791

Index

a – – pyridyldiimine-ligated Fe and Co complexes acceptor materials molecular design and 540–542 engineering 662 alkynylindoles 740 – fullerene-based acceptors 662–669 allenoates and electron-deficient , – non-fullerene-based acceptors 669–671 phosphine-catalyzed reaction mechanisms of acenes 760–761 574–577 Actinomycetales 157 Alstonia actinophylla 54 actinomycete bacteria 166 Alzheimer’s disease 785 actinophyllic acid 54–56 formation 506–508 Actinotalea fermentans 155 amination and halogenation, asymmetric acylimine and acyliminium 747 351–352 acyl transfer method 230 2-amino-2-deoxyglycosides 188 aerobic oxidation mechanistic study anion–π-interactions 529–530 – mechanistic characterization anomeric/gauche effect 414 – – kinetic investigations 629–634 anthradithiophene (ADT) 762 – recent progress 627–629 aplykurodinone-1 60–62 agelagalastatin 184 aqueous ascorbate procedure 253 agostic interaction 290 Arixtra (fondaparinux) 196 Agrobacterium sp. 194 aromatic hydrazide and oligomers aldol reaction 367–371 487–497 alkane metathesis 284 polymerization, cooperative in Arthrobacter protophormiae 205 393–394 arylamide oligomers alkene polymerization, novel catalysis for – flexible 492 537–538 – modified 494–497 – early transition metal complexes 544 arylazides 111 – – chelating bis(phenoxy)-ligated group 4 metal aryl dienyl ketones Nazarov cyclization complexes 549–551 mechanism 580–583 – – phenoxyimine-ligated group 4 metal ascorbate 252 complexes 544–549 Aspergillus fumigatus 46 – – pyridylamine-ligated Hf complexes aspidophytine 43 551–553 aspirin 714 – late transition metal complexes 538 asymmetric allylic alkylation (AAA) 344–345, – – diimine-ligated Ni and Pd complexes 346 538–540 asymmetric anti-Mannich reactions 588–590 – – phenoxyimine-ligated Ni complexes asymmetric organocatalysis 378, 379 542–544 – early status of 377–378

Organic Chemistry – Breakthroughs and Perspectives, First Edition. Edited by Kuiling Ding and Li-Xin Dai. © 2012 Wiley-VCH Verlag GmbH & Co. KGaA. Published 2012 by Wiley-VCH Verlag GmbH & Co. KGaA. 792 Index

automated microscope 96 – – carbohydrate-immune-adjuvant QS-21Aapi avidin 108–109 total synthesis 208 azide–alkyne cycloadditions 249–251 – – lipoteichoic acid total synthesis 210–212 – – lobatoside E total synthesis 208 b – – moenomycin A total synthesis 208–210 – chemical glycosylation 182–183 Bacillus licheniformis 194  Bacillus subtilis 167 ––with2-carboxybenzyl glycosides (CB Batis maritima 155 donors) 184, 185 Beilstein CrossFire 112 – – with glycosyl o-alkynylbenzoates 184, 186 benzamide foldamers 488–490 – – new methods for controlling benzo[1,2-b :3,4-b]dithiophene (BDT) 655 186–189 benzophenones 111 – – with PTFAI donors 183–184 β-mercaptoamino acids 231, 244 – enzymatic and chemoenzymatic methods 193–195 β-peptides 510–511 – heparin and heparan sulfate oligosaccharides biology and organic chemistry 783, see also 195–196 individual entries – – chemical synthesis 196–198 biomimetic C–H oxidation methods 312–315 – – enzymatic synthesis 198–200 biophysics and structural biology 236–237 – homogeneous glycoproteins synthesis 200, biotinylated probes 108–110 201 bipinnatin J 21–22 – – convergent glycopeptide synthesis coupled biyouyanagin A and analogs total synthesis and with native chemical ligation 200, 202 biological evaluation 15–18, 17 – – glycoproteins chemoenzymatic glycosylation bleomycin 151 remodeling 204–206 block conjugated copolymers 656, 658–660 – – site-selective glycosylation via protein ‘‘tag Broad Institute Chemical Biology Program 102 and modify’’ strategy 202–204 Brønsted acid–Lewis base 379 – oligosaccharide assembly new strategies bryostatins 10–11 – – automated synthesis 189–191 bulk heterojunction solar cells organic materials – – one-pot sequential glycosylations 192–193 and chemistry 643–645 carbonates 714–715 – acceptor materials molecular design and carbon–carbon bond formation, asymmetric engineering 662 336 – – fullerene-based acceptors 662–669 – allylic alkylations 344–345 – – non-fullerene-based acceptors 669–671 – asymmetric additions involving carbon – conjugated polymers molecular design and nucleophiles 337–341 engineering 645 – asymmetric catalysis – – block conjugated copolymers 656, 658–660 – – involving coupling processes 345–347 – – homopolymers 645–650 – – involving metathesis 348 – – with pendant conjugated side chains – asymmetric hydroformylations 336–337 655–656 – cycloadditions 341–344 – – push–pull copolymers 650–655 carbon dioxide 685–686 – – solution-processed small-molecule donor – as C1-building in C–C coupling reactions materials 660–662 702–703 – catalytic C–O bond formation utilizing c 703–704 C(sp3)–H cleavage early investigations – – cyclic carbonates synthesis 707–710 289–293 – – linear carbonates synthesis 704–707 Caenorhabditis elegans 96 – catalytic reductions to formic acid and calcineurin 113 methanol 686 Campylobacter jejuni 206 – – catalytic reduction to formic acid carbohydrate synthesis, towards glycobiology 695–702 181–182 – – catalytic reduction to methanol – carbohydrate-containing complex natural 691–695 compounds synthesis 206, 208 – – electrochemical reduction 686–689 Index 793

– – photochemical reduction 689–691 – target elucidation and validation 106 – current industrial processes using – – genetics-based approaches 114–116 710–711 – – hypothesis-driven approaches 112–114 – – carbonates 714–715 – – methods employing affinity chromatography – – carboxylic acids 713–714 106–108 ––methanol 713 – – urea 711–712 – – methods employing biotinylated probes carbon nucleophiles, asymmetric additions 108–110 involving 337 – – methods employing radiolabeled and – 1,2-additions 339 fluorescent and photoaffinity probes – 1,4-additions 340–341 110–112 – direct aldol and aldol type transformations chiral Brønsted acids 376–377 338–339 cholate oligomers 486–487, 512–514 carbon tunneling computational prediction click chemistry 247 566–568 carboxylic acids 713–714 click reaction, see click chemistry catalyst activator effect 547 CN-PPVs 669–670 C–C coupling reactions, CO2 as C1-building in C–O bond formation, utilizing CO2 703–704 702–703 – cyclic carbonates synthesis 707–710 CCL-5 derivative synthesis 240, 241 – linear carbonates synthesis 704–707 cDNA microarrays 114 communesin F 56, 58–59 central dogma 81 computational organic chemistry 561–563 CF -C bonds 3 – bifurcations on potential energy surfaces of – asymmetric CF3-C bond-forming reactions 437–443 organic reactions 563–566 – transition-metal-mediated aromatic – – carbon tunneling computational prediction trifluoromethylations 443–445 566–568 C–F bond formation reactions, novel – – contra-steric stereochemistry predictions in fluorinating reagents 416–428 cyclobutene ring-opening reactions chain walking polymerization 538 568–571 chelating bis(phenoxy)-ligated group 4 metal – ideal synthesis 583–586 complexes 549–551 – – catalysts discovery for 6π electrocyclizations ChemBank 102, 112 chemical biology 81–83, 121 586–588 – forward chemical genetics 88–89 – – chiral organocatalyst computational design – historical aspects 83–85 for asymmetric anti-Mannich reactions – scope 85–88 588–590 chemical genetics 86 – – gold-catalyzed cycloisomerization chemical libraries preparation 90, 121 computation-guided development – available 93–95 590–592 – diversity-oriented synthesis 92–93 – – Rh (I)-catalyzed cycloaddition for – natural product-inspired synthesis 90–92 chemical ligation 224, 225 cyclooctenones synthesis 593–595 chemical space and biological space, see also – reaction mechanisms 571–574 chemical biology; chemical libraries – – metal carbenoid O–H insertion mechanism preparation into water 577–580 – screening strategies 95 – – Nazarov cyclization mechanism of aryl – – binding assays 96–100 dienyl ketones 580–583 – – challenges in 100–102 – – phosphine-catalyzed reaction mechanisms – – chemical approaches to stem cell biology 103–106 of allenoates and electron-deficient – – data management and informatics analysis alkenes 574–577 102–103 conformation-directed cyclization 65 – – phenotypic assays 95–96 – cyclosporin and ramoplanin 65–69 794 Index

conjugated polymers molecular design and cyclopeptides 65, 66 engineering 645 cyclopropanation 341–342 – block conjugated copolymers 656, 658–660 cyclosporin 65–69 – homopolymers 645–650 – with pendant conjugated side chains d 655–656 density functional theory (DFT) 260, 562 – push–pull copolymers 650–655 diarylethenes 779 – solution-processed small-molecule donor diastereoselectivity 371 materials 660–662 diazirines 111 cooperative catalysis 385–387 2,3-dichloro-5,6-dicyanobenzoquinone (DDQ) – in alkene polymerization 393–394 733, 734 – in asymmetric reactions Diels–Alder reaction 342–343, 667 – – anion binding concept and 391–392 N,N-diethylaminosulfur trifluoride (DAST) – – catalyst higher order structure as function 419 determinant 389–391 difluoromethyl motifs, novel methods for 445 – – in twentieth century 387–389 – electrophilic difluoromethyl reagents and – in hydrogen activation and generation approaches 451–452 – – frustrated Lewis pairs 396–398 – nucleophilic difluoromethyl building blocks – – ligand–metal cooperation 394–396 and approaches 445–451 coordination bonds formation 503 dihydrojuenol 19 coralloidolide E 22 diimine-ligated Ni and Pd complexes 538–540 cortistatin A 11 dimethyl carbonate (DMC) 704–706, 715 cross-dehydrogenative coupling 729 dipropargylamines 747 – reaction of alkane C–H bonds diptericin 238 – – alkane alkylation (sp3 –sp3) 737 diversity-oriented synthesis (DOS) 2–3, – – alkane arylation (sp3 –sp2) 737–739 92–93 – reaction of allylic and benzylic C–H bonds – biomimetic 3–6, 5, 6 – – allylic alkylation (sp3 –sp3) 735–736 – of skeletally and stereochemically diverse – – benzylic alkylation (sp3 –sp3) 736–737 small molecules 3, 4 – – benzylic alkynylation (sp3 –sp) 736 diverted total synthesis (DTS) 7 – reaction of α-C–H bond of nitrogen in – of migrastatins 7–9, 8, 9 ––alkylation(sp3 –sp3) 732–734 domino process 36 ––alkynylation(sp3 –sp coupling) 730–732 – aspidophytine 43 – – arylation (sp3 –sp2 coupling) 732 – hirsutellone B total synthesis 36–40 – reaction of α-C–H bond of oxygen in ethers – minfiensine 40–41 (sp3 –sp3) 734–735 – phalarine 41–43 cryptophycin 91–92 domino reactions by catalysis 378 CuAAC 247–248 donor materials, solution-processed – azide–alkyne cycloadditions 249–251 small-molecule 660–662 – catalysts and ligands 251–258 Drosophila 96 – mechanistic aspects 258–263 DrugBank 102 – 1-iodoalkynes 264–266 drug western method 114 – reaction application examples 266 – – compound libraries synthesis for biological e screening 266–268 Ecteinascidia turbinate 35 – – copper-binding adhesives 268–269 ecteinascidin 743, 35 – sulfonyl azides reactions 269–270 – synthetic studies and biological evaluation – – 1-sulfonyl triazoles 271–272 13–15 cyclic carbonates synthesis 707–710 6π electrocyclizations 586–588 cyclobutene ring-opening reactions 568–571 electron donor–acceptor molecules 772 cyclodipeptides 147 electrophilic fluorinations 423–428 cyclometallation 305 electrophilic trifluoromethylating reagents and – C(aryl)–H functionalization via 288–289 reactions 433–437 cycloparaphenylenes 522–524 ELISA data manager 103 Index 795 enamine catalysis 367–374, 378 g endiandric acids 73 galanthamine-like molecules, biomimetic enediynes 136, 137 diversity-oriented synthesis of 3–6, 5,6 enolates 52 genetics-based approaches 114–116 Enterobacter 165 genome mining, for terpene biosynthesis epoxidation, asymmetric 351 160–162 erythromycin 75, 76 glycine peptoids, N-substituted 511–512 Escherichia coli 155, 167, 168, 198, 203, glycobiology, see carbohydrate synthesis, 206, 257 towards glycobiology ethylene copolymerization, with cyclic alkenes glycoproteins synthesis, homogeneous 200, 548 201 ethylene polymerization 544–545 – chemoenzymatic glycosylation remodeling ethylene–styrene copolymers 393 204–206 eudesmane terpenes total synthesis, by – convergent glycopeptide synthesis coupled site-selective C–H oxidations 19–21 with native chemical ligation 200, 202 eudesmantetraol 22 – site-selective glycosylation via protein ‘‘tag and expressed protein ligation 226–227 modify’’ strategy 202–204 glycorandomization method 194 f glycosidases 193 first functionalization 280, 293, 328 glycosylation – chemical, advances in 182–183 – alkane dehydrogenation 297–298  – alkane metathesis 298–300 ––with2-carboxybenzyl glycosides (CB – methane and higher n-alkanes selective donors) 184, 185 functionalization 294–296 – – with glycosyl o-alkynylbenzoates 184, 186 fischerindole 52,53 – – new methods for controlling fluorinated Ti-FI catalysts, living polymerization stereochemistry 186–189 546–547 – – with PTFAI donors 183–184 fluorine effects 414 – one-pot sequential 192–193 fluorobis(phenylsulfonyl)methane (FBSM) – remodeling, chemoenzymatic 204–206 454–455, 457–459 – site-selective, via protein ‘‘tag and modify’’ foldamers 479–480 strategy 202–204 glycosyl oxocarbenium ions 219 formic acid, CO2 catalytic reduction to 695–696 glycosyltransferases 193 – heterogeneous catalysis 696–697 gold-catalyzed cycloisomerization – homogeneous catalysis 697–702 computation-guided development 590–592 forward chemical genetics 86, 88–89 green chemistry 725, 726, 728, 755, 787 Friedel–Crafts reaction 23–24 green solvents 727 Frontier molecular orbital (FMO) 562, 563 frustrated Lewis pairs 396–398, 693 fullerene-based acceptors 662–669 h function-oriented synthesis (FOS) 9 Haemophilus influenza 182 – bryostatins 10–11 halogen bonding 528–529 – potent and practical antiangiogenic agents hapalindoles 52, 53 discovery and cortistatin A 11 heparin and heparan sulfate oligosaccharides furanocembranoids 21–22, 24 195–196 further functionalization 280, 293, 328 – chemical synthesis 196–198 – emerging metal-catalyzed methods – enzymatic synthesis 198–200 311–321 heparin pentasaccharide 197 – molecular complexity building using heteracalixaromatics 525–527 transition metal-mediated reactions 303 heteroaromatic amide foldamers 490–492 – philosophy 300–301 heterocyclic oligomers 484–486 – steroid functionalization using free radical hetero-Diels–Alder (HDA) 342–343 chemistry 301–303 heteropentacenes 762 796 Index

hexa-peri-hexabenzocoronenes (HBCs) 765, j 766 Journal of the American Chemical Society 92 hexathiapentacene 761 1-hexene selective production, by ethylene k trimerization 548–549 kinetically controlled ligation 234, 235 high-throughput assays 96–100, 99 13C kinetic isotopic effects (KIEs) 565, 567–568 high-throughput screening (HTS) 28 kinetics 604, 606, 612–615, 618–620, 622–624, Hirsutella nivea 36 626, 635 hirsutellone B total synthesis 36–40 – investigation hirsutine 50–52 – – according to aryl halide type 610–612 histone deacetylase inhibitors 784 – – aerobic oxidation and 629–634 homoduplex 497–499 Kolbe–Schmitt process 713 homopolymers 645–650 hydrazide foldamers 487–488 l hydrazides ligation, peptide 231 late metals 556 hydrocarbon chemistry challenges leucines 162 293–300 leukemia inhibitory factor (LIF) 104 hydrogenation, asymmetric 348–350 Lewis acid 587, 588 hydrogen bonding ligand design principles, for post-metallocenes – catalysis 378–379, 382 556–557 – quadruple 527–528 ligation–desulfurization approach 231 Hypericum chinese 15 linear carbonates synthesis 704–707 hyperolactone 16 lipitor (atorvastatin) 30 hypothesis-driven approaches 112–114 lipoteichoic acid total synthesis 210–212 liquid crystals (LCs) 765, 769 lobatoside E total synthesis 208 i ideal synthesis 583–586 m – catalysts discovery for 6π electrocyclizations macrocycles 65 586–588 – amides formation 506–508 – chiral organocatalyst computational design for – compounds 522–527 asymmetric anti-Mannich reactions – coordination bonds formation 503 588–590 – reversible and hydrazone bonds – gold-catalyzed cycloisomerization formation 508–509 computation-guided development – 1,2,3-triazoles formation 503–505 590–592 macromolecular self-assembly 514–516 – Rh (I)-catalyzed cycloaddition for magic bullet approach 84 cyclooctenones synthesis 593–595 367–374 idraparinux 196 medicinal chemistry 783 744 Mesorhizobium loti 157 iminium catalysis 378 metal carbenoid O–H insertion mechanism into iminium ions 744–747 water 577–580 52 metal-catalyzed asymmetric transformations indolocarbazoles 153 335 industrial processes, using CO2 – asymmetric carbon–carbon bond formation – carbonates 714–715 336 – carboxylic acids 713–714 – – allylic alkylations 344–345 – methanol 713 – – asymmetric additions involving carbon – urea 711–712 nucleophiles 337–341 insulin total synthesis 223–224 – – asymmetric catalysis involving coupling intein 227 processes 345–347 interleukin-2 239 – – asymmetric catalysis involving metathesis 1-iodoalkynes 264–266 348 isochromenes 742 – – asymmetric hydroformylations 336–337 Index 797

– – cycloadditions 341–344 native chemical ligation (NCL) 226, 244 – asymmetric oxidations 351 – convergent glycopeptide synthesis coupled – – asymmetric amination and halogenation with 200, 202 351–352 natural products 1–2, 125 – – asymmetric epoxidation 351 – diversity-oriented synthesis (DOS) 2–3 – asymmetric reductions 348 – – biomimetic 3–6, 5, 6 – – asymmetric hydrogenation 348–350 – – of skeletally and stereochemically diverse – – asymmetric transfer hydrogenation 350 small molecules 3, 4 metallocarbenoid insertion 315–318 – diverted total synthesis (DTS) 7 metallonitrenoid insertion 318–321 – – of migrastatins 7–9, 8, 9 methanol 713 – function-oriented synthesis (FOS) 9 –CO2 catalytic reduction to 691–692 – – bryostatins 10–11 – – enzymatic approaches 694–695 – – potent and practical antiangiogenic agents – – heterogeneous catalysis 692 discovery and cortistatin A 11 – – homogeneous catalysis 693–694 – -inspired synthesis 90–92 methyl halide transferases (MTHs) 155 – target-oriented synthesis (TOS) 11–13 migrastatins 7–9, 8, 9 – – biyouyanagin A and analogs total minfiensine 40–41 synthesis and biological evaluation moenomycin A total synthesis 208–210 15–18, 17 molecular recognition 480 – – diverse carbogenic complexity total – aromatic hydrazide and amide oligomers synthesis within resveratrol class 487–497 23–24, 25 – cholate oligomers 486–487 – – ecteinascidin 743 synthetic studies and – heterocyclic oligomers 484–486 biological evaluation 13–15 – m-phenyleneethnylene oligomers 480–483 – – eudesmane terpenes total synthesis by – naphthalene-incorporated ethylene glycol site-selective C–H oxidations 19–21 oligomers 483–484 – – furanocembranoids 21–22 molecular tweezers 494–497 – – vindoline total synthesis and structural molecular wire approach 779 analogs 18–19 monastrol 114 natural products, and synergy with synthetic monofluoromethylated organic molecules, methodology 33–35 catalytic asymmetric synthesis of chiral – conformation-directed cyclization 65 452–459 – – cyclosporin and ramoplanin 65–69 m-phenyleneethnylene oligomers 480–483 – domino process 36 Mucor hiemalis 205 – – aspidophytine 43 multicomponent reactions 43, 46 – – hirsutellone B total synthesis 36–40 – hirsutine 50–52 ––minfiensine 40–41 – spirotryprostatin B 46, 48–50 ––phalarine 41–43 multimolecular systems 785–787 – multicomponent reactions 43, 46 multiple fragment condensation 232–235 – – hirsutine 50–52 multiplexed automated genome engineering – – spirotryprostatin B 46, 48–50 (MAGE) 167 – oxidative anion coupling murine embryonic stem (mES) cells 104 – – actinophyllic acid 54–56 Mycobacterium tuberculosis 36 – – communesin F 56, 58–59 Myxococcus xanthus 168 – – direct coupling and total synthesis reactions 52–54 n – pattern recognition 60 naphthalene diimide (NDI) 768 – – aplykurodinone-1 60–62 naphthalene-incorporated ethylene glycol – – vinigrol 63–65 oligomers 483–484 N-benzyl α-peptides 503 National Cancer Institute Initiative for Chemical noncovalent interactions Genetics 102 –anion–π-interactions 529–530 National Center for Biotechnology Information – halogen bonding 528–529 (NCBI) 102 – quadruple hydrogen bonding 527–528 798 Index

non-fullerene-based acceptors 669–671 – actinophyllic acid 54–56 nonribosomal peptides (NRPs) 126 – communesin F 56, 58–59 – archetypical paradigms 139 – direct coupling, and total synthesis reactions – atypical paradigms 139–141, 142 52–54 – hybrid NRPS–PKS paradigms 141, 143 oxidative kinetic resolution (OKR) 511–512 n-type organic semiconductors 766–769 nucleolin 113 p nucleophilic addition of terminal alkynes in pathway engineering, see pharmaceutical water 741 natural products biosynthesis – acylimine and acyliminium Ions 747 pattern recognition 60 – direct conjugate addition of terminal alkynes – aplykurodinone-1 60–62 in water 748–749 – vinigrol 63–65 – imines 744 pentacene 761, 764, 773 – iminium ions 744–747 peptide–amide bond formation strategies – multiple and tandem addition of terminal 146–147 alkynes to C=N bonds 747–748 – terminal alkynes direct addition to ketones in peptides 90 water 743–744 periplanone B 73 – terminal alkynes direct nucleophilic addition perylenediimide (PDI) 660, 669 to 741–743 perylene diimide (PDI) 768 nucleophilic fluorinations 416–423 phage display 115 nucleophilic trifluoromethylating reagents, phalarine 41–43 trifluoromethyl-metal reagents, and chemical pharmaceutical natural products biosynthesis transformations 429–433 125–126 nucleus-independent chemical shift (NICS) – expanded paradigms in biosynthetic logic index 563 – – thio-template biosynthesis 126–146 – natural product biosynthesis research o 147–148 orbital symmetry conservation 562 – – comparative gene cluster analyses and organic field effect transistor (OFET) 761–762, biochemical characterization 148–151, 764, 767 152 organic photovoltaic (OPV) solar cells 643, 661, – – synthetic metagenomics for improved 676–678 methyl halide production 155–156 organic solar cells (OSCs) 768, 769, 770, 771, – – unique combinatorial strategies for different 773 pathways 151, 153–155 organocatalysis 588–590 – natural product production scope and diversity organofluorine chemistry 413–414 understanding 156–157 – fluorine-containing functionality synthetic – – cryptic gene cluster awakening 163–164 approaches 415–416 – – genome mining for terpene biosynthesis – – catalytic asymmetric synthesis of chiral 160–162 monofluoromethylated organic molecules – – genome sequencing, scanning, and 452–459 chemical potential screening 157–159 – – efficient trifluoroalkylation reactions – – genomisotopic approach for orphan gene 428–445 clusters 162–163 – – novel fluorinating reagents and C–F bond – – heterologous production 165–168 formation reactions 416–428 – – natural product pathways activation through – – novel methods for difluoromethyl motifs mixed culturing 164–165 445–452 – peptide–amide bond formation strategies organogels 499–500 146–147 oxidative addition phenoxyimine-ligated group 4 metal complexes – of haloarenes to trialkylphosphine–Pd(0) 544 complexes 608–615 – 1-hexene selective production, by ethylene – ligands influence on 605–608 trimerization 548–549 oxidative anion coupling – catalyst activator effect 547 Index 799

– ethylene copolymerization, with cyclic alkenes post-translational modifications 237–239 548 power conversion efficiency (PCE) 643, 668, – high activity for ethylene polymerization 677, 769 544–545 profiling technique 112 – living polymerization mediated by fluorinated -catalyzed Mannich reaction 367–374 Ti-FI catalysts 546–547 propargylamines 744 – propylene stereospecific polymerization propargylic alcohols 741 547–548 propylene stereospecific polymerization – wide-ranging control over the PE molecular 547–548 weight 545–546 prostaglandins 75 phenoxyimine-ligated Ni complexes 542–544 protein biopharmaceuticals 240–241 phosphonucleolin 113 protein chemical synthesis 221–222 photocrosslinking 111, 112 – applications photon harvesting 676 – – biophysics and structural biology 236–237 photophores 111 – – post-translational modifications photovoltaic materials 786 237–239 – organic π-conjugated molecules for 769–773 – – protein biopharmaceuticals 240–241 phthalascidin 14–15, 30 – – protein probes 239–240 physical chemistry 782–783 – current technology Pichia pastoris 206 – – cys limitation overcoming 231–232 π-conjugated molecules, organic 759–760 – – general protocol 227–228 – for n-type organic semiconductors 766–769 – – illustrative example 235–236 – for photovoltaic materials 769–773 – – multiple fragment condensation 232–235 – for p-type organic semiconductors 760–766 – – thioester synthesis 228–231 pillar[n]arenes 524–525 – history 222 platencin 148, 149 – – chemical ligation 224, 225 platensimycin 148, 149 – – expressed protein ligation 226–227 pluripotin 105 – – insulin total synthesis 223–224 pollution and toxicity 787–788 – – small peptides synthesis 222–223 poly(3-alkylthiophene)s (P3ATs) 647–650, 649 – – solid-phase peptide synthesis 224, 225 poly(3-hexylthiophene) (P3HT) 645, 647, 648, protein probes 239–240 650, 654, 655, 660, 667–669 protein splicing 227 poly(p-phenylenevinylene) (PPV) derivatives Pseudomonas aeruginosa 165 645–647, 668 Pseudomonas fluorescens 162 poly(thienylenevinylene) (PTVs) 679 p-type organic semiconductors, organic polyalkenes 537 π-conjugated molecules for 760–766 polycyclic aromatic hydrocarbons (PAHs) 765, PubChem 102, 112 766 pull-down approach 106 polyethylene 537 push–pull copolymers 650–655 – wide-ranging control over molecular weight pyridylamine-ligated Hf complexes 551–553 545–546 pyridyldiimine-ligated Fe and Co complexes polyketide synthases (PKS) 540–542 – ACP independent and noniterative type II pyrroles 52 138 – archetypical paradigms 126–129, 128 q – iterative type I, in bacteria 134–138 quantum chemistry (QC) 562 – modular type I, and broken colinearity rule quantum mechanics (QM) 561–562, 566 129, 130 – new enzymology complementing established r type 1 paradigms 129, 131, 132–134 radiolabeled and fluorescent and photoaffinity polypropylene (PP) 537 probes 110–112 polythiophene derivatives 647 ramoplanin 67 post-metallocene catalysts, see alkene rapamycin chemical modifications 91 polymerization, novel catalysis for reaction acceleration 497 800 Index

reaction mechanisms 571–574 Streptomyces coelicolor 157, 160, 162, 164, 167, – metal carbenoid O–H insertion mechanism 168 into water 577–580 Streptomyces flavoviridis 151 – Nazarov cyclization mechanism of aryl dienyl Streptomyces platensis 148 ketones 580–583 Streptomyces verticillus 151 – phosphine-catalyzed reaction mechanisms of Streptomycetes 166, 168 allenoates and electron-deficient alkenes structural analog design 19 574–577 structure–activity relationships (SARs) 94 – theory and 782 Strychnos minfiensis 40 reductive elimination sulfonyl azides reactions 269–270 – case study of oxidative coupling reaction – 1-sulfonyl triazoles 271–272 626–627 1-sulfonyl triazoles 271–272 – general aspects of 624–626 supercritical carbon dioxide (scCO2) 727 resveratrol class, diverse carbogenic complexity supramolecular liquid crystals 502 total synthesis within 23–24, 25 supramolecular organic chemistry 477–478 reverse chemical genetics 86–88 – catalysis 510 reverse vesicles 501 ––β-peptides 510–511 reverse water gas shift (RWGS) reaction 692 – – chiral n-substituted glycine peptoids reversible imine and hydrazone bonds 511–512 formation 508–509 – – cholate oligomers 512–514 Rh (I)-catalyzed cycloaddition, for – foldamers 479–480 cyclooctenones synthesis 593–595 – homoduplex 497–499 Rhodococcus sp 194 – macrocycles ribosomal paradigms of peptide natural – – amides formation 506–508 products 143– – – coordination bonds formation 503 rubifolide 22 – – reversible imine and hydrazone bonds ‘‘Rule-of-Five’’ 1, 28 formation 508–509 – – 1,2,3-triazoles formation 503–505 s – macromolecular self-assembly 514–516 Saccharomyces cerevisiae 155 – molecular recognition 480 Saccharopolyspora 157 – – aromatic hydrazide and amide oligomers saframycin 141, 142 487–497 Salinispora 157 – – cholate oligomers 486–487 schizophrenia 785 – – heterocyclic oligomers 484–486 sequential ligation – – m-phenyleneethnylene oligomers 480–483 – His tag-assisted 233 – – naphthalene-incorporated ethylene glycol – one-pot 233 oligomers 483–484 – solid phase 234 – organogels 499–500 small laboratory information management – supramolecular liquid crystals 502 system (SLIMS) 103 – vesicles 501 small-molecule microarrays 97, 98 Suzuki coupling 651, 652–653 small peptides synthesis 222–223 Synphonota geographica 60 solid-phase peptide synthesis (SPPS) 224, 225, synthetic chemistry, and sustainability 228–230, 238, 244, 245 725–726 Sorangium cellulosum 168 – chemical feedbacks 726–727 spirotryprostatin B 46, 48–50 – cross-dehydrogenative coupling 729 Staphylococcus aureus 92 – – reaction of alkane C–H bonds 737–739 steroid functionalization using free radical – – reaction of allylic and benzylic C–H bonds chemistry 301–303 735–737 Stille coupling 651, 654 – – reaction of aryl C–H bonds 739–740 Streptoalloteichus hindustanus 151 – – reactions of α-C–H bond of nitrogen in Streptococcus pneumoniae 210 amines 730–734 Streptomyces 7, 157, 166 – – reaction of α-C–H bond of oxygen in ethers Streptomyces avermitilis 156, 160, 162, 166, 167 (sp3 –sp3) 734–735 Index 801

– green solvents 727 – C(aryl)–H functionalization via – nucleophilic addition of terminal alkynes in cyclometallation 288–289 water 741 – C(sp3)–H cleavage early investigations – – acylimine and acyliminium ions 747 289–293 – – direct conjugate addition of terminal alkynes – catalytic, via metal insertion 303–311 in water 748–749 – challenges 281–282 ––imines 744 – cleavage mechanisms, by transition metals – – iminium ions 744–747 282–285 – – multiple and tandem addition of terminal – early work in metal-mediated C(aryl)–H alkynes to C=N bonds 747–748 cleavage 285–288 – – terminal alkynes direct addition to ketones – first functionalization 293 in water 743–744 – – alkane dehydrogenation 297–298 – – terminal alkynes direct nucleophilic addition – – alkane metathesis 298–300 to aldehydes 741–743 – – methane and higher n-alkanes selective – reactions 728–729 functionalization 294–296 synthetic reactions, case study of mechanisms in – further functionalization 603–604 – – emerging metal-catalyzed methods – aerobic oxidation mechanistic study 311–321 – – mechanistic characterization 629–634 – – molecular complexity building using – – recent progress 627–629 transition metal-mediated reactions 303 – coupling reactions mechanistic study – – philosophy 300–301 604–605 – – steroid functionalization using free radical – – oxidative addition 605–615 chemistry 301–303 – – reductive elimination 624–627 transition metal complexes 538 – – transmetallation 615–624 –early – – chelating bis(phenoxy)-ligated group 4 metal complexes 549–551 t – – phenoxyimine-ligated group 4 metal tagged library screening 107 complexes 544–549 tallysomycin 151 – – pyridylamine-ligated Hf complexes target-oriented synthesis (TOS) 11–13 551–553 – biyouyanagin A and analogs total synthesis –late and biological evaluation 15–18, 17 – – diimine-ligated Ni and Pd complexes – diverse carbogenic complexity total synthesis 538–540 within resveratrol class 23–24, 25 – – phenoxyimine-ligated Ni complexes – ecteinascidin 743 synthetic studies and 542–544 biological evaluation 13–15 – – pyridyldiimine-ligated Fe and Co complexes – eudesmane terpenes total synthesis by 540–542 site-selective C–H oxidations 19–21 transition states 563–564, 569 – furanocembranoids 21–22 transmetallation – vindoline total synthesis and structural – general aspects of 615–617 analogs 18–19 – in organozinc compounds coupling reaction Taxol (paclitaxel) 168 621–624 terpenoids 160, 161 – in Stille reaction 617–621 tetrathiafulvalene (TTF) 760 1,2,3-triazoles formation 503–505 therapeutic proteins 240 trifluoroalkylation reactions, efficient 428–429 thioester synthesis 228–231 –CF3-C bonds 437–445 thiol auxiliary method 231 – electrophilic trifluoromethylating reagents and thiopeptides 144–146 reactions 433–437 three-hybrid system 98 – nucleophilic trifluoromethylating reagents, torquoselectivity 568–569 trifluoromethyl-metal reagents, and transfer hydrogenation, asymmetric 350 chemical transformations 429–433 transition metal-catalyzed C–H triptolide 110 functionalization 279–280 tris(benzyltriazolyl)methylamine (TBTA) 257 802 Index

tropinone 46 vindoline total synthesis and structural tubulin 114 analogs 18–19 tumor-associated carbohydrate antigens vinigrol 63–65 (TACAs) 182 vinylcyclopropanes (VCPs) 593 Virgaria nigra F-5408 63 u urea 711–712 w uretupamine 98 water splitting 395, 396 welwitindolinone 52,53 v withaferin A 109 vancomycin 115 vesicles 501 z vinblastine 30 zorbamycin 151