinowski, is difficult to overstate. His sound advice, good company, and enthusiasm for trying new things ensured the tropical sunny climate in our group that is so necessary for fruitful (and, above all, enjoyable) research. Besides, his involvement in the group life outside the lab made all of us group members feel like team members, not just a loose bunch of colleagues. I am also deeply indebted to Prof. Dr. Herbert Mayr, not only for his continuous generous support and help, but also for running such a cool, all-star research group, which provided a great many social occasions. I thank SFB 749 for the financial support of this project, specifically Mrs. Birgit Carell, for her support and understanding of my worries and troubles of all kinds. Furthermore, my sincere gratitude goes to Prof.