1)oxidation of alkenes to diols

14 Pages·2014·1.92 MB·English

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Commercialavailableperoxides*
Inorganicperoxides
Na2O2 CaO2 Li2O2 BaO2 Ni2O3 NiO2 xH2O H2O2(30%) ZnO2 NaBO3 4H2O MgO2 TbO2 SrO2 Na2CO3 1.5H2O
sodium calcium lithium barium nickel nickel(II) hydrogen zinc sodium magnesium terbium Stronium sodium
peroxide peroxide peroxide peroxide peroxide peroxide peroxide peroxide perborate peroxide peroxide peroxide percarbonate
$109/100g $27/100g $32/50g $146/500g $106/5g $350/4L $75/1kg complex $30/1g $38/100g
hydrate tetrahydrate $91/2.5kg
$40/250g
$40/1g $94/1kg
(NH ) S O Na S O K S O 2K SO KHSO K SO 5[Bu N+] SO ] HSO ] SO ]
42 2 8 2 2 8 2 2 8 2 5 4 2 4 4 5 4 4
ammonium sodium potassium Oxone® OXONE®
persulfate persulfate persulfate monopersulfate tetrabutylammoniumsalt
$39/100g $87/2.5kg $70/500g compound $156/25g
$60/1kg
Organicperoxides-1
O
CO3H O
HOO tBu
OO O O O O H3C(H2C)9H2C O O CH2(CH2)9CH3
tBuOOH urea H2O2 BzOOBz OOH tBu O
Cl
O
tert-Butyl Urea Benzoyl mCPBA Cyclobutane 2-Butanone tert-Butyl Lauoyl
hydroperoxide hydrogen peroxide $81/100g maloyl peroxide peroxide peroxide
solution(5-6M) peroxide $92/500g peroxide $129/500mL $134/1L $81/100g
$47/25mL $88/250g $100/1g
Cl
O O
Cl O OMe Me O OMe Me Ph OMe Me O O O O O
O O O Me O Me O Ph O O tBu
Cl Ph Me Me Me
Me
O
2,4-Dichlorobenzoyl Cl tert-Butyl tert-Butylperacetatesolution, Dicumyl tert-Butylperoxy 1,1-Bis(tert-amylperoxy)cyclohexane
peroxide,50%inDBP peroxybenzoate 50%inmineralspirits peroxide 2-ethylhexyl solution,80%inmineralspirits
$59/100g $86/500mL $77/500mL $123/500g carbonate $74/500g
Me $77/500mL
Me Et
O O O OtBu Me O OtBu O O O O
O tBu O OtBu O O O O O
O OtBu O O O
OH Et Me
Me Me Me O O Et O O
O Me
tert-Butyl 1,3-Bis(2-tert-butylperoxyisopropyl)1,1-Bis(tert-butylperoxy)-3,3,5- 3,6,9-Triethyl- 2,4-Pentanedione 2,2-Di(tert-butylperoxy)
monoperoxymaleate benzene trimethylcyclohexane 3,6,9-trimethyl-1,4,7-triperoxonane peroxidesolution butane
$75/5g $150/250g $78/500mL $62/100g $45/500mL $86/500mL
*PricesarebasedonAldrichInventory(pricefromothersupplierswillnotbenoted);anyresoucelessthan10mgwillnotbeincluded

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Hydrogenperoxidebasedoxidants: Me Me OTMS Me Me OH
TBHP,MoO2(acac)2
H O (NH ) Mo O 4H O Prep:H2O2andMoreagentmixingforthereaction;stablepowder O
2 2Hydrog4e6npe7rox2i4de 2 Application:1)[Mo]Amongthebestcatalystfortheepoxidations benzene,CF3CO2H
ammoniumheptamolybdate sinceitischeapandeasyhandling;2)monoanddi-subustituted Me 60°C,72h Me
alkenesreactveryslowly 85%
selectivelyonmorehinderedalcohol
Tetrahedron.Lett.1981,2595.
OH O
O
Me H2O2+[Mo] Me O Cl1.TBHP,pyridine,CCl4,0°C Cl
TBA,K2CO3,THF,6d O 2.96°C
44%
HO 90% HO
Isr.J.Chem.1984,134. J.Am.Chem.Soc.1975,2281.
O O O O O O Me O
H Me H2O2+[Mo] Me OEtCu(CTlOB4H)P6H2O Me OEt OMe O
HO TBA,K2CO3,THF,4d HO H Ph CH3CN,80°C O Ph OOtBu NC tBuOO OEt
OtBu
HO O 45% 66%
H 73% H 88% somenoticeableexamples
withoutthebase,epoxidationcanoccur J.Org.Chem.2010,5065-5071.
J.Am.Chem.Soc.1992,7375.
OtBu
OtBu OtBu
TBHP: P(Srheapr:p7l0e-s9s0'% aAqulderoicuhs solpurtoiocnedourreanhydtorous psroeluptaioren in hayndhryodcraorubson soTlvBeHnPts) O TFBeHCPl3,(0T.M1SeqN)3 OOtBuN3 D(3HmQ)o2lP%y)r OOtBuN3 O N3 O O N3 O N3
Application:1)oxidation ofalkenestodiols;2) oxidation ofallylic orbenzylic or H H
tBu propargylicpositionswithSeO2andTBHP3)epoxidationwidelyapplied;4)vicinal R CH2Cl2,0°C R R=H R
O OH diolcanbecleavedbyTBHPwithMoO2;5)alcoholcanbeoxidizedbyTBHPwith R=H,alkyl,aryl moderatetohighee 32%,93%ee 35%,96%ee90%,racemic
tbutylhydroperoxide Se or Cr compound; 6) sulfide can be oxidized to sulfoxide or sulfone; 7) 30-40%yield
phosphanescanbeoxidizedtophphosphineoxide;8)aminecanbeoxidizedtoN- Org.Lett.2013,3832. somenoticeableexamples
oxide or imine; 9) Kharasch reaction; 10) peroxy acetal can be made from
AntillahaschiralBronstedAcidcatalyzedperoxidationofimineonAngew.Chem.Int.Ed.2010,6589.
aldehydeorketonewithTBHP;12)alkylhalidecanbeconvertedtoalkylalcohol
fromGrignardreagentwithTBHP.
Me tBuOOH,AgOTf Me Br AgOTf Me
OH OH
Me TBHP,SeO2(5%mol) Me HO TBHP,VO(acac)2 O Me Br Br CH2Cl2,0°C Me OOH MeOH Me O O
tBuOH benzene,40°C,50h OH 50%
O 78% TetrahedronLett.1983,543-546.
60%
J.Chem.Soc.Perkin.Trans.1.1985,267. Tetrahedron.Lett.1976,3157.
mCPBAanditsfamilies:
O H Prep:stablein85%purity,100%purityispossible,storedinpolyethylene
TBHP,CrO3(5%) Cl O containerinfridge
O Application:1)epoxidationofalkenes(electron-riched);2)B-Vreaction;
CH2Cl2 O 3)Rubottumoxidation;4)oxidationofsulfidetosulfoxide(tandemedwith
47%(9%sm) soleSeO2gaveoxidationonbothsides meta-chloroperbenzoicacid Mislow-Evansrearrangement);5)oxidationofselenidesandphosphanes
andphosphites;
Tetrahedron.Lett.1983,2321.
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mCPBA,EtOAc Persulfatebasedperoxidereagents:
CH2Cl2,Na2CO3(aq.) OH
I CO2Me 5-20°C,1hour CO2Me K2S2O8/(NH4)2S2O8 Acaptp.(lkiicnaattiiocanl:ly1)slooxwiditzoingacpidr;im2a)ryoaxinddizisnegcoentdhaerrytoalcaolhdoelhsydtoealdehoyxdideizwin/go
65-67% potassium/ammonium aldehydeorketonestobenzoicacidwithmetalcatalysts;4)oxidizingaliphatic
amines to aldimines or nitriles with Cu(II)/Ni(II) as catalyst; 5)oxidizing
peroxydisulfate
J.Am.Chem.Soc.1983,2908. carboxylicacidtoperacidunderphasetransfercondition;
Elbsoxidation:
O H
OH
Cl O O+Me N Me HCl Atepmpplicfoartihoignh:1y)ieoldxi;d2a)tioenpooxfyaklceotohnoelactarnoobme MeO O 1.K2S2O8 MeO O
Me H Me preparedinonestepfromallylicalcohol;3) 2.NaOH
forced conditions lead to lactone or ester
mhyedtrao-cchhlloorriodpeerbenzoicacid-2,2,6,6-tetramethylpiperidine fromalcohol OH O 40% OH O
O
Me flavanolbasedstructure throughp-hydroxysulfateestersalts
Me O Me H
1.mCPBA,TMPHCl
Me H Chem.Rev.1951,49,91.
2.hydrazine HO Boyland-Simsoxidation: Me Me
HO Me Me Me Me Me Me N
68% N N SO - N
J.Org.Chem.1961,3615. (H4N)O3S O O SO3(NH4) O 3 OSO K+
3
KOH
NO
2 Characterization:Stableatambienttemperatureaswhitecrystal; OSO K
Application:epoxidationofalkenes;B-Vreaction o/p=2/1,22% 3
O J.Org.Chem.1992,2266.
H O C-Hoxidation:
O
Me
p-Nitrobenzoicperoxide
OH
K2S2O8,NaOAc,Cu(II)
PNPBA,CHCl3
MeCN-HOAc,80°C
reflux,23h
80%
69%
Angew.Chemie.Engl.1979,407. J.Org.Chem.1986,3693.
Me
O H O CO2Me Me K2S2O8,Fe(II) O O
O NaOAc-HOAc Me
Ph
O reflux
OOH 81%
CO H Oxidationofalkenes: Tetrahedron.1980,3559.
Perbenzoicacid tButyl4-benzoylperObenzoate p-Metho3xyl NH NH2
eroeepfxatorcexatimimdoaneint/liyoeoxnliikd/oBear-tVmiosCnuPlfiBdAe PwA(3rpi6tehp0plt:inBcfmruaott,myioclonhcmyo:drlporreaowsrg-eptpedoemntroodpxierniedrgafelutb.uxerenozfinoAiitcIiBaaNtcio)idnof Pwprraeessps:uircrfreraaodrmMbiaoetneercydsultpereywrrbilatigheldhnetz2howyicidtkheWacOiwd2hh,iigcahhs N N NNR H2KO92S,182%O08°C N N NNR K2S2O8HE2StOOH4,/HHO2OAcCHaOroOS'sOOa2cHid+ 6800%°C OOHH
radicalreaction; stable as mCPBA; adenosine Peroxymonosulfuricacid
Utilization:verysimilarasmCPBA Chem.Pharm.Bull.1992,1656. J.Org.Chem.1960,1901.
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Oxidationofalcohols: NO2 O O O O
O O (ArSO3)2
OH(NH4)2S2O8,Cu(II) S O O S X X
O
AcOH,100°C O O X=OR,NR2 around60% ONs
O N
96% 2
p-Nitrobenzenesulfonylperoxide J.Org.Chem.1990,1267.
J.Org.Chem.1983,4914. J.Org.Chem.1991,1014.
OH OH Application:Pseudohalogenreagentwhosereactivityiscomparabletothatofchlorine;
Na2S2O8 -hydroxyketonecanbemadefromenolderivatives(OTMS,OAc,NR2)
CN O
H2O,60°C
CN CO H
40% 3 Preparation:o-sulfobenzoicanhydrideand30%H2O2inacetone,stablein
acetone;
Bulll.Acad.Sci.USSR,Div.Chem.Sci.1984,2099.
SO H Utilization:epoxidationandhydroxylationhavebeenreported;sometimestheB-V
C-Hoxidation: 3 reactiongavebetterresultcomparedtoperaceticacid-BoronEtherate
O o-Sulfoperbenzoicacid
CO2H Na2S2O8
O
Ag(I),Cu(II), O Preparation:insuwithKO2andsulfonylchloride
Me MeCN,80°C O Application:epoxidationofalkenes(basicconditionepoxidation);
56% S oxidationofbenzylicposition(fewcase);oxidativedesulfurizationof
Tetrahedron.Lett.1985,2525. O OK thiocarbonylcompounds(sulfurylureatourea)
H PoNtaOss2ium experimentssuggestedaradical 2KHSO5oKxHoSnOe4 K2SO4
o-Nitrobenzeneperoxysulfonate
underdimethyldioxirineitem
K2S2O8 Me 2+
R N HOAc/KOAc
H2OR,1=0H0°C O R [Ag] R OH
86% R=H NAgN S2O82- isomerdistribution
O N N subs. 2-OAc 3-OAc 4-OAc yield(%)
CONHMe
anisole 68 0.6 31 63
biphenyl 21 0 79 18
Bis(2,2'-bipyridyl)silver(II)peroxydisulfate naphthalene 95 5 - 63
Na2S2O8,K2CO3 Me 4-bromoanisole 100 0 0 35
N oneelectronoxidantofelectron-richaromaticcompounds
4-fluoroanisole 0 0 100 35
H2RO=,1O0M0e°C canbealsoincatalyticversionwithK2S2O8 4-t-Butylanisole 100 0 0 63
O
76%
R=OH Symmetricperoxidereagents:
NO2 Ph Alternatename:DBP;relativeunstable;
Application:1)widelyusedasradicalinitiator;classicanti-Markovnikov
O
reaction;Miniscireactionofradicalfromalkylhalides,dioxane,DMFandeven
OSOO O S Ph X X Ph (ArSO3)2Ph X OOSOAr MeOH XPh O O O coyfcalroohmexaatincse;tuosperdotinonhaytderdohxyeltaetrioonaroofmeantoiclactoempounds;usedasbenzoyloxylation
O O X=Se,Te,S 16-98% OMe Ph
dibenzoylperoxide
J.Am.Chem.Soc.1979,5687.
NO
2
m-Nitrobenzenesulfonylperoxide
Preparation:potassiumcarbonate,sulfonylchlorideandhydrogenperoxide;
Application:moderatearomaticsubstitutiontogivearylsulfonates,whichcanbehydrolyzedtophenols

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DMDOandTFDO:(itisworthytogiveanothergroupmeetingonthesetworeagents!) H2O2 BF3 Et2O Utilization:B-Vreactionusing90%H2O2andBF3 Et2O,much
O O Preparation:recenteasyOrganicSynthesisprocedure; hydrogenperoxide-Borontrifluoride strongercondition;moderatehydroxylationofareneswithHFas
additive
Application:Epoxidationofkindsofalkenes!C-Hactivationofalkaneswiththe
Me Me
retentionofthestereochemistry;readilyoxidizeaminesandsulfide. MeO C MeO C
Dimethyldioxirane 2 2
oxidationofvincinaldiols:
HN 1.H2O2,BF3 OEt2,CH2Cl2 HN
OH OH maskedduring 2.TMSNCO
HO 1.2eqDMDO O 1.2eqDMDO oxidation MeO N MeO N
H
acetone,0°C acetone,0°C OH NH2
OH 98% OH >98%OeHe 96% >98%Oee HO J.Am.Chem.Soc.1992,1375. O
Tetrahedron.Lett.1993,4559. J.Org.Chem.1993,3600.
O O
O O PUrteilpizaartaitoionn::eGpouxilildaautmone'sofperoxctreedmuerei,nsetratballekeinnefrsidsguechfoarsaCwFe3ek; O OH O OH Pthreeppraersaetinocne:opfhNthaaOlicHaonrhMydgrOideandH2O2in
Me CF3 substitutedalkenes;oxidationofhinderedphenolssuchas2,6-di-t-butyl OH and O- Utilization:epoxidationofalkenes,B-Vrxns;
methyl(trifluoromethyl)dioxirane phenol;somemagicC-Hoxidation O O Mg2+ 6H2O andoxidationofamine,sulfideandselenium
O monoperoxyphthalicacid
OH H
1eq.TFDO
+ tBuMe SiOOH Hg(OTf)
2 2 soluableinmostsolvent,mercury,toxic!
0°C,7min hydroperoxide-mercurytriflate
H H
86% 13%
1.peroxide,Hg* BrHg OOtBu
Tetrahedron.Lett.1992,7929.
2.KBr,H2O-CH2Cl2
3eq.TFDO I OOtBu I OOtBuAgOTf,CH2Cl2 O O
I2,CH2Cl2 +
H H
CH2Cl2,0C,3h 63% >45%
OH
H 85% H NaI,acetone
O O 50%
H H
J.Org.Chem.1992,5052. usedinperoxy-mercurationtoepoxidation(byCorey)
J.Chem.Soc.Perkin.Trans.1.1991,1923.
Metal-basedperoxides:
NaBO3 4H2O otoxiodxizidinagntasgseuncthfoarsaHv2aOri2e,tyMoefCfOun3cHtioonramlCgrPoBuAps;;Inchgeeanpe/rsaal,fen/ocotngvoeondiefonrtalternative Ce(OH)3O2H fruenacdtiiloynaavlagilraobulpes,sstuacbhlearsedalcsoohlido.lm(aillddeohxyiddeiz)i,npghreenaogle(tnotfor
sodiumperborate dihydroxylation,B-Vreactionthoughwhichwasreportedbefore;industrylevelviable cerium(IV)trihydroxidehydroperoxide quinone)andamine(toazocompound)
alternativetohydrogenperoxidefortheoxidativedecompositionof
organophsphorusesterwastes
OAc
NaBO3 4H2O LiOOH PreparedinsituwithLiOHandH2O2;
Utlization:cleavageofdifferentkindsofamideligands,suchasEvan's
Ac2O,H2SO4,reflux OH lithiumhydroperoxide oxazolidones,Davis'sultamauxiliary,andMyer'spseudoephenamineauxiliary;
estercanbealsocleaved.
59% relativeharshcondition
Synth.Comm.1988,937.
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R O Preparation:yellowcrystalfromPalladium(II)acetateand R
m.p.52°Cw/detonation; F C O O tBu
SeOOH Preparation:diphenyldiselenidewith30%H2O2 3 Pd O tUritflluizoartoioacne:taiclkaecniedsatnodmTeBthHyPlketone O
Application:majorforB-Vreaction;andoxidizingagentformultiple O Pd
R R=HorNO2 functionalgroupssuchashydrazyliminetocyanogroups palladTiurimfluto-rBouatcyeltPaeteroxide keTyfiOntermedOiateX
Benzeneperoxyseleninicacid
generalmechnism: differentfromWacker
Me Me Me Pd OTf oxidation
F C O O tBu Me
CHO H2O2,DNPDS OCHO KOH OCHO + 3 Pd O + R
R R R
CH2Cl2,20°C MeOH O O
H2O2canbeusedasoxidantforthistransformation:
94%,suitableforphenolwithEDGgroups Varation:Pd(PPh3)4+aq.H2O2
Me
Tetrahedron.1987,2853.
O [Pd],tBuOOH,benzene O Me Me
Blackhydrouspowder
NiO2 Utilization:oxidationofprimaryalcoholstocarboxylicacidinaqueousmedia,or 50°C,12h Ph O OH
Ph O Me
oxidizeallylic,benzylicalcoholtoaldehydeinorganicsolvent;oxidizephenolsto
Nickel(II)Peroxide 71%
polymericmixturesandquinones;oxidizealcoholoraldehydetoamideinammonia
solution;oxidizeaminetocyanoordiazocompounds;dehydrogenationof J.Chem.Soc.Chem.Comm.1983,1245.
unsaturatedhertocycles
Peracidseries:
HMPA
O O Preparation:MoO3,30%hydrogenperoxidewithHMPA,free- O Thesoleperoxidewhichcanbegeneratedinsitu(industralfavored)
Mo flowingyellowcrystal OH Electrophilicreagentcapableofreactingwithmanyfunctionalgroups;preparedinsituin
O N O AoxpidpalitcioantioNn,:Sc,oPm.monreagentOfoHrhydroxylationofenolates; perOaceticacid ifnodrmusattriyonfowrheepnoxcidaarrtyioinngonfoveagceidtasbelnesoitiilvaengdrofautptys;a(tceidrmeisntaelrsa;lkbernoeasdararengseluogfgeispho);xiidnes
O O
somecases,differentregioselectivitiescanbeobservedcomparingtomCPBA;oxidation
ofarenestophenolsinlowyield;B-Vreaction;aminetonitroso,sulfidetosulfone
oxydiperoxymolybdenum(Py)-HMPA Me
TMS TMS
notsensitivetoequilibration Me NaOAc,MeCO3H
comparedtoDavis'reagent 86%
Me Et CH2Cl2,7°C Me Et
O O O OO
PhN OO O Ph O M o O H Chem.L7e8t%t.1983,1771.
Ph OOMOo O N Ph O O O 3-butenolides,mCPBAiscomparedworseforthisreaction
H
Oxoperoxobis(N-phenylbenzo- OAc OAc
hydroxamato)molybdenum(VI) Me2mNolybdenum(VI)Me RuCl3,MeCO3H OH
Oepxoidxaytdioantioonfporfimalakeryniacnadlcsoehcoolnsd(anroytacolcmohmoolsn) oAfpupnlifcuantcitoionn:aelinzaendtisoismeplelectaivlkeeenpeosxidatioin MeO2C MeCN/H2O/CH2Cl2 MeO2C O
55%
O PdPPh3 NC Ph (PPh3)2PdO2 L PdO O 23-50°C LPd O J.Org.Chem.1993,2929.
PpheorosOxpyhlibnies()tpPraipPllhhaed3niuyml- NC Ph TH7F2,%0°C NLCNC PhPThFA 95% NLCNC Me OTBS NaORAucC,Al3c,OMHe,CEOtO3HAc,rtMe OTBSOAc
PUrtielipzaartaiotino:nM:Pildd(oPxPidha3t)io4nanodfaOlk2enes, J.Organo.Met.1975,115. NC O Ph O NH 99% O NH
sulfurcompounsandoxime NC Ph
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O H HO
O H Preparation:insituwithTf2Oand90%H2O2orUrea H2O2; Preparedfrom90%hydrogen O
F C Application:thestrongestorganicperoxyacid;verypowerful O peroxideandmaleicanhydride
3 O O epoxidationreagents,morethanmCPBA;diolsarethesubsquently O Utilization:forepoxidation;B-V
Trifluoroperaceticacid hydrolysisbyTFA;B-Vreactionisfacile;variousofheteroatomscanbe CO H reaction(mostcommon)nobuffer
oxidized Peroxyma2leicacid needed;oxidizeaminetonitrogroup
-TetralylHydroperoxide
H O H
unusuallystableperoxidebutstillneed PreparedfromthetetralinandO
Me cautions;forepoxidation,itisfaster Utilization:forepoxidation,usua
N N Ph OOH comparingtoTBHPandhigheryield;a mCPBAorTBHP/Moissuperior;
TFPAA,H2O2 cumylhydroMpeeroxide rseullifaobxliederefaogrmenattifoonrewnitahnTtioi(sOeiPlerc)t4ivaend oloxwidyaiteioldnofaromaticstogiveph
CH2Cl2,23-0°C diethyltartrate
76% Me Me preparedfromdiphenylpyrazole,90%hydrogenperoide(caution!)
anddibromo-5,5'-dimethylhydantoin
OMe OMe Ph Ph
1fastrate2mildreaction3stablereagent
J.Org.Chem.1983,5199.
Br N N OOH Utilization:oxygentransferreagents;heteroatomandalkeneoxida
Miscellaneousperoxides: fasterN,Soxidationcomparedto(samemagnitude)flavinhydrope
pyrazolylperoxide
O O H stableat-30°Cforyears and(twoorders)acyclicazohydroperoxidesand105morethanH2O
H O
H N N
O-ethyElpteOroxycaOrbOoHnicacid 2 H HO Et3SiOOOH PRreeapcatirveidtyf:rovmerytrileiktehythlseilacnoemabnodoOfo3,zostnaebl(eoxfoidraativfeewclmeainvuatgeesoafta-7lk8e
hydrogenperoxide-urea triethylsilylHydrotrioxide Et3SiH(reductiontoalcoholoraldehyde)
Preparation:notstabletostore;ethyl stablewhitepowder;utilizedasanhydrous
chloroformatewithhydrogenperoxideinsitu "hydrogenperoxide"inorganicsolventforthe O O H
Utilization:epoxidationofalkenesonbiphase standardreactionssuchasepoxidation,B-V Et3SiO3H TBSOTf Me O
condition,cheapandevironmentallybenign reactionsandoxidationreactions MeO CH2Cl2 O O OO
CF H 48% OMe
3 N H OMe
F3C OOH2H R OO Tetrahedron.Lett.1985,4485.
2-Hydroperoxy-
hexafluoro-2-propanol R=PhorMe O Preparation:fromSO3andTMSOOTMSusingascrudeat-30°C
PUrtielipzaartaiotino:ne:phoexixdaaftluioonr;ooaxciedtiozneeawldiethhy3d0e%toorac9i0d%wiHth2oOu2t Peroxyacetimidicbeatcteidrl(ePaavyinngegorxoiduaptitohna)nHO-OH Me3SiO OS OOSiMe3 Adepcpolmicpaotisoen(:esxtrpolonsgeo)xaidtartn!tU;Bse-Vimomxideadniatteinlyn.onproticsolvent;
touchingalcohol;oxidizesulfidetosulfoxideandsulfones weakreactivityforepoxidation,to alkenestoketones;sulfidestosulfoxides,pyridinetopyridine-oxide
showacetonitrileassolventcanhelp Bis(trimethylsilyl)
epoxidationusingotherperoxides monoperoxysulfate
Ph3COOH oxidantusefulforenantioselectivemetal- HN H Me peroxide Me
triphenylmethyl catalyedepoxidationofallylicalcoholsand O
Hydroperoxide enantioselectiveoxidationofsulfidesto Cl3C O CH2Cl2,-30°C O
sulfoxides(moderatetopoorresult) highyield
Trichloroperoxy-
O acetamidicacid J.Org.Chem.1990,93.
O existinpollutedair,easyto
Me O NO2 generateperoxyradical;not Preparedwithtrichloroacetonitrile
usefulcomparingtomCPBA and30%H2O2;mostofthetime
Peroxyacetynitrate whichcanbesubstitutedby
andH2O2 commonreagentsforepoxidation