Stereoselective Alkene Synthesis

282 Pages·2012·6.96 MB·English

by  Mitsuru Shindo

327
Topics in Current Chemistry
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Jianbo Wang
Editor
Stereoselective Alkene
Synthesis
With contributions by
I.Chataigner(cid:1)Y.Gu(cid:1)S.Hara(cid:1)Y.Hu(cid:1)X.Lei(cid:1)H.Li(cid:1)J.Maddaluno(cid:1)
K. Matsumoto (cid:1) M. De Paolis (cid:1) M. Shindo (cid:1) W.-Y. Siau (cid:1) S.-K. Tian (cid:1)
J. Wang (cid:1) Y. Zhang (cid:1) Y. Zhang (cid:1) X.P. Zhang (cid:1) Y. Zhao
Editor
JianboWang
PekingUniversity
Beijing
China
ISSN0340-1022 ISSN1436-5049(electronic)
ISBN978-3-642-31823-8 ISBN978-3-642-31824-5(eBook)
DOI10.1007/978-3-642-31824-5
SpringerHeidelbergNewYorkDordrechtLondon
LibraryofCongressControlNumber:2012943861
#Springer-VerlagBerlinHeidelberg2012
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Preface
Thestereoselectivesynthesisofolefinshasbeenoneofthemajortopicsinthearena
of organic synthesis for many decades. The methods for olefin synthesis have
evolved from classic elimination reactions to more modern methods such as the
Wittig reaction and its variants, cross-coupling reactions and olefin metathesis.
Numerousreviewsareavailableonthesetopics.Thepurposeofthisspecialvolume
is to cover the most recent advances in this ever-growing field, with a focus on
stereocontrolinC=Cdoubleformation.
Twochaptersinthisvolumehighlighttherecentdevelopmentofthewidelyused
methods for olefin synthesis, namely Wittig reactions (Chapter 7) and olefin
metathesis (Chapter 6). For olefin metathesis, the focus is put on its applications
in complex natural product synthesis. Owing to the importance of introducing
fluorineatoms toorganic molecules, the methods for the stereoselective synthesis
ofmonofluoroalkeneshavebeensummarizedinChapter3.1,3-Dienes,asaspecial
typeofolefin,widelyexistinnaturalproducts,andalsofindvariousapplicationsin
organic synthesis. Therefore, stereoselective synthesis of 1,3-dienes is considered
asanimportantpartofolefinsynthesis.Thisisalsoincludedinthisspecialvolume
(Chapter4).
Stereoselectivesynthesisoftetrasubstitutedalkenesremainsachallengingtask.
A unique solution to this problem is to use torquoselectivity-controlled olefina-
tion of carbonyl compounds with ynolates, which is summarized in Chapter 1.
Ingeneral,thestereoselectivesynthesisofZ-alkenes,whicharethermodynamically
less favorable, is more difficult than the synthesis of corresponding E-isomers.
In Chapter 2, various methods for stereoselective synthesis of Z-alkenes are
reviewed.Finally,theC=Cdoublebondformationthroughcatalyticcarbenetrans-
formation has recently emerged as a new approach toward olefin synthesis. Two
chapters covering olefin synthesis based on catalytic carbene transformations are
included(Chapter5andChapter8).
Having read all the chapters, I hope that readers are left with the notion
that stereoselective olefin synthesis is still a rapidly growing area with constant
emergenceofnovelsyntheticmethods.
v
vi Preface
I would like to thank Prof. Henry N. C. Wong for his encouragement and
support, Karin Bartsch and Elizabeth Hawkins for their assistance in the whole
process. Iwouldalsoliketothankthe referees fortheir invaluablecommentsand
suggestions. Finally, this book would not have been possible without the partici-
pation of the authors, to whom I am deeply indebted for their enduring patience
throughoutthisproject.
Beijing,June8,2012 JianboWang
Contents
StereoselectiveSynthesisofTetrasubstitutedAlkenesvia
Torquoselectivity-ControlledOlefinationofCarbonylCompounds
withYnolates ................................................................... 1
MitsuruShindoandKenjiMatsumoto
StereoselectiveSynthesisofZ-Alkenes ...................................... 33
Woon-YewSiau,YaoZhang,andYuZhao
StereoselectiveSynthesisofMono-fluoroalkenes ........................... 59
ShojiHara
RecentAdvancesinStereoselectiveSynthesisof1,3-Dienes ............... 87
MichaelDePaolis,IsabelleChataigner,andJacquesMaddaluno
SelectiveOlefinationofCarbonylCompoundsviaMetal-Catalyzed
CarbeneTransferfromDiazoReagents .................................... 147
YangHuandX.PeterZhang
SelectiveAlkeneMetathesisintheTotalSynthesisofComplex
NaturalProduct .............................................................. 163
XiaoguangLeiandHouhuaLi
OlefinationReactionsofPhosphorus-StabilizedCarbonNucleophiles .. 197
YonghongGuandShi-KaiTian
AlkeneSynthesisThroughTransitionMetal-CatalyzedCross-Coupling
ofN-Tosylhydrazones ........................................................ 239
YanZhangandJianboWang
Index .......................................................................... 271
vii
.
TopCurrChem(2012)327:1–32
DOI:10.1007/128_2012_313
#Springer-VerlagBerlinHeidelberg2012
Publishedonline:6March2012
Stereoselective Synthesis of Tetrasubstituted
Alkenes via Torquoselectivity-Controlled
Olefination of Carbonyl Compounds
with Ynolates
MitsuruShindoandKenjiMatsumoto
Abstract The efficient synthesis of tetrasubstituted alkenes by the olefination of
carbonyl compounds with ynolates is described. This reaction involves the cyclo-
additionofynolateswithcarbonylgroups,followedbyelectrocyclicring-opening
oftheresultingb-lactoneenolates.Orbitalsymmetryduringtheelectrocyclicring
opening requires conrotatory motion. The direction of this rotation (inward or
outward)determinestheE/Zgeometrytothetetrasubstitutedolefinproductthrough
torquoselectivity. Theoretical calculations revealed that several secondary orbital
interactionsareessentialforthehightorquoselectivity.Thismethodologyisanovel
olefinationforconstructingmultisubstitutedolefins.
Keywords Electrocyclic reaction (cid:1) Olefination (cid:1) Secondary orbital interaction (cid:1)
Torquoselectivity(cid:1)Ynolate
Contents
1 Introduction................................................................................... 2
2 PreparationofYnolates...................................................................... 3
3 OlefinationofAldehydes..................................................................... 6
4 OlefinationofKetones....................................................................... 7
4.1 UnfunctionalizedKetones.............................................................. 7
4.2 StereoelectronicEffect................................................................. 10
4.3 Torquoselectivity....................................................................... 10
4.4 a-Alkoxyketones....................................................................... 13
4.5 a-Amino,a-Thio,a-Selenoketones.................................................... 14
4.6 AlkynylKetones........................................................................ 16
M.Shindo(*)andK.Matsumoto
InstituteforMaterialsChemistryandEngineering,KyushuUniversity,6-1,Kasugako-en,
Kasuga816-8580,Japan
e-mail:[email protected]
2 M.ShindoandK.Matsumoto
5 OlefinationofAcylsilanes,Acylgermanes,andAcylstannanes............................ 18
5.1 Olefination.............................................................................. 18
5.2 PropertiesandReactionsofIntramolecularlyActivatedAlkenylsilanes,
Alkenylgermanes....................................................................... 19
5.3 HypervalentSiliconesandGermanes................................................. 20
5.4 ReactionsofSilalactones.............................................................. 21
5.5 Pd-CatalyzedFluoride-FreeCrossCouplingofAlkenylsilanesandGermanes..... 21
6 OlefinationofEsters.......................................................................... 23
6.1 Olefination.............................................................................. 23
6.2 Homologation.......................................................................... 24
6.3 SyntheticApplications................................................................. 25
7 OlefinationofAldimines..................................................................... 28
8 Conclusion.................................................................................... 28
References........................................................................................ 30
1 Introduction
Stereoselective olefination of carbonyl groups giving tetrasubstituted alkenes is a
hot topic in synthetic organic chemistry, because there have been very few
reports on this process [1, 2]. These moieties are sometimes contained in natural
products, such as materials of the Stemona alkaloids [3] and kainoid amino acids
[4],drugssuchastamoxifen[5],anddipeptidemimetics(Fig.1)[6,7].Importantly,
tetrasubstituted olefins also contribute extensively to material sciences in such
capacities as photoswitches based on photochromism [8]. Besides being useful
final products, stereodefined tetrasubstituted olefins would be potential precursors
for various asymmetric transformations generatingcontiguousstereogeniccenters
such as hydrogenations [9], dihydroxylations [10, 11], epoxidations [12, 13],
conjugate additions [14, 15], and Heck reaction [16]. Even with the significance
of these olefins, conventional direct olefination methods such as the Wittig and
O O
OMe OMe
O O
O O HN
O
CO2H
N N
HO C
2 CO H
2
Isodomic acid G
Stemonamide Stemonamine
HO C
2 HN
O
NH O
O
HN
H
NMe2 NH N
H2N O
O HN
Tamoxifen cyclic RGD peptidemimetics
Fig.1 Biologicallyactivecompoundswithtetrasubstitutedolefins