Name Reactions

Jie Jack Li

Name Reactions

Fifth Edition

A Collection of Detailed Mechanismsand Synthetic Applications

ISBN 978-3-319-03978-7 ISBN 978-3-319-03979-4 (eBook)DOI 10.1007/978-3-319-03979-4Springer Cham Heidelberg New York Dordrecht London

Library of Congress Control Number: 2014930574

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CA, USA

Jie Jack LiDepartment of ChemistryCollege of Arts and SciencesUniversity of San FranciscoSan Francisco

To Prof. Claire Castro

Preface

Four years have gone by since the fourth edition was published and much has

happened since then. Professionally, I have moved from industry to academia to

teach organic and medicinal chemistry. This change is reflected in my choice to

include most of the basic name reactions so that this book will be useful for my

undergraduate students. I have also had the opportunity to make corrections to

several quinoline- and isoquinoline-related mechanisms. In addition, new name

reactions have emerged, and new references appeared for old name reactions. I

have added 27 new name reactions to reflect the latest developments in organic

chemistry and updated synthetic applications for each old name reaction. By

popular demand, a brief biographical description of the inventor of nearly everyname reaction has been added to this edition.

As in previous editions each reaction is delineated by its detailed step-by-step,

electron-pushing mechanism, supplemented with the original and the latest

references, especially review articles. Now, with the addition of many synthetic

applications, this book is not only an indispensable resource for senior undergradu-

ate and graduate students for learning mechanisms and the synthetic utility of name

reactions and preparing for their exams, but it is also a good reference book for all

organic chemists in both industry and academia.

the manuscript. I also wish to thank Prof. Neil K. Garg at UCLA and his students,

Grace Chiou, Adam Goetz, Liana Hie, Dr. Travis McMahon, Tejas Shah, Noah

Fine Nathel, Joel M. Smith, Amanda Silberstein, and Evan D. Styduhar for

proofreading the final version of the manuscript. Their knowledge and input have

tremendously enhanced the quality of this book. Any remaining errors are, of

course, solely my own responsibility.

ix

I wish to thank Dr. Jonathan W. Lockner at Scripps Research Institute and

Dr. Jun Cindy Shi of Bristol-Myers Squibb for their help in preparing and proofreading

As always, I welcome your critique! Please send your comments to this email

address: lijiejackli@gmail.com.

October 2013 Jie Jack Li

x Preface

San Francisco, CA

Table of Contents

Preface ..................................................................................................................... ix Abbreviations ........................................................................................................ xix Alder ene reaction .................................................................................................... 1 Aldol condensation ................................................................................................... 3 Algar–Flynn–Oyamada reaction .............................................................................. 6 Allan–Robinson reaction .......................................................................................... 8 Arndt–Eistert homologation ................................................................................... 10 Baeyer–Villiger oxidation ...................................................................................... 12 Baker–Venkataraman rearrangement ..................................................................... 14 Bamford–Stevens reaction ..................................................................................... 16 Baran reagents ........................................................................................................ 18 Barbier reaction ...................................................................................................... 21 Bargellini reaction .................................................................................................. 23 Bartoli indole synthesis .......................................................................................... 24 Barton radical decarboxylation .............................................................................. 26 Barton–McCombie deoxygenation ........................................................................ 28 Barton nitrite photolysis ......................................................................................... 30 Barton–Zard reaction .............................................................................................. 32 Batcho–Leimgruber indole synthesis ..................................................................... 34 Baylis–Hillman reaction ......................................................................................... 36 Beckmann rearrangement ....................................................................................... 39 Abnormal Beckmann rearrangement ............................................................ 40 Beirut reaction ........................................................................................................ 42 Benzilic acid rearrangement ................................................................................... 44 Benzoin condensation ............................................................................................. 46 Bergman cyclization ............................................................................................... 48 Biginelli reaction .................................................................................................... 50 Birch reduction ....................................................................................................... 52 Bischler–Möhlau indole synthesis ......................................................................... 54

xi

Bischler–Napieralski reaction ................................................................................ 56 Blaise reaction ....................................................................................................... 58 Blum–Ittah aziridine synthesis .............................................................................. 60 Boekelheide reaction .............................................................................................. 62 Boger pyridine synthesis ........................................................................................ 64 Borch reductive amination ..................................................................................... 66 Borsche–Drechsel cyclization ................................................................................ 68 Boulton–Katritzky rearrangement .......................................................................... 70 Bouveault aldehyde synthesis ................................................................................ 72 Bouveault–Blanc reduction .................................................................................... 74 Boyland–Sims oxidation ........................................................................................ 75 Elbs oxidation ................................................................................................ 76 Bradsher reaction .................................................................................................... 77 Brook rearrangement .............................................................................................. 79 Brown hydroboration ............................................................................................. 81 Bucherer carbazole synthesis ................................................................................. 83 Bucherer reaction ................................................................................................... 85 Bucherer–Bergs reaction ........................................................................................ 87 Büchner ring expansion .......................................................................................... 89 Buchwald–Hartwig amination ............................................................................... 91 Burgess reagent ...................................................................................................... 95 Burke boronates ...................................................................................................... 97 Cadiot–Chodkiewicz coupling ............................................................................. 100 Cadogan–Sundberg indole synthesis .................................................................... 102 Camps quinoline synthesis ................................................................................... 104 Cannizzaro reaction .............................................................................................. 106 Carroll rearrangement .......................................................................................... 108 Castro–Stephens coupling .................................................................................... 110 C H activation ..................................................................................................... 112 Catellani reaction ......................................................................................... 112 Sanford reaction .......................................................................................... 115 White catalyst .............................................................................................. 117 Yu C H activation ...................................................................................... 121 Chan alkyne reduction .......................................................................................... 123 Chan–Lam C–X coupling reaction ....................................................................... 125 Chapman rearrangement ...................................................................................... 128 Chichibabin pyridine synthesis ............................................................................ 130

Ciamician–Dennsted rearrangement .................................................................... 135 Claisen condensation ............................................................................................ 136 Claisen isoxazole synthesis .................................................................................. 138 Claisen rearrangements ........................................................................................ 140 para-Claisen rearrangement ........................................................................ 142 Abnormal Claisen rearrangement ............................................................... 144

Chugaev elimination ............................................................................................ 133

xii Table of Contents

Eschenmoser–Claisen amide acetal rearrangement .................................... 146 Ireland–Claisen (silyl ketene acetal) rearrangement ................................... 148 Johnson–Claisen (orthoester) rearrangement .............................................. 150 Clemmensen reduction ......................................................................................... 153 Combes quinoline synthesis ................................................................................. 155 Conrad–Limpach reaction .................................................................................... 157 Cope elimination reaction .................................................................................... 159 Cope rearrangement ............................................................................................. 161 Anionic oxy-Cope rearrangement ............................................................... 163 Oxy-Cope rearrangement ............................................................................ 164 Siloxy-Cope rearrangement ......................................................................... 166 Corey–Bakshi–Shibata (CBS) reagent ................................................................. 168 Corey Chaykovsky reaction ................................................................................ 171 Corey–Fuchs reaction ........................................................................................... 174 Corey–Kim oxidation ........................................................................................... 176 Corey–Nicolaou macrolactonization .................................................................... 178 Corey–Seebach reaction ....................................................................................... 180 Corey–Winter olefin synthesis ............................................................................. 182 Criegee glycol cleavage ........................................................................................ 185 Criegee mechanism of ozonolysis ........................................................................ 187 Curtius rearrangement .......................................................................................... 188 Dakin oxidation .................................................................................................... 190 Dakin–West reaction ............................................................................................ 192 Danheiser annulation ............................................................................................ 194 Darzens condensation ........................................................................................... 196 Delépine amine synthesis ..................................................................................... 198 de Mayo reaction .................................................................................................. 200 Demjanov rearrangement ..................................................................................... 202 Tiffeneau–Demjanov rearrangement ........................................................... 203 Dess–Martin periodinane oxidation ..................................................................... 206 Dieckmann condensation ..................................................................................... 209 Diels–Alder reaction ............................................................................................. 211 Inverse electronic demand Diels–Alder reaction ........................................ 213 Hetero-Diels–Alder reaction ....................................................................... 215 Dienone–phenol rearrangement ........................................................................... 217 Doebner quinoline synthesis ................................................................................ 219 Doebner–von Miller reaction ............................................................................... 221 Dötz reaction ........................................................................................................ 223 Dowd–Beckwith ring expansion .......................................................................... 225 Dudley reagent ..................................................................................................... 227 Erlenmeyer Plöchl azlactone synthesis ............................................................... 229 Eschenmoser’s salt ............................................................................................... 231 Eschenmoser–Tanabe fragmentation ................................................................... 233 Eschweiler–Clarke reductive alkylation of amines .............................................. 235

xiiiTable of Contents

Evans aldol reaction ............................................................................................. 237 Favorskii rearrangement ....................................................................................... 239 Quasi-Favorskii rearrangement ................................................................... 242 Feist–Bénary furan synthesis ............................................................................... 243 Ferrier carbocyclization ........................................................................................ 245 Ferrier glycal allylic rearrangement ..................................................................... 247 Fiesselmann thiophene synthesis ......................................................................... 250 Fischer–Speier esterification ................................................................................ 252 Fischer indole synthesis ....................................................................................... 253 Fischer oxazole synthesis ..................................................................................... 255 Fleming–Kumada oxidation ................................................................................. 257 Tamao Kumada oxidation .......................................................................... 259 Friedel–Crafts reaction ......................................................................................... 260 Friedel–Crafts acylation reaction ................................................................ 260 Friedel–Crafts alkylation reaction ............................................................... 262 Friedländer quinoline synthesis ............................................................................ 264 Fries rearrangement .............................................................................................. 266 Fukuyama amine synthesis .................................................................................. 268 Fukuyama reduction ............................................................................................. 270 Gabriel synthesis .................................................................................................. 272 Ing–Manske procedure ................................................................................ 273 Gabriel–Colman rearrangement ........................................................................... 275 Gassman indole synthesis .................................................................................... 276 Gattermann–Koch reaction .................................................................................. 278 Gewald aminothiophene synthesis ....................................................................... 279 Glaser coupling .................................................................................................... 282 Eglinton coupling ........................................................................................ 284 Gomberg–Bachmann reaction .............................................................................. 287 Gould–Jacobs reaction ......................................................................................... 289 Grignard reaction .................................................................................................. 291 Grob fragmentation .............................................................................................. 293 Guareschi–Thorpe condensation .......................................................................... 295 Hajos–Wiechert reaction ...................................................................................... 297 Haller–Bauer reaction .......................................................................................... 299 Hantzsch dihydropyridine synthesis .................................................................... 300 Hantzsch pyrrole synthesis ................................................................................... 302 Heck reaction ........................................................................................................ 304 Heteroaryl Heck reaction ............................................................................ 307 Hegedus indole synthesis ..................................................................................... 309 Hell–Volhard–Zelinsky reaction .......................................................................... 310 Henry nitroaldol reaction ..................................................................................... 312 Hinsberg synthesis of thiophenes ......................................................................... 314 Hiyama cross-coupling reaction ........................................................................... 316 Hofmann elimination ............................................................................................ 318

xiv Table of Contents

Hofmann rearrangement ....................................................................................... 319 Hofmann–Löffler–Freytag reaction ..................................................................... 321 Horner–Wadsworth–Emmons reaction ................................................................ 323 Houben–Hoesch reaction ..................................................................................... 325 Hunsdiecker–Borodin reaction ............................................................................. 327 Jacobsen–Katsuki epoxidation ............................................................................. 329 Japp–Klingemann hydrazone synthesis ............................................................... 331 Jones oxidation ..................................................................................................... 333 Collins oxidation ......................................................................................... 335 PCC oxidation ............................................................................................. 336 PDC oxidation ............................................................................................. 337 Julia–Kocienski olefination .................................................................................. 338 Julia–Lythgoe olefination ..................................................................................... 340 Kahne glycosidation ............................................................................................. 342 Knoevenagel condensation ................................................................................... 344 Knorr pyrazole synthesis ...................................................................................... 347 Koch–Haaf carbonylation ..................................................................................... 349 Koenig–Knorr glycosidation ................................................................................ 350 Kostanecki reaction .............................................................................................. 353 Kröhnke pyridine synthesis .................................................................................. 354 Krapcho reaction .................................................................................................. 356 Kumada cross-coupling reaction .......................................................................... 357 Lawesson’s reagent .............................................................................................. 360 Leuckart–Wallach reaction ................................................................................... 362 Li A3 reaction ....................................................................................................... 364 Lossen rearrangement ........................................................................................... 367 McFadyen–Stevens reduction .............................................................................. 369 McMurry coupling ............................................................................................... 370 MacMillan catalyst ............................................................................................... 372 Mannich reaction .................................................................................................. 374 Markovnikov’s rule .............................................................................................. 376 Anti-Markovnikov ....................................................................................... 377 Martin’s sulfurane dehydrating reagent ............................................................... 379 Masamune–Roush conditions for the Horner–Emmons reaction ........................ 382 Meerwein’s salt .................................................................................................... 384 Meerwein–Ponndorf–Verley reduction ................................................................ 386 Meisenheimer complex ........................................................................................ 388 [1,2]-Meisenheimer rearrangement ...................................................................... 390 [2,3]-Meisenheimer rearrangement ...................................................................... 391 Meyers oxazoline method .................................................................................... 393 Meyer–Schuster rearrangement ............................................................................ 395 Michael addition ................................................................................................... 397 Michaelis–Arbuzov phosphonate synthesis ......................................................... 399 Midland reduction ................................................................................................ 401

xvTable of Contents

Minisci reaction .................................................................................................... 403 Mislow–Evans rearrangement .............................................................................. 405 Mitsunobu reaction ............................................................................................... 407 Miyaura borylation ............................................................................................... 409 Moffatt oxidation .................................................................................................. 411 Morgan–Walls reaction ........................................................................................ 413 Pictet–Hubert reaction ................................................................................. 413 Mori–Ban indole synthesis ................................................................................... 415 Mukaiyama aldol reaction .................................................................................... 417 Mukaiyama Michael addition .............................................................................. 419 Mukaiyama reagent .............................................................................................. 421 Myers Saito cyclization ....................................................................................... 423 Nazarov cyclization .............................................................................................. 424 Neber rearrangement ............................................................................................ 426 Nef reaction .......................................................................................................... 428 Negishi cross-coupling reaction ........................................................................... 430 Nenitzescu indole synthesis ................................................................................. 432 Newman Kwart rearrangement ........................................................................... 434 Nicholas reaction .................................................................................................. 436 Nicolaou IBX dehydrogenation ........................................................................... 438 Noyori asymmetric hydrogenation ....................................................................... 440 Nozaki–Hiyama–Kishi reaction ........................................................................... 443 Nysted reagent ...................................................................................................... 445 Oppenauer oxidation ............................................................................................ 447 Overman rearrangement ....................................................................................... 449 Paal thiophene synthesis ...................................................................................... 451 Paal–Knorr furan synthesis .................................................................................. 452 Paal–Knorr pyrrole synthesis ............................................................................... 454 Parham cyclization ............................................................................................... 456 Passerini reaction .................................................................................................. 458 Paternó–Büchi reaction ........................................................................................ 460 Pauson–Khand reaction ........................................................................................ 462 Payne rearrangement ............................................................................................ 464 Pechmann coumarin synthesis ............................................................................. 466 Perkin reaction ...................................................................................................... 468 Perkow vinyl phosphate synthesis ....................................................................... 470 Petasis reaction ..................................................................................................... 472 Petasis reagent ...................................................................................................... 474 Peterson olefination .............................................................................................. 476 Pictet–Gams isoquinoline synthesis ..................................................................... 478 Pictet–Spengler tetrahydroisoquinoline synthesis ............................................... 480 Pinacol rearrangement .......................................................................................... 482 Pinner reaction ...................................................................................................... 484 Polonovski reaction .............................................................................................. 486

x iv Table of Contents

Polonovski–Potier reaction ................................................................................... 488 Pomeranz–Fritsch reaction ................................................................................... 490 Schlittler–Müller modification .................................................................... 492 Pavorov reaction ................................................................................................... 493 Prévost trans-dihydroxylation .............................................................................. 495 Prins reaction ........................................................................................................ 496 Pschorr cyclization ............................................................................................... 499 Pummerer rearrangement ..................................................................................... 501 Ramberg–Bäcklund reaction ................................................................................ 503 Reformatsky reaction ........................................................................................... 505 Regitz diazo synthesis .......................................................................................... 507 Reimer–Tiemann reaction .................................................................................... 509 Reissert reaction ................................................................................................... 510 Reissert indole synthesis ...................................................................................... 512 Ring-closing metathesis (RCM) ........................................................................... 514 Ritter reaction ....................................................................................................... 517 Robinson annulation ............................................................................................. 519 Robinson–Gabriel synthesis ................................................................................. 521 Robinson–Schöpf reaction ................................................................................... 523 Rosenmund reduction ........................................................................................... 525 Rubottom oxidation .............................................................................................. 527 Rupe rearrangement ............................................................................................. 529 Saegusa oxidation ................................................................................................. 531 Sakurai allylation reaction .................................................................................... 533 Sandmeyer reaction .............................................................................................. 535 Schiemann reaction .............................................................................................. 537 Schmidt rearrangement ......................................................................................... 539 Schmidt’s trichloroacetimidate glycosidation ...................................................... 541 Scholl reaction ...................................................................................................... 543 Shapiro reaction .................................................................................................... 544 Sharpless asymmetric amino hydroxylation ........................................................ 546 Sharpless asymmetric dihydroxylation ................................................................ 549 Sharpless asymmetric epoxidation ....................................................................... 552 Sharpless olefin synthesis ..................................................................................... 555 Shi asymmetric epoxidation ................................................................................. 557 Simmons–Smith reaction ..................................................................................... 560 Skraup quinoline synthesis ................................................................................... 562 Smiles rearrangement ........................................................................................... 564 Truce Smile rearrangement ........................................................................ 566 Sommelet reaction ................................................................................................ 568 Sommelet–Hauser rearrangement ........................................................................ 570 Sonogashira reaction ............................................................................................ 572 Staudinger ketene cycloaddition .......................................................................... 574 Staudinger reduction ............................................................................................. 576

x iivTable of Contents

Stetter reaction ...................................................................................................... 578 Stevens rearrangement ......................................................................................... 580 Still–Gennari phosphonate reaction ..................................................................... 582 Stille coupling ...................................................................................................... 584 Stille–Kelly reaction ............................................................................................. 586 Stobbe condensation ............................................................................................. 587 Stork–Danheiser transposition ............................................................................. 589 Strecker amino acid synthesis .............................................................................. 591 Suzuki–Miyaura coupling .................................................................................... 593 Swern oxidation .................................................................................................... 595 Takai reaction ....................................................................................................... 597 Tebbe reagent ....................................................................................................... 599 TEMPO oxidation ................................................................................................ 601 Thorpe Ziegler reaction ....................................................................................... 603 Tsuji–Trost reaction ............................................................................................. 605 Ugi reaction .......................................................................................................... 608 Ullmann coupling ................................................................................................. 611 van Leusen oxazole synthesis .............................................................................. 613 Vilsmeier–Haack reaction .................................................................................... 615 Vinylcyclopropane cyclopentene rearrangement ................................................ 617 von Braun reaction ............................................................................................... 619 Wacker oxidation ................................................................................................. 620 Wagner–Meerwein rearrangement ....................................................................... 622 Weiss–Cook condensation ................................................................................... 624 Wharton reaction .................................................................................................. 626 Williamson ether synthesis .................................................................................. 628 Willgerodt–Kindler reaction ................................................................................ 629 Wittig reaction ...................................................................................................... 632 Schlosser modification of the Wittig reaction ............................................. 634 [1,2]-Wittig rearrangement .................................................................................. 636 [2,3]-Wittig rearrangement .................................................................................. 638 Wohl–Ziegler reaction .......................................................................................... 640 Wolff rearrangement ............................................................................................ 642 Wolff–Kishner reduction ..................................................................................... 644 Woodward cis-dihydroxylation ............................................................................ 646 Yamaguchi esterification ..................................................................................... 648 Zaitsev’s elimination rule ..................................................................................... 650 Zhang enyne cycloisomerization ......................................................................... 652 Zimmerman rearrangement .................................................................................. 654 Zincke reaction ..................................................................................................... 656 Zinin benzidine (semidne) rearrangement ........................................................... 659 Index ..................................................................................................................... 661

x ivii Table of Contents

Abbreviations and Acronyms

Polymer support

(DHQ)2-PHAL 1,4-bis(9-O-Dihydroquinine)-phthalazine(DHQD)2-PHAL 1,4-bis(9-O-Dihydroquinidine)-phthalazine[bimim]Cl•2AlCl3 1-Butyl-3-methylimidazolium chloroaluminuminate

3CC Three-component condensation

4CC Four-component condensation

9-BBN 9-Borabicyclo[3.3.1]nonane

A Adenosine

Ac Acetyl

ADDP 1,10-(azodicarbonyl)dipiperidineAIBN 2,20-azobisisobutyronitrileAlpine-borane® B-isopinocampheyl-9-borabicyclo[3.3.1]-nonane

AOM p-Anisyloxymethyl ¼ p-MeOC6H4OCH2-

Ar Aryl

B: Generic base

BINAP 2,20-bis(Diphenylphosphino)-1,10-binaphthylBn Benzyl

Boc tert-ButyloxycarbonylBQ Benzoquinone

BT Benzothiazole

Bz Benzoyl

Cbz Benzyloxycarbonyl

CuTC Copper thiophene-2-carboxylate

DABCO 1,4-Diazabicyclo[2.2.2]octane

dba Dibenzylideneacetone

DBU 1,8-Diazabicyclo[5.4.0]undec-7-ene

DCC 1,3-Dicyclohexylcarbodiimide

DDQ 2,3-Dichloro-5,6-dicyano-1,4-benzoquinone

xix

Δ Solvent heated under reflux

de Diastereoselctive excess

DEAD Diethyl azodicarboxylate

DIAD Diisopropyl azodidicarboxylate

DIBAL Diisobutylaluminum hydride

DIPEA Diisopropylethylamine

DMA N,N-dimethylacetamide

DMAP 4-N,N-dimethylaminopyridine

DME 1,2-Dimethoxyethane

DMF N,N-dimethylformamide

DMFDMA N,N-dimethylformamide dimethyl acetal

DMS Dimethylsulfide

DMSO Dimethylsulfoxide

DMSY Dimethylsulfoxonium methylide

DMT Dimethoxytrityl

DPPA Diphenylphosphoryl azide

dppb 1,4-bis(Diphenylphosphino)butanedppe 1,2-bis(Diphenylphosphino)ethanedppf 1,10-bis(Diphenylphosphino)ferrocenedppp 1,3-bis(Diphenylphosphino)propanedr Diastereoselctive ratio

DTBAD Di-tert-butylazodicarbonateDTBMP 2,6-Di-tert-butyl-4-methylpyridine

E1 Unimolecular elimination

E1cB 2-Step, base-induced β-elimination via carbanion

E2 Bimolecular elimination

EAN Ethylammonium nitrate

EDCI 1-Ethyl-3-(3-dimethylaminopropyl)carbodiimide

EDDA Ethylenediamine diacetate

ee Enantiomeric excess

Ei Two groups leave at about the same time and bond to

each other as they are doing so

Eq Equivalent

Et Ethyl

EtOAc Ethyl acetate

HMDS Hexamethyldisilazane

HMPA Hexamethylphosphoramide

HMTA Examethylenetetramine

HMTTA 1,1,4,7,10,10-Hexamethyltriethylenetetramine

IBX o-iodoxybenzoic acidImd Imidazole

KHMDS Potassium hexamethyldisilazide

LAH Lithium aluminum hydride

LDA Lithium diisopropylamide

LHMDS Lithium hexamethyldisilazide

xx Abbreviations and Acronyms

LTMP Lithium 2,2,6,6-tetramethylpiperidide

M Metal

m-CPBA m-chloroperoxybenzoic acidMCRs Multicomponent reactions

Mes Mesityl

MPM Methyl phenylmethyl

MPS Morpholine-polysulfide

Ms Methanesulfonyl

MTBE Methyl tertiary butyl ether

MVK Methyl vinyl ketone

MWI Microwave irradiation

NBS N-bromosuccinimide

NCS N-chlorosuccinimide

NIS N-iodosuccinimide

NMP 1-Methyl-2-pyrrolidinone

Nos Nosylate (4-nitrobenzenesulfonyl)

N-PSP N-phenylselenophthalimide

N-PSS N-phenylselenosuccinimide

Nu Nucleophile

PCC Pyridinium chlorochromate

PDC Pyridinium dichromate

PE Premature ejaculation

Piv Pivaloyl

PMB para-Methoxybenzyl

PPA Polyphosphoric acid

PPTS Pyridinium p-toluenesulfonatePT Phenyltetrazolyl

PyPh2P Diphenyl 2-pyridylphosphine

Pyr Pyridine

Red-Al Sodium bis(methoxy-ethoxy)aluminum hydride

Red-Al Sodium bis(methoxy-ethoxy)aluminum hydride (SMEAH)

Salen N,N0-disalicylidene-ethylenediamine

SET Single electron transfer

SIBX Stabilized IBX

SM Starting material

SMEAH Sodium bis(methoxy-ethoxy)aluminum hydride

SN1 Unimolecular nucleophilic substitution

SN2 Bimolecular nucleophilic substitution

SNAr Nucleophilic substitution on an aromatic ring

SSRI Selective serotonin reuptake inhibitor

TBABB tetra-n-butylammonium bibenzoate

TBAF tetra-n-butylammonium fluoride

TBAO 1,3,3-Trimethyl-6-azabicyclo[3.2.1]octane

TBDMS tert-Butyldimethylsilyl

xxiAbbreviations and Acronyms

TBDPS tert-ButyldiphenylsilylTBS tert-Butyldimethylsilyl

t-Bu tert-ButylTDS Thexyldimethylsilyl

TEA Triethylamine

TEMPO 2,2,6,6-Tetramethylpiperidinyloxy

TEOC Trimethysilylethoxycarbonyl

Tf Trifluoromethanesulfonyl (triflyl)

TFA Trifluoroacetic acid

TFAA Trifluoroacetic anhydride

TFP Tri-2-furylphosphine

THF Tetrahydrofuran

TIPS Triisopropylsilyl

TMEDA N,N,N0,N0-tetramethylethylenediamine

TMG 1,1,3,3-Tetramethylguanidine

TMP Tetramethylpiperidine

TMS Trimethylsilyl

TMSCl Trimethylsilyl chloride

TMSCN Trimethylsilyl cyanide

TMSI Trimethylsilyl iodide

TMSOTf Trimethylsilyl triflate

Tol Toluene or tolyl

Tol-BINAP 2,20-bis(di-p-tolylphosphino)-1,10-binaphthylTosMIC ( p-tolylsulfonyl)methyl isocyanide

Ts Tosyl

TsO Tosylate

UHP Urea-hydrogen peroxide

xxii Abbreviations and Acronyms