Classics in Total Synthesis III: Further Targets, Strategies, Methods

772 Pages·2011·19.537 MB·English

by  K. C. Nicolaou, Jason S. Chen

®WILEY-VCH
Nicolaou Chen
(cid:127)
Classics
in Total Synthesis Ml
Further Targets, Strategies, Methods
Abbreviations
Ac acetyl DME ethylene glycol dimethyl ether
acac acetoacetate DMF M/V-dimethylformamide
AD asymmetric dihydroxylation DMP Dess-Martin periodinane
AIBN 2,2'-azobisisobutyronitrile DMPU 1.3-dimethyl-3,4,5,6-tetrahydro-
Alloc allyloxycarbonyl 2(1#)-pyrimidinone
aq. aqueous DMS dimethyl sulfide
AQN anthraquinone DMSO dimethyl sulfoxide
ATP adenosine triphosphate DNA deoxyribonucleic acid
9-BBN 9-borabicyclo[3.3.1]nonane DOSP (/V-dodecylbenzenesulfonyl)prolinate
BHT t-butylhydroxytoluene DPPA diphenylphosphoryl azide
BINOL 2,2'-dihydroxy-1,1'-binaphthyl dppb 1.4-bis(diphenylphosphino)butane
Bn benzyl dppf diphenylphosphinoferrocene
Boc t-butoxycarbonyl dr diastereomeric ratio
brsm based on recovered starting material EDC l-(3-dimethylaminopropyl)-3-ethyl-
Bz benzoyl carbodiimide hydrochloride
CAN cerium(IV) ammonium nitrate ee enantiomeric excess
cat. catalytic or catalyst Fm 9-fluorenylmethyl
CBS Corey-Bakshi-Shibata Fmoc 9-fluorenylmethoxycarbonyl
Cbz benzyloxycarbonyl GI 50% growth inhibitory concentration
50
cod 1,5-cyclooctadiene GTP guanosine triphosphate
coe cyclooctene HFIP hexafluoroisopropanol
Cp cyclopentadienyl HMDS hexamethyldisilylazine
Cp* pentamethylcyclopentadienyl HMPA hexamethylphosphoramide
CSA 10-camphorsulfonic acid hv light
cy cyclohexyl HOAt l-hydroxy-7-azabenzotriazole
Cys cysteine HOBt 1-hydroxybenzotriazole
A heat HPLC high-pressure liquid chromatography
DABCO 1,4-diazabicyclo[2.2.2]octane IBX o-iodoxybenzoic acid
DAST (diethylamino)sulfur trifluoride IC 50% inhibitory concentration
50
dba trans,trans-dibenzylideneacetone imid. imidazole
DBU l,8-diazabicyclo[5.4.0]undec-7-ene Ipc isopinocampheyl
DCC 1.3-dicyclohexylcarbodiimide Keq equilibrium constant
DDQ 2.3-dichloro-5,6-dicyano-1,4-benzo- kre relative rate
|
quinone KHMDS potassium hexamethyldisilylazide
de diastereomeric excess LD 50% lethal dose
50
DEAD diethyl azodicarboxylate LDA lithium diisopropylamide
DEIPS diethylisopropylsilyl LiHMDS lithium hexamethyldisilylazide
DHP 3,4-dihydro-27/-pyran LUMO lowest unoccupied molecular orbital
DHQ dihydroquinine m-CPBA m-chloroperoxybenzoic acid
DHQD dihydroquinidine Mes mesityl or mesitoyl or mesitylene-
DIBAL-H diisobutylaluminum hydride sulfonyl
DIP-C1 diisopinocamphenyl chloroborane MIC minimum inhibitory concentration
DMAP 4-dimethylaminopyridine mol. molecular
DMDO 2,2-dimethyldioxirane MOM methoxymethyl
MPPIM methyl l-(3-phenylpropanoyl)- RNA ribonucleic acid
2-oxaimidazolidine carboxylate SEM 2-(trimethylsilyl)ethoxymethyl
MS molecular sieves Su succinimide
Ms methanesulfonyl TADDOL a,a,a',a'-tetraaryl-l,3-dioxolan-
pwave microwave 4,5-dimethanol
NADPH nicotinamide adenine dinucleotide TBAF tetra-n-butylammonium fluoride
phosphate TBAI tetra-n-butylammonium iodide
NaHMDS sodium hexamethyldisilylazide TBDPS f-butyldiphenylsilyl
NBS yV-bromosuccinimide TBS t-butyldimethylsilyl
NCS yV-chlorosuccinimide TEMPO 2,2,6,6-tetramethy1-1-piperidiny1-
NIS AModosuccinimide oxy, free radical
NMM AAmethylmorpholine Teoc 2-(trimethylsilyl)ethoxycarbonyl
NMP Ay-methylpyrrolidine TES triethylsilyl
NMO 4-methylmorpholine A-oxide Tf trifluoromethanesulfonate
NMR nuclear magnetic resonance TFA trifluoroacetic acid
NOE nuclear Overhauser effect TFAA trifluoroacetic anhydride
NOESY nuclear Overhauser enhancement TFP tri(o-furyl)phosphine
spectroscopy thexyl 1,1,2-trimethylpropyl
Ns 2-nitrobenzenesulfonyl THF tetrahydrofuran
PCC pyridinium chlorochromate THP tetrahydropyranyl
PDC pyridinium dichromate TIPS triisopropylsilyl
PHAL phthalazine TLC thin-layer.chromatography
PHOX phosphinooxazoline TMEDA MAA/V'^'-tetramethylethyl-
Phth phthalyl enediamine
Piv pivaloyl TMS trimethylsilyl
PMB 4-methoxybenzyl TMSE 2-(trimethylsilyl)ethyl
PMP 4-methoxyphenyl tol tolyl
PP pyrophosphate TON turnover number
PPTS pyridinium 4-toluenesulfonate TPAP tetra-n-propylammonium
py pyridine perruthenate
Red-Al® sodium bis(2-methoxyethoxy) Ts 4-toluenesulfonyl
aluminum hydride V-ATPase vacuolar-type proton ATPase
Further Reading from Wiley-VCH
Nicolaou, K.C. / Sorensen, E.J.
Classics in Total Synthesis - Targets, Strategies, Methods
1996
ISBN 978-3-527-29284-4 (Hardcover)
ISBN 978-3-527-29231-8 (Softcover)
Nicolaou, K.C. / Snyder, S.A.
Classics in Total Synthesis II - More Targets, Strategies, Methods
2003
ISBN 978-3-527-30685-5 (Hardcover)
ISBN 978-3-527-30684-8 (Softcover)
Carreira, E.M. / Kvaerno, L.
Classics in Stereoselective Synthesis
2009
ISBN 978-3-527-32452-1 (Hardcover)
ISBN 978-3-527-29966-9 (Softcover)
Nicolaou, K.C. / Montagnon, Tamsyn
Molecules that Changed the World
2008
ISBN 978-3-527-30938-2 (Hardcover)
Corey, E.J. / Czako, B. / Kiirti, L.
Molecules and Medicine
2008, ISBN 978-0-470-26096-8 (Hardcover)
2007, ISBN 978-0-470-22749-7 (Softcover)
Corey, E.J. / Cheng, X.-M.
The Logic of Chemical Synthesis
1995
ISBN 978-0-471-11594-6 (Softcover)
Classics in Total
K. C. Nicolaou and
J. S. Chen
Synthesis III
Further Targets, Strategies, Methods
With a Foreword by
E.J. Corey
-
WILEY
VCH
WILEY-VCH GmbH & Co. KGaA
Prof. Dr. K.C. Nicolaou
Department of Chemistry and Department of Chemistry and Biochemistry
The Scripps Research Institute University of California, San Diego
10550 N. Torrey Pines Road 9500 Gilman Drive
La Jolla, California 92037 USA La Jolla, California 92093 USA
Dr. Jason S. Chen
Department of Chemistry
The Scripps Research Institute
10550 N. Torrey Pines Road
La Jolla, California 92037 USA
_
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Dedication
To the idea of internationalism and to those pioneers and educators
who set the foundations of chemistry, the central science that pro-
foundly changed the world and promises to solve some of the
most pressing global challenges of today and tomorrow.

Foreword
-
I had the enjoyable task of reviewing prepublication copies of Clas
sics in Total Synthesis 1(K.C. Nicolaou and E.J. Sorensen) and 11
(K.C. Nicolaou and S.A. Snyder), and writing a Foreword for each
of these now much-acclaimed accounts of the total synthesis of
some 60 complex naturally occurring molecules. It was really a
pleasure, since both books were written to a very high standard in
terms of chemical content, pedagogy, and clarity. So, I hastened
to accept K.C. Nicolaou’s kind invitation to write another Foreword
for this book, Classics111,which splendidly follows in thefootsteps
of theearlier works with accounts of 42syntheses of 25 challenging
natural products. In aggregate, Classics I-III elegantly and effec-
tively chronicle monumental scientific achievement across a broad
front.
In my Foreword to the first volume in the series I expressed the
hope that Classics I would “be successful and followed by a conti-
nuing series”.My wish has now materialized, much to the benefitof
the whole field of chemical synthesis. Students, teachers, and
researchers will greatly profit from studying Classics III, as they
did from the two predecessors. The Introduction that follows this
Foreword contains an engaging summary of the objectives and phi-
losophy of the authors. I recommend that you read it now, even
though I know that you will be tempted to plunge straight into the
exciting chemistry that comes after.
We live at a time when the field of chemistry is underappreciated
- probably through a profound lack of understanding of the good
that the chemical sciences have contributed to the welfare of
humans. We should be thankful that many intellectually gifted
and energetic young people overlook this fact and undertake syn-
thetic chemistry as a career out of admiration for its beauty and
the enjoyment that comes from discovery and creative achievement
in synthesis. No doubt, the achievements of the past and the love of
science transmitted by their teachers are influential. Fortunately,
there remains much to accomplish and learn, and there is much
inspiration to be gained on the pages of this fine book. This volume,
as with the two before, will serve as an antidote to the public indif-
ference of chemistry. My thanks to K.C. Nicolaou and Jason Chen
for the hard work and commitment to sustaining progress in syn-
thetic chemistry that led to this admirable book.
E.J. Corey
Harvard University
Cambridge, MA
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