Organic Reactions, Volume 69

579 Pages·2007·6.57 MB·English

by  Scott E. Denmark

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10 9 8 76 5 43 2 1
CONTENTS
CHAPTER PAGE
1. DIOXIRANE OXIDATIONSOF COMPOUNDSOTHERTHAN ALKENES
Waldemar Adam, Cong-Gui Zhao, and Kavitha Jakka . . . . . . . . . . 1
2. ELECTROPHILIC FLUORINATIONWITH N–F REAGENTS
Je´roˆmeBaudoux and Dominique Cahard . . . . . . . . . . . . . . . . . . 347
CUMULATIVE CHAPTER TITLESBY VOLUME . . . . . . . . . . . . . . . . . . . . . . . 673
AUTHOR INDEX, VOLUMES 1–69 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 687
CHAPTERAND TOPIC INDEX, VOLUMES 1–69 . . . . . . . . . . . . . . . . . . . . . . 693
vii
CHAPTER 1
DIOXIRANE OXIDATIONS OF COMPOUNDS
OTHER THAN ALKENES
WALDEMAR ADAM
Institute for Organic Chemistry, Wu¨rzburg University,
D-97074 Wu¨rzburg, Germany
and
Department of Chemistry, University of Puerto Rico,
Rio Piedras, Puerto Rico 00931
CONG-GUI ZHAO and KAVITHA JAKKA
Department of Chemistry, The University of Texas at San Antonio,
San Antonio, Texas 78249
CONTENTS
PAGE
ACKNOWLEDGMENTS . . . . . . . . . . . . . 3
INTRODUCTION . . . . . . . . . . . . . . 4
MECHANISM . . . . . . . . . . . . . . 5
Allenes,Alkynes,andArenes . . . . . . . . . . 5
HeteroatomSubstrates . . . . . . . . . . . . 5
AlkanesandSilanes . . . . . . . . . . . . 7
SCOPEANDLIMITATIONS . . . . . . . . . . . . 8
Allenes,Alkynes,andArenes . . . . . . . . . . 9
HeteroatomSubstrates . . . . . . . . . . . . 15
Nitrogen . . . . . . . . . . . . . . 16
SulfurandSelenium . . . . . . . . . . . . 20
Phosphorus . . . . . . . . . . . . . 26
Oxygen . . . . . . . . . . . . . . 27
Halogens . . . . . . . . . . . . . . 29
AlkanesandSilanes . . . . . . . . . . . . 30
Alkanes . . . . . . . . . . . . . . 30
Silanes . . . . . . . . . . . . . . 36
OrganometallicCompounds . . . . . . . . . . . 37
COMPARISONWITHOTHERMETHODS . . . . . . . . . . 41
Allenes,Acetylenes,andArenes . . . . . . . . . . 41
[email protected]
OrganicReactions,Vol.69,EditedbyLarryE.Overmanetal.
2007OrganicReactions,Inc.PublishedbyJohnWiley&Sons,Inc.
1
2 ORGANICREACTIONS
HeteroatomSubstrates . . . . . . . . . . . . 42
AlkanesandSilanes . . . . . . . . . . . . 43
EXPERIMENTALCONDITIONS . . . . . . . . . . . 44
EXPERIMENTALPROCEDURES . . . . . . . . . . . 44
2-Hydroxy-2-methylpropanoic Acid[OxidationofanAlkynewithDMD(isol.)] 44
cis-Bicyclo[5.3.0]decan-2-one[OxidationofanAlkynewithTFD(isol.)] . . 45
6-Hydroxy-2,2-dimethyl-3-oxacyclohexanone [OxidationofanAllenewithDMD
(isol.)] . . . . . . . . . . . . . . 45
6-Hydroxy-5,5-dimethyl-3-oxacyclohexanone [OxidationofanAllenewithDMD
(isol.)] . . . . . . . . . . . . . . 46
2,5-Hexamethylene-1,4-dioxaspiro[2.2]pentane [DiepoxidationofaCyclicAllene
withDMD(isol.)] . . . . . . . . . . . . 46
2,3-Epoxy-2,3-dihydro-2,3-dimethylbenzo[b]furan [EpoxidationofaBenzofuran
withDMD-d (isol.)] . . . . . . . . . . . 46
6
1,2-Epoxyacenaphthene [EpoxidationofanArenewithDMD(isol.)] . . . 47
Bisbenzo[3(cid:1),4(cid:1)]cyclobuta[1(cid:1),2(cid:1):1,2:1(cid:1)(cid:1),2(cid:1)(cid:1):3,4]biphenyleno[1,8b-b:2,3-b(cid:1):4,4
a-b(cid:1)(cid:1)]trisoxirene[EpoxidationofanArenewithDMD(insitu)] . . . . 47
MethylBoc-β-(2,3-dihydro-2-oxo-indol-3-yl)alaninate [OxidationofanIndole
withDMD(isol.)] . . . . . . . . . . . . 48
1-Nitrobutane[OxidationofaPrimaryAliphaticAminewithDMD(isol.)] . 48
1,3,5-Trinitrobenzene[OxidationofaPrimaryAromaticAminewithDMD(isol.)] 49
o-Nitroanisole[OxidationofaPrimaryAromaticAminewithDMD(insitu)] . 49
1-Oxyl-2,2,6,6-tetramethyl-4-hydroxypiperidine [OxidationofaHindered
SecondaryAminewithDMD(isol.)] . . . . . . . . 49
PyridineN-Oxide,MethodA[OxidationofPyridinewithDMD(insitu)] . . 50
PyridineN-Oxide,MethodB[OxidationofPyridinewithDMD(isol.)] . . 50
Thiophene1,1-Dioxide[OxidationofThiophenewithDMD(isol.)] . . . 50
S-Ethyl-S-methyl-N-(acetyl)sulfoximine[OxidationofaSulfiliminewith .
DMD(isol.)] . . . . . . . . . . . . . 51
MethylPhenylSulfoxide[OxidationofaThioetherwithDMD(isol.)] . . 51
Diethyl4-Nitrophenylphosphate [OxidationofaThiophosphatewithDMD(isol.)] 51
Tetraphenylselenophene1-Oxide[OxidationofaSelenophenewithDMD(isol.)] 52
1,6-Di-tert-butyl-2,2,5,5-tetramethyl-7,8-diselenabicyclo[4.1.1]octane 7-endo,
8-endo-Dioxide[OxidationofaSelenoetherwithDMD(isol.)] . . . . 52
Triphenylphosphine Oxide[OxidationofaPhosphinewithDMD(isol.)] . . 53
Singlet-OxygenGenerationbyOxidationofN,N-DimethylanilineN-Oxidewith
DMD(isol.) . . . . . . . . . . . . . 53
[(2S,4S,5S)-5-Acetylamino-4-benzoyloxy-2-methoxycarbonyltetrahydropyran-2-yl]
Propen-2-ylN-Acetyl-2(cid:1),3(cid:1)-di-O-acetyl-5(cid:1)-cytidylate[OxidationofaPhosphitetoa
PhosphatewithDMD(isol.)] . . . . . . . . . . 53
1-[(Trifluoromethyl)sulfonyl]methylcyclohexene [OxidationofanIodo-alkanewith
DMD(isol.)] . . . . . . . . . . . . . 54
trans-2-Iodocyclohexanol [OxidationofIodocyclohexanewithDMD(isol.)] . 54
(S)-4-Cyano-2,2-dimethyl-1,3-dioxalane [ConversionofaHydrazoneintoaNitrile
withDMD(isol.)] . . . . . . . . . . . . 54
2-(2-Chloro-4-hydroxyphenyl)-2-phenylpropionitrile [TandemNuleophilic
Addition/Conversion ofaNitrobenzeneintoaPhenolwithDMD(isol.)] . . 55
Methyl3-Phenyl-2,2-dihydroxy-3-oxopropionate [OxidationofaPhosphoranetoa
KetoneHydratewithDMD(isol.)] . . . . . . . . . 55
Benzoin.MethodA[OxidationofaBenzylAlcoholtoanArylKetonewithDMD
(isol.)] . . . . . . . . . . . . . . 56
(R)-Benzoin.MethodB[CatalyticAsymmetricOxidationofHydrobenzoin] . 56
2,3,22,23-Tetra-O-acetyl-25-hydroxybrassinolide [HydroxylationofaTertiary
CarbonCenterwithTFD(isol.)] . . . . . . . . . 57
DIOXIRANEOXIDATIONSOFCOMPOUNDSOTHERTHANALKENES 3
1,3-Dihydroxyadamantane[DihydroxylationofAdamantanewithTFD(isol.)] . 57
Cycloheptanone[OxidationofaSecondaryAlcoholtoaKetoneunderInSitu
CatalyticConditions] . . . . . . . . . . . 58
Methyl(S∗,S∗)-6-Ethyl-2-hydroxytetrahydropyran-2-carboxylate [Hydroxylation
ofaSecondaryCarbonCenterunderInSituCatalyticConditions] . . . 58
(R)-Methylphenyl(1-naphthyl)silanol [HydroxylationofaSilanewithTFD(isol.)] 59
(η5-Pentamethylcyclopentadienyl)trioxorhenium [OxidationofaRheniumComplex
withDMD(isol.)] . . . . . . . . . . . . 59
EthylPhenylpropiolate[OxidationofaFischerCarbeneComplexwithDMD
(isol.)] . . . . . . . . . . . . . . 59
[Dicarbonyl(η5-pentamethylcyclopentadienyl)ferrio]-1,1-dihydroxydisilane
[HydroxylationofanIron-ComplexedSilanewithDMD(isol.)] . . . 60
TABULARSURVEY . . . . . . . . . . . . . 60
Table1A.OxidationofAllenesandAlkynesbyIsolatedDioxiranes . . . 62
Table1B.OxidationofAllenesandAlkynesbyInSituGeneratedDioxiranes . 88
Table2A.OxidationofArenesandHeteroarenesbyIsolatedDioxiranes . . 91
Table2B.OxidationofArenesandHeteroarenesbyInSituGeneratedDioxiranes . 122
Table3A.NitrogenOxidationbyIsolatedDioxiranes . . . . . . 124
Table3B.SulfurandSeleniumOxidationbyIsolatedDioxiranes . . . . 157
Table3C.PhosphorusOxidationbyIsolatedDioxiranes . . . . . 186
Table3D.OxygenOxidationbyIsolatedDioxiranes . . . . . . 188
Table3E.HalogenOxidationbyIsolatedDioxiranes . . . . . . 192
Table3F.NitrogenOxidationbyInSituGeneratedDioxiranes . . . . 196
Table3G.SulfurOxidationbyInSituGeneratedDioxiranes . . . . . 203
Table3H.OxidationofOtherHeteroatomsbyInSituGeneratedDioxiranes . . 209
Table4A.C=YOxidationbyIsolatedDioxiranes . . . . . . . 210
Table4B.C=YOxidationbyInSituGeneratedDioxiranes . . . . . 229
Table5A.C–HOxidationbyIsolatedDioxiranes . . . . . . . 231
Table5B.RegioselectiveC–HOxidationbyIsolatedDioxiranes . . . . 294
Table5C.C–HOxidationbyInSituGeneratedDioxiranes . . . . . 301
Table5D.AsymmetricC–HOxidationbyInSituGeneratedOpticallyActive .
Dioxiranes . . . . . . . . . . . . . . 311
Table5E.Si–HOxidationbyIsolatedDioxiranes . . . . . . . 313
Table6.OxidationofOrganometallicsbyIsolatedDioxiranes . . . . 315
Table7.MiscellaneousOxidationsbyIsolatedDioxiranes . . . . . 333
REFERENCES . . . . . . . . . . . . . . 335
ACKNOWLEDGMENTS
Generous financial support from the Deutsche Forschungsgemeinschaft
(Schwerpunktprogramm “Peroxidchemie: Mechanistische und Pra¨parative
AspektedesSauerstofftransfers” and Sonderforschungsbereich SFB 347 “Selek-
tiveReaktionenMetall-aktivierterMoleku¨le”), the Fonds derChemischenIndus-
trie, the NIH-MBRS Program (Grant S06 GM 08194), the Welch Foundation
(Grant AX-1593), and the DAAD (Deutscher Akademischer Austauschdienst) is
gratefully appreciated. The authors also thank Dr. Chantu R. Saha-Mo¨ller and
Mrs. Ana-Maria Krause for their help in preparing the tabular and graphical
material.
4 ORGANICREACTIONS
INTRODUCTION
Epoxidations, heteroatom oxidations, and Y–H insertions constitute the best
investigated oxidations by dioxiranes. An overview of these transformations is
displayed in the rosette of Scheme 1. These preparatively useful oxidations have
been extensively reviewed during the last decade.1–14 In a previous chapter,15
we presented the epoxidation of double bonds [π bonds in simple alkenes and
those functionalized with electron donors (ED), electron acceptors (EA), and
with both ED and EA substituents; case 1 in the rosette] with either isolated or
in situ generated dioxiranes. The recent developments in the dioxirane-mediated
asymmetric epoxidation have also been extensively covered there.15 The present
chapter concerns the remaining oxidations in the rosette of Scheme 1, that is,
epoxidation of the double bonds in the cumulenes, such as allenes (transforma-
tion2),acetylenes(transformation3),andarenes(transformation4);theoxidation
of heteroatom functionalities, mainly lone pairs on sulfur (transformation 5),
on nitrogen (transformations 6 and 7), and on oxygen as the deoxygenation of
N-oxides (transformation 8); the oxidation of C=Y functionalities (e.g., trans-
formation 9), Y–H insertions (σ bonds) such as C–H in alkanes (transformation
10) and Si–H in silanes (transformation 11); and the oxidation of organometallic
substrates including metal (transformation 12) and ligand-sphere oxidation.
Np O MnV (salen)
Ph O
Si
OH
Me
12
11 1
O
Ph
Np MnIII
OH 10 PhSi H(salen) 2 O
Ph Me
H (cid:127)
O
O N2 O
9 3
Ph Ph Ph Ph O
O
HO OH
N+
8 O– NMe 4
3
SAr
1O2 + O O
NH
N 7 2
5
6
Me Me
O N Me S(O)Ar or SO2Ar
NO
2
Scheme 1. An overview of dioxiraneoxidations(Np=1-naphthyl).
DIOXIRANEOXIDATIONSOFCOMPOUNDSOTHERTHANALKENES 5
MECHANISM
Allenes, Alkynes, and Arenes
Although the products of the dioxirane oxidation of allenes, alkynes, and
arenes are usually more complex than those of the epoxidation of simple C=C
double bonds, the initial step of the oxidation is usually epoxidation. Therefore,
thesamemechanismthathasbeenextensivelydiscussedinthepreviouschapter15
also applies in these reactions. The oxygen transfer proceeds with complete
retention of the initial olefin configuration through the concerted spiro transi-
tion state.15 An example is shown in Eq. 1, in which the oxidation of the chiral
alleneproceedsinnearlyquantitativeyield(95%)withpreservationofthestarting
allene configuration in the spiro-bisepoxide.16
O
H O O H
(cid:127) (95%) (Eq. 1)
H acetone, K2CO3, H O
rt, 20 min
Since the initial epoxidation products of the allenes, alkynes, and arenes
are usually labile substances, they may undergo subsequent reactions, which
include further oxidation by dioxirane other than epoxidation. For example,
in the dimethyldioxirane (DMD) oxidation of the phenanthrene derivative in
Scheme 2,17 the second oxidation by DMD involves C–H insertion instead of
epoxidation.
O
O
O
(77%)
acetone
OH O
epoxidation C-H insertion
OH
rearrangement
O (100%)
OH O
Scheme 2. DMD oxidationof 9-hydroxyphenanthrene.
Heteroatom Substrates
Throughadetailedstudyofthecompetitiveoxidationofthesulfideversussulf-
oxide functionalities in thianthrene 5-oxide (SSO),18 a pronounced electrophilic
character has been demonstrated for DMD and methyl(trifluoromethyl)dioxirane
(TFD).19,20 Thus,dioxiranesprefertooxidizethesulfideoverthesulfoxidefunc-
tionality, a typical behavior of an electrophilic oxidant (Scheme 3). Also, the
6 ORGANICREACTIONS
OS OO CCHH33 (CF3) OS + O S O
S S S
O
SSO
(major) (minor)
Scheme 3. Competitive oxidationof the sulfide vs. sulfoxide functionalitiesin thianth-
rene-5-oxide (SSO) by the dioxiranesDMDand TFD.
kinetic data6 for the oxidation of sulfides and sulfoxides have revealed the elec-
trophilic character of dioxiranes. Thus, the heteroatom oxidations by dioxirane
aregenerallyexplained in termsof aS 2-typeattackof theheteroatom lonepair
N
on the dioxirane peroxide σ∗-orbital.21,22
A possible single-electron-transfer (SET) mechanism in N-oxidations23,24 has
been discounted21 on the basis of kinetic experiments by comparing the relative
rates of oxygen transfer by DMD with those of alkylation by methyl iodide. For
the latter, an S 2 mechanism unequivocally applies. Similar reactivities (linear
N
correlationofrates)forN-oxidationalsoestablishtheS 2pathwayfordioxirane
N
oxidations.ThisconclusionissupportedbyakineticstudyoftheDMDoxidation
of substituted N,N-dimethylanilines.25
The heterolytic mechanism is presumably also valid for a variety of oxygen-
type nucleophiles, e.g., amine N-oxides, ClO−, HO−, HOO−, RO−, ROO−,
RC(O)OO−, and −OS(O) OO−, which all catalyze the decomposition of dioxi-
2
ranes with the evolution of molecular oxygen.26,27 A typical case is illustrated
with 4-dimethylaminopyridine N-oxide in Scheme 4.26 The chemiluminescence
emitted by the generated singlet oxygen confirms the heterolytic nature of the
dioxiranedecomposition.26 Furthersupportforthismechanismhasbeenprovided
by theoretical work, from which it was concluded that the oxidation of primary
amines by DMD does not proceed by a radical process.28
O
O
S 2
N
NMe
2
NMe
2
S 2
Me2N N O– + O O N N 1O2 +
O O N
O
O
3O
2
hν (1268 nm)
Scheme 4. S 2 Mechanismfor the N-oxide-induceddecompositionof DMD.
N
DIOXIRANEOXIDATIONSOFCOMPOUNDSOTHERTHANALKENES 7
Alkanes and Silanes
Two mechanisms have been suggested for the insertion of an oxygen atom
into the Y–H bond of alkanes and silanes. Abundant evidence, which includes
kinetics,29 kineticisotopeeffects,30 andstereoselectivity,31 allunequivocallysup-
port a concerted oxenoid-type mechanism (Figure 1).
Nonetheless, radical reactivity has been observed recently and interpreted
in terms of the dioxirane diradical as the active oxidant, in particular, the so-
called“molecule-inducedhomolysis.”32–35Ithasalsobeenproposed36thatalkane
hydroxylationmayproceedbyarate-determiningoxygeninsertionintothealkane
C–Hbondtogenerateacagedradicalpair,followedbyveryfastcollapse(oxygen
rebound) to hydroxylated products (Scheme 5).
That hydroxylation of (R)-2-phenylbutane proceeds with 100% retention to
furnish (S)-2-phenylbutan-2-ol for both DMD37 and TFD31 sheds serious doubt
on the involvement of out-of-cage radical intermediates in such C–H oxidations
(Eq. 2).
O O k
Et H + slow
Ph
(R)
=/
H H k = 1011s–1 H
rot
O O O O O O
Et Et Ph
Ph Ph Et
(S) radical pair (R) radical pair
k k > 1011s–1
conc reb
fast k
diff
Et OH radical chain Et OH + HO Et
Ph Ph Ph
(S) (S) (R)
Scheme 5. Concerted oxenoid-type (k ) vs. oxygen-rebound (k ) mechanisms for
conc reb
C–H insertionby DMD.
H DMD or TFD HO
(>90%)
Ph Et Ph Et (Eq. 2)
(R) 70.9% ee (S) 71.0% ee
R
R R
δ+
H O O CH3(CF3)
δ–
Figure 1. Concerted oxenoid-typetransitionstate for C–H insertion.