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- Herausgeber: John Wiley & Sons
- Kategorie: Wissenschaft und neue Technologien
- Sprache: Englisch
From Boron Trifluoride to Zinc, the 52 most widely used reagents in organic synthesis are described in this unique desktop reference for every organic chemist. The list of reagents contains classics such as N-Bromosuccinimide (NBS) and Trifluoromethanesulfonic Acid side by side with recently developed ones like Pinacolborane and Tetra-n-propylammonium Perruthenate (TPAP). For each reagent, a concise article provides a brief description of all important reactions for which the reagent is being used, including yields and reaction conditions, an overview of the physical properties of the reagent, its storage conditions, safe handling, laboratory synthesis and purification methods. Advantages and disadvantages of the reagent compared to alternative synthesis methods are also discussed. Reagents have been hand-picked from among the 5000 reagents contained in EROS, the Encyclopedia of Reagents for Organic Synthesis. Every organic chemist should be familiar with these key reagents that can make almost every reaction work.
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Contents
Cover
e-EROS Editorial Board
Title Page
Copyright
Preface
Short Note on InChIs and InChIKeys
General Abbreviations
Bis(dibenzylideneacetone)palladium(0)
Original Commentary
First Update
Second Update
9-Borabicyclo[3.3.1]nonane Dimer
Original Commentary
Boron Trifluoride Etherate
N-Bromosuccinimide
Original Commentary
First Update
n-Butyllithium
Original Commentary
First Update
N,N′-Carbonyl Diimidazole
Original Commentary
First Update
Cerium (IV) Ammonium Nitrate
Original Commentary
First Update
m-Chloroperbenzoic Acid
Original Commentary
First Update
N-Chlorosuccinimide
Original Commentary
First Update
Second Update
Chlorotrimethylsilane
Original Commentary
First Update
Chlorotris(triphenylphosphine)-rhodium(I)
Original Commentary
First Update
(Diacetoxyiodo)benzene
Original Commentary
First Update
Diazomethane
Methylation of Heteroatoms
Esterification of Carboxylic Acids and Other Acidic Functional Groups
Methylation of Alcohols and Other Less Acidic Functional Groups
The Arndt–Eistert Synthesis
Other Reactions of α-Diazo Ketones Derived from Diazomethane
The Vinylogous Wolff Rearrangement
Insertions into Aldehyde C–H Bonds
Additions to Ketones
Cycloadditions with Diazomethane
Additions to Electron-Deficient Species
Miscellaneous Reactions
Related Reagents
2,3-Dichloro-5,6-dicyano-1,4-benzo-quinone
Original Commentary
First Update
Diisobutylaluminum Hydride
Original Commentary
First Update
4-Dimethylaminopyridine
Original Commentary
First Update
Dimethyldioxirane
Original Commentary
First Update
1-Ethyl-3-(3′-dimethylaminopropyl)carbodiimide Hydrochloride
Peptide Coupling Reagent
Amide Formation
Ester Formation
Protein Modification
Oxidation of Primary Alcohols
Miscellaneous Reactions
Related Reagents
N-Iodosuccinimide
Original Commentary
First Update
Second Update
Iodotrimethylsilane
Original Commentary
First Update
2-Iodoxybenzoic acid
Lithium Aluminum Hydride
Original Commentary
First Update
Lithium Diisopropylamide1, 2
Original Commentary
First Update
Lithium Naphthalenide
Original Commentary
Manganese Dioxide
Osmium Tetroxide
First Update
Second Update
Oxalyl Chloride
Original Commentary
First Update
Oxalyl Chloride–Dimethylformamide
Ozone
Original Commentary
First Update
Pinacolborane
Original Commentary
First Update
Potassium Hexamethyldisilazide
Original Commentary
First Update
Second Update
Potassium Monoperoxysulfate
Original Commentary
First Update
Second Update
Potassium tert-Butoxide
Original Commentary
First Update
Ruthenium(II), Tris(2,2′-bipyridine-κN1,κN1′)-, (OC-6-11)-
Samarium(II) Iodide
Original Commentary
First Update
Scandium Trifluoromethanesulfonate
Sodium Azide
Original Commentary
First Update
Sodium Borohydride
Original Commentary
First Update
Second Update
Sodium Cyanoborohydride
Original Commentary
First Update
Sodium Hexamethyldisilazide
Original Commentary
First Update
Sodium Hydride
Original Commentary
First Update
Sodium Periodate
Original Commentary
First Update
Tetrabutylammonium Fluoride
Original Commentary
Tetrakis(triphenylphosphine)palladium(0)
Tetra-n-propylammonium Perruthenate
Original Commentary
First Update
p-Toluenesulfonyl Chloride
Original Commentary
First Update
Triethylsilane
Original Commentary
First Update
Trifluoromethanesulfonic Acid
Original Commentary
First Update
Trifluoromethanesulfonic Anhydride
Original Commentary
First Update
Second Update
Trimethylsilyl Trifluoromethane sulfonate
Original Commentary
First Update
Trimethylsilyldiazomethane
Original Commentary
First Update
Zinc–Acetic Acid
List of Contributors
Index
End User License Agreement
List of Tables
Table 1
Table 2
Table 1
Table 2
Table 1
Table 1
Table 2
List of Illustrations
Scheme 1
Scheme 1
Scheme 2
Scheme 3
Scheme 4
Scheme 5
Scheme 6
Scheme 7
Scheme 8
Scheme 9
Scheme 10
Scheme 11
Scheme 12
Scheme 13
Scheme 14
Scheme 15
Scheme 16
Scheme 17
Scheme 18
Scheme 19
Scheme 21
Scheme 22
Scheme 23
Scheme 1
Scheme 2
Guide
Cover
Table of Contents
Begin Reading
Chapter 1
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e-EROS Editorial Board
Editor-in-ChiefPhilip L. FuchsPurdue University, West Lafayette, IN, USA
Executive EditorsAndré B. CharetteUniversité de Montréal, Montréal, Québec, Canada
Tomislav RovisColorado State University, Fort Collins, CO, USA
Jeffrey W. BodeETH Zürich, Switzerland
Founding EditorLeo A. PaquetteThe Ohio State University, Columbus, OH, USA
Essential Reagents for Organic Synthesis
Edited by
Philip L. Fuchs
Purdue University, West Lafayette, IN, USA
André B. Charette
Université de Montréal, Montréal, Québec, Canada
Tomislav Rovis
Colorado State University, Fort Collins, CO, USA
Jeffrey W. Bode
ETH Zürich, Switzerland
This edition first published 2016 © 2016 John Wiley & Sons Ltd
Registered officeJohn Wiley & Sons Ltd, The Atrium, Southern Gate, Chichester, West Sussex, PO19 8SQ,United Kingdom
For details of our global editorial offices, for customer services and for information about how to apply for permission to reuse the copyright material in this book please see our website at www.wiley.com.
The right of the author to be identified as the author of this work has been asserted in accordance with the Copyright, Designs and Patents Act 1988.
All rights reserved. No part of this publication may be reproduced, stored in a retrieval system, or transmitted, in any form or by any means, electronic, mechanical, photocopying, recording or otherwise, except as permitted by the UK Copyright, Designs and Patents Act 1988, without the prior permission of the publisher.
Wiley also publishes its books in a variety of electronic formats. Some content that appears in print may not be available in electronic books.
Designations used by companies to distinguish their products are often claimed as trademarks. All brand names and product names used in this book are trade names, service marks, trademarks or registered trademarks of their respective owners. The publisher is not associated with any product or vendor mentioned in this book. This publication is designed to provide accurate and authoritative information in regard to the subject matter covered. It is sold on the understanding that the publisher is not engaged in rendering professional services. If professional advice or other expert assistance is required, the services of a competent professional should be sought.
Library of Congress Cataloging-in-Publication Data
Names: Fuchs, Philip L., 1945- editor. | Charette, A. B. (André B.), 1961- editor. | Rovis, Tomislav, 1968- editor. | Bode, J. W. (Jeffrey W.), editor.
Title: Essential reagents for organic synthesis / edited by Philip L. Fuchs, Andre B. Charette, Tomislav Rovis, Jeffrey W. Bode.
Description: Chichester, UK ; Hoboken, NJ : John Wiley & Sons, 2016. | Includes index.
Identifiers: LCCN 2016021468| ISBN 9781119278306 (paperback) | ISBN 9781119279877 (epub)
Subjects: LCSH: Chemical tests and reagents. | Organic compounds–Synthesis.
Classification: LCC QD77 .E77 2016 | DDC 547/.2–dc23 LC record available at https://lccn.loc.gov/2016021468
A catalogue record for this book is available from the British Library.
ISBN: 9781119179573
Preface
This handbook is a subset of the Encyclopedia of Reagents for Organic Synthesis (EROS), a knowledge base with detailed information on organic-chemical reagents and catalysts. As of mid-2016, the online collection offers reviews on 4959 different reagents and catalysts that are regularly updated. To keep up with the continual evolution in the field, about 200 new or updated reagent articles are added per year to the online database.
In addition to the complete collection that is available only online (see http://wileyonlinelibrary.com/ref/eros), a number of highly focused single-volume handbooks in print and electronic format on editor-selected subjects have been published (Handbook for Reagents in Organic Synthesis,HROS). Recent titles in the HROS series include:
Reagents for Organocatalysis
Edited by Tomislav Rovis (2016)
Reagents for Heteroarene Functionalization
Edited by André B. Charette (2015)
Catalytic Oxidation Reagents
Edited by Philip L. Fuchs (2013)
Reagents for Silicon-Mediated Organic Synthesis
Edited by Philip L. Fuchs (2011)
Sulfur-Containing Reagents
Edited by Leo A. Paquette (2010)
Reagents for Radical and Radical Ion Chemistry
Edited by David Crich (2009)
Data mining of EROS user downloads guided by editorial adjudication has yielded the present collection of 52 often-used reagents that will facilitate the daily laboratory endeavor of every organic chemist. The collection contains oxidants (15), reductants (10), metal and organic catalysts (11), Brønsted and Lewis acids (8), and bases (6), to cite a fewgeneral mechanistic categories.
We hope that this handbook will prove to be an invaluable primary resource for both beginning graduate students and experienced Ph.D. researchers.
Philip L. Fuchs
Purdue University, West Lafayette, IN, USA
André B. Charette
Université de Montréal, Montréal, Québec, Canada
Tomislav Rovis
Colorado State University, Fort Collins, CO, USA
Jeffrey W. Bode
ETH Zürich, Switzerland
Short Note on InChIs and InChIKeys
The IUPACInternational Chemical Identifier (InChITM) and its compressed form, the InChIKey, are strings of letters representing organic chemical structures that allow for structure searching with a wide range of online search engines and databases such as Google and PubChem. While they are obviously an important development for online reference works, such as Encyclopedia of Reagents for Organic Synthesis (e-EROS), readers of this volume may be surprised to find printed InChI and InChIKey information for each of the reagents.
We introduced InChI and InChIKey to e-EROS in autumn 2009, including the strings in all HTML and PDF files. While we wanted to make sure that all users of e-EROS, the second print edition of EROS, and all derivative handbooks would find the same information, we appreciate that the strings will be of little use to the readers of the print editions, unless they treat them simply as reminders that e-EROS now offers the convenience of InChIs and InChIKeys, allowing the online users to make best use of their browsers and perform searches in a wide range of media.
If you would like to know more about InChIs and InChIKeys, please go to the e-EROS website: www.wileyonlinelibrary.com/ref/eros and click on the InChI and InChIKey link.
General Abbreviations
Ac
acetyl
acac
acetylacetonate
AIBN
2,2′-azobisisobutyronitrile
Ar
aryl
BBN
borabicyclo[3.3.1]nonane
BCME
dis(chloromethyl)ether
BHT
butylated hydroxytoluene (2,6-di-
t
-butyl-
p
-cresol)
BINAL-H
2,2′-dihydroxy-1,1′-binaphthyl-lithium aluminum hydride
BINAP
2,2′-bis(diphenylphosphino)-1,1′-binaphthyl
BINOL
1,1′-bi-2,2′-naphthol
bipy
2,2′-bipyridyl
BMS
borane–dimethyl sulfide
Bn
benzyl
Boc
t
-butoxycarbonyl
BOM
benzyloxymethyl
bp
boiling point
Bs
brosyl (4-bromobenzenesulfonyl)
BSA
N,O
-bis(trimethylsilyl)acetamide
Bu
n
-butyl
Bz
benzoyl
CAN
cerium(IV) ammonium nitrate
Cbz
benzyloxycarbonyl
CDI
N,N
′-carbonyldiimidazole
CHIRAPHOS
2,3-bis(diphenylphosphino)butane
Chx
=Cy
cod
cyclooctadiene
cot
cyclooctatetraene
Cp
cyclopentadienyl
CRA
complex reducing agent
CSA
10-camphorsulfonic acid
CSI
chlorosulfonyl isocyanate
Cy
cyclohexyl
d
density
DABCO
1,4-diazabicyclo[2.2.2]octane
DAST
N,N
′-diethylaminosulfur trifluoride
dba
dibenzylideneacetone
DBAD
di-
t
-butyl azodicarboxylate
DBN
1,5-diazabicyclo[4.3.0]non-5-ene
DBU
1,8-diazabicyclo[5.4.0]undec-7-ene
DCC
N,N
′-dicyclohexylcarbodiimide
DCME
dichloromethyl methyl ether
DDO
dimethyldioxirane
DDQ
2,3-dichloro-5,6-dicyano-1,4-benzoquinone
de
diastereomeric excess
DEAD
diethyl azodicarboxylate
DET
diethyl tartrate
DIBAL
diisobutylaluminum hydride
DIEA
=DIPEA
DIOP
2,3-
O
-isopropylidene-2,3-dihydroxy-1,4-bis-(diphenylphosphino)butane
DIPEA
diisopropylethylamine
diphos
DIPT
diisopropyl tartrate
DMA
dimethylacetamide
DMAD
dimethyl acetylenedicarboxylate
DMAP
4-(dimethylamino)pyridine
DME
1,2-dimethoxyethane
DMF
dimethylformamide
dmg
dimethylglyoximato
DMPU
N,N
′-dimethylpropyleneurea
DMS
dimethyl sulfide
DMSO
dimethyl sulfoxide
DMTSF
dimethyl(methylthio) sulfonium tetrafluoroborate
dppb
1,4-bis(diphenylphosphino)butane
dppe
1,2-bis(diphenylphosphino)ethane
dppf
1,1′-bis(diphenylphosphino)ferrocene
dppp
1,3-bis(diphenylphosphino)propane
DTBP
di-
t
-butyl peroxide
EDA
ethyl diazoacetate
EDC
1-ethyl-3-(3-dimethylaminopropyl)-carbodiimide
EDCI
=EDC
ee
enantiomeric excess
EE
1-ethoxyethyl
Et
ethyl
ETSA
ethyl trimethylsilylacetate
EWG
electron withdrawing group
Fc
ferrocenyl
Fmoc
9-fluorenylmethoxycarbonyl
fp
flash point
Hex
n
-hexyl
HMDS
hexamethyldisilazane
HMPA
hexamethylphosphoric triamide
HOBt
l-hydroxybenzotriazole
HOBT
HOSu
N
-hydroxysuccinimide
Im
imidazole (imidazolyl)
Ipc
isopinocampheyl
IR
infrared
KHDMS
potassium hexamethyldisilazide
LAH
lithium aluminum hydride
LD
50
dose that is lethal to 50% of test subjects
LDA
lithium diisopropylamide
LDMAN
lithium 1-(dimethylamino)naphthalenide
LHMDS
=LiHMDS
LICA
lithium isopropylcyclohexylamide
LiHMDS
lithium hexamethyldisilazide
LiTMP
lithium 2,2,6,6-tetramethylpiperidide
LTMP
=LiTMP
LTA
lead tetraacetate
lut
lutidine
m
-CPBA
m
-chloroperbenzoic acid
MA
maleic anhydride
MAD
methylaluminum bis(2,6-di-
t
-butyl-4-methylphenoxide)
MAT
methylaluminum bis(2,4,6-tri-
t
-butylphenoxide)
Me
methyl
MEK
methyl ethyl ketone
MEM
(2-methoxyethoxy)methyl
MIC
methyl isocyanate
MMPP
magnesium monoperoxyphthalate
MOM
methoxymethyl
MoOPH
oxodiperoxomolybdenum(pyridine)-(hexamethylphosphoric triamide)
mp
melting point
MPM
=PMB
Ms
mesyl (methanesulfonyl)
MS
mass spectrometry; molecular sieves
MTBE
methyl
t
-butyl ether
MTM
methylthiomethyl
MVK
methyl vinyl ketone
n
refractive index
NaHDMS
sodium hexamethyldisilazide
Naph
naphthyl
NBA
N
-bromoacetamide
nbd
norbornadiene (bicyclo[2.2.1]hepta-2,5-diene)
NBS
N
-bromosuccinimide
NCS
N
-chlorosuccinimide
NIS
N
-iodosuccinimide
NMO
N
-methylmorpholine
N
-oxide
NMP
N
-methyl-2-pyrrolidinone
NMR
nuclear magnetic resonance
NORPHOS
bis(diphenylphosphino)bicyclo[2.2.1]-hept-5-ene
Np
PCC
pyridinium chlorochromate
PDC
pyridinium dichromate
Pent
n
-pentyl
Ph
phenyl
phen
1,10-phenanthroline
Phth
phthaloyl
Piv
pivaloyl
PMB
p
-methoxybenzyl
PMDTA
N,N,N′,N
′′
,N
′′
-pentamethyldiethylene-triamine
PPA
polyphosphoric acid
PPE
polyphosphate ester
PPTS
pyridinium
p
-toluenesulfonate
Pr
n
-propyl
PTC
phase transfer catalyst/catalysis
PTSA
p
-toluenesulfonic acid
py
pyridine
RAMP
(R)-1-amino-2-(methoxymethyl)pyrrolidine
rt
room temperature
salen
bis(salicylidene)ethylenediamine
SAMP
(
S
)-1-amino-2-(methoxymethyl)pyrrolidine
SET
single electron transfer
Sia
siamyl (3-methyl-2-butyl)
TASF
tris(diethylamino)sulfonium difluorotrimethylsilicate
TBAB
tetrabutylammonium bromide
TBAF
tetrabutylammonium fluoride
TBAD
TBAI
tetrabutylammonium iodide
TBAP
tetrabutylammonium perruthenate
TBDMS
t
-butyldimethylsilyl
TBDPS
t
-butyldiphenylsilyl
TBHP
t
-butyl hydroperoxide
TBS
=TBDMS
TCNE
tetracyanoethylene
TCNQ
7,7,8,8-tetracyanoquinodimethane
TEA
triethylamine
TEBA
triethylbenzylammonium chloride
TEBAC
TEMPO
2,2,6,6-tetramethylpiperidinoxyl
TES
triethylsilyl
Tf
triflyl (trifluoromethanesulfonyl)
TFA
trifluoroacetic acid
TFAA
trifluoroacetic anhydride
THF
tetrahydrofuran
THP
tetrahydropyran; tetrahydropyranyl
Thx
thexyl (2,3-dimethyl-2-butyl)
TIPS
triisopropylsilyl
TMANO
trimethylamine
N
-oxide
TMEDA
N,N,N
′,
N
′-tetramethylethylenediamine
TMG
1,1,3,3-tetramethylguanidine
TMS
trimethylsilyl
Tol
p
-tolyl
TPAP
tetrapropylammonium perruthenate
TBHP
t
-butyl hydroperoxide
TPP
tetraphenylporphyrin
Tr
trityl (triphenylmethyl)
Ts
tosyl (
p
-toluenesulfonyl)
TTN
thallium(III) nitrate
UHP
urea–hydrogen peroxide complex
Z
=Cbz
B
Bis(dibenzylideneacetone)palladium(0)
9-Borabicyclo[3.3.1]nonane Dimer
Boron Trifluoride Etherate
N
-Bromosuccinimide
n
-Butyllithium
