PERACETIC ACID 1
General Considerations. Peracetic acid oxidizes simple
Peracetic Acid1
alkenes, alkenes carrying a variety of functional groups (such as
ethers, alcohols, esters, ketones, and amides), some aromatic com-
O
H
pounds, furans, sulfides, and amines. It oxidizes ²-lactams in the
presence of catalysts. Ketones and aldehydes undergo oxygen in-
O
O
sertion reaction (Baeyer Villiger oxidation).
[79-21-0] C2H4O3 (MW 76.06)
Epoxidation of Alkenes. Peracetic acid is a comparatively
InChI = 1/C2H4O3/c1-2(3)5-4/h4H,1H3
safe reagent for small-scale reactions. In industry, to avoid the
InChIKey = KFSLWBXXFJQRDL-UHFFFAOYAD
hazards involved in handling large quantities of the reagent, it is
prepared in situ. Peracetic acid prepared in this fashion is widely
(electrophilic reagent capable of reacting with many functional
used for epoxidation of vegetable oils and fatty acid esters. To
groups; delivers oxygen to alkenes, sulfides, selenides, and
the substrate in acetic acid containing catalytic (1% by weight)
amines)
ć%
quantities of H2SO4 maintained around 50 C is added gradually,
Alternate Name: peroxyacetic acid.
with stirring, 50% H2O2 at such a rate that there is no buildup in the
ć% ć%
Physical Data: mp 0 C; bp 25 C/12 mmHg; d 1.038 g cm-3 at
concentration of H2O2. The peracid is consumed as it is formed
ć%
20 C.
(eq 1). The addition of H2O2 is usually completed in 2 h and then
ć%
Solubility: sol acetic acid, ethyl acetate, CHCl3, acetone, ben-
the temperature is raised to and maintained at 60 C until all the
zene, CH2Cl2, ethylene dichloride, water.
H2O2 is consumed (about 3 h). The reaction mixture is diluted
Form Supplied in: 40% solution in acetic acid (d 1.15 g cm-3)
with water, at which point the epoxides (being water-insoluble)
having approximately the following composition by weight:
separate out. The use of hexane during the reaction minimizes
peracetic acid, 40 42%; H2O2, 5%; acetic acid, 40%; H2SO4,
epoxide ring opening. Since the catalyst (H2SO4) is essential for
1%; water, 13%; diacetyl peroxide, nil; other organic com-
the speedy formation of peracetic acid, in situ methods can be
pounds, nil; stabilizer, 0.05%. A solution of the peracid in ethyl
used for preparing only those epoxides which can tolerate the
acetate is also available commercially.
presence of the acid catalyst. Epoxides of fatty acid esters are
Analysis of Reagent Purity: assay using iodometry;2 estimation
obtained in good yields if the reaction temperature and time taken
of diacetyl peroxide.3
for completion of the reaction are properly controlled.
Preparative Methods: prepared in the laboratory by reacting
Acetic Acid with hydrogen peroxide in the presence of cat-
H+
alytic quantities (1% by weight) of Sulfuric Acid; when 30% MeCO2H + H2O2 MeCO3H + H2O (1)
H2O2 is used the concentration of the peracid reagent obtained
is less than 10%.1a If a stronger solution of the reagent is
Peracetic acid in ethyl acetate is a better reagent for preparing
required, 70 90% H2O2 must be used. Caution: for hazards
epoxides from alkenes than the reagent in acetic acid since the
see Hydrogen Peroxide. Hydrogen Peroxide Urea (which is
large quantities of acetic acid in the latter reagent facilitate epoxide
commercially available and is safe to handle) has been used as
ring opening. However, since the reagent in acetic acid is more
a substitute for anhydrous hydrogen peroxide.3 In the prepa-
readily available, it is normally used for epoxidation; the sulfuric
ration of peracetic acid from acetic anhydride and H2O2, the
acid present in the commercial sample has to be neutralized by
dangerously explosive diacetyl peroxide may become the major
adding sodium acetate before the epoxidation. After epoxidizing
product if the reaction is not carried out properly.1a
the alkene with peracetic acid, the reaction mixture is diluted with
Purification: peracetic acid is rarely prepared in pure undiluted
water. The unreacted peracid, acetic acid, and traces of hydrogen
form for safety reasons. The commercially available material
peroxide are removed in the aqueous layer. The separated epoxide
contains acetic acid, water, H2O2, and H2SO4. After neutral-
is filtered if it is a solid; when the epoxide is a liquid, the organic
ization of the sulfuric acid, this reagent is satisfactory for most
layer is separated using a small quantity of solvent, if needed.
reactions. If water is undesirable, an ethyl acetate solution of the
Another method of workup is to remove unreacted peracid and
reagent may be used. Details for the preparation of the H2O2-
acetic acid through evaporation under reduced pressure.
free reagent are available.4
Epoxidation of terminal alkenes with organic peracids is slug-
Handling, Storage, and Precautions: peracetic acid is an explo-
gish since the double bond is not electron rich (eq 2).6
sive compound but is safe to handle at room temperature in or-
ganic solutions containing less than 55%. Use in a fume hood.
MeCO3H, NaOAc
Na2CO3, CH2Cl2
Since peroxides are potentially explosive, a safety shield should
O
(2)
ć%
generally be used.5 Peracetic acid can be stored at 0 C with es-
20 °C, 4 d
sentially no loss of active oxygen and at rt with only negligible 53%
losses over several weeks.
Adequately substituted acrylic esters furnish epoxides in good
yields. Ethyl crotonate has been epoxidized in kg quantities
according to eq 3;7 the workup is simple, involving direct frac-
Original Commentary
tionation of the reaction mixture. For the preparation of epoxide
(1) from ethyl crotonate using Trifluoroperacetic Acid, the yield
A. Somasekar Rao & H. Rama Mohan
is 73%.8 The sensitive allylic epoxide (2) has been prepared
Indian Institute of Chemical Technology, Hyderabad, India
according to eq 4.9 This procedure has been applied successfully
Avoid Skin Contact with All Reagents
2 PERACETIC ACID
O2N
for the preparation of allylic epoxides from 1,3-cyclopentadiene,
1,3-cycloheptadiene, and 1,3-cyclooctadiene.
10 equiv MeCO3H
CH2Cl2, 23 °C, 18 h
CO2Et O CO2Et
MeCO3H, EtOAc
(3)
85 °C, 5.5 h
75%
(1)
O2N O2N
O O
O
40% MeCO3H
+ (8)
Na2CO3, CH2Cl2
(4)
rt
69%
(2)
73:27
A systematic study of the epoxidation of the acyclic allyl
Epoxidation of the triene (3)2 is regioselective, involving re-
alcohol (7) has been carried out, employing several reagents.14
action at the tetrasubstituted double bond (eq 5). Epoxidation of
Epoxidation with peracetic acid generated from urea/H2O2
(3) using m-Chloroperbenzoic Acid furnishes the monoepoxide
showed small syn selectivity (eq 9). m-CPBA epoxidation of (7)
in 76% yield.10 Epoxidation of the diene (4) was regio- and stereo-
furnished in 87% yield a 40:60 mixture of the epoxy alcohols (8)
selective (eq 6);11 the more substituted double bond was epoxi-
and (9).
dized from the less hindered side.
OH
urea H2O2
MeCO3H, CH2Cl2
Ac2O, Na2HPO4
Na2CO3, 15 °C
(5)
O
CH2Cl2
79 84%
62%
(3)
(7)
OH OH
MeCO3H (2.9 equiv)
H H
TBDMSO
EtOAc, 25 °C, 10.5 h
O O
+ (9)
H
72%
O
O
O
(4)
H H
(8) 57:43 (9)
TBDMSO
(6)
H
O
O
Epoxidation of Alkenes via Peracids Generated In Situ.
Alkenes have been epoxidized by reacting them with peracids
generated in situ. The system consisting of molecular oxygen and
Epoxidation of the unsaturated Å‚-lactone (5) furnished stereo-
aldehydes, particularly isobutyraldehyde and Pivalaldehyde, con-
selectively the epoxide (6), involving approach of the reagent from
verts various alkenes to epoxides in high yields when they are
the more hindered side of the double bond (eq 7).12 This selectivity
ć%
reacted at 40 C for 3 6 h (eq 10).15
is observed only when acetic acid is the solvent. The selectivity
was much less when m-CPBA was used.
Me2CHCHO (1.5 equiv)
C5H11 H C5H11 O H
EDC, O2 bubbling
(10)
40 °C, 3 h
O O O
H H
100%
MeCO3H, AcOH
O O O
25 °C, 16 h
+ (7)
96%
Oxidation of Furans. 2,5-Disubstituted furans are oxidatively
O O
cleaved by peracids; for example, see eq 11.16 m-CPBA can also be
(5) (6) 89:11
used for this reaction. 3-Butenolides have been synthesized by
oxidizing 2-trimethylsilyl furans with peracetic acid; as in eq 12.17
NaOAc (1.2 equiv)
Moderate stereoselectivity is observed during the epoxidation
TMS
TMS
MeCO3H (4 equiv)
of sterically unbiased 3,3-diarylcyclopentenes; the major product
CH2Cl2, 7 °C, 1 h
is formed through approach of the electrophile from the side trans Et (11)
Et
70%
O O O
to the better electron donor (eq 8).13
A list of General Abbreviations appears on the front Endpapers
PERACETIC ACID 3
MeCO3H
Ruthenium- and Osmium-catalyzed Oxidations. Ä…-Ketols
NaOAc, CH2Cl2
have been synthesized by reacting alkenes with peracetic acid
(12)
TMS R O R
O O
7 °C, 3.5 h
in the presence of a Ruthenium(III) Chloride catalyst.26 Ä…-Ketol
78%
R = Me2CHCH2CH2-
(19) was synthesized from the alkene (18) chemo- and stereoselec-
tively (eq 15). The two-phase aqueous system is essential for this
This reaction does not proceed smoothly when there is a reaction. Conjugated dienes, allylic azides, and Ä…,²-unsaturated
hydroxyl group in the furfuryl position; however, the reaction is esters have been oxidized with this reagent.
facile if the furfuryl OH is blocked. The reaction does not take
OAc OAc
place if electron-withdrawing groups are present on the furan ring.
RuCl3, MeCO3H
OH
m-CPBA is not a good reagent for this oxidation. An interesting
MeCN, H2O, CH2Cl2
(15)
application of this reaction has been published.18
55%
MeO2C MeO2C O
(18) (19)
Oxidation of Aromatic Compounds. Suitably substituted
aromatic compounds are oxidized efficiently to the quinones by
peracetic acid. The quinone (10) is obtained in 22% yield by oxi- The methylene group adjacent to the nitrogen of ²-lactams has
dizing naphtho[b]cyclobutene.19 Slow addition of 1,5-dihydroxy- been oxidized with peracetic acid in the presence of a ruthe-
naphthalene to excess peracetic acid furnished juglone (11) in
nium catalyst (eq 16).27 Peracetic acid is the best oxidant for
46 50% yield.20
this reaction. Instead of ruthenium, OsCl3 can be used to cat-
alyze the oxidation.28 The peracetic acid required for the reaction
O O
can be generated in situ from acetaldehyde and molecular oxygen
(eq 17).29
OTBDMS OTBDMS
5% Ru cat
O OH O
OAc
NaOAc, AcOH, MeCO3H
(10) (11)
(16)
in EtOAc, rt, 2.5 h
NH NH
99%
O O
Baeyer Villiger Oxidation. A systematic study of the
99% de
Baeyer Villiger reaction of the bicyclic ketone (12) has been
carried out employing different organic peracids.21 Selective
Ru cat, MeCHO, O2
formation of lactone (13) was highest when peracetic acid was MeCO2H, NaOAc
OAc
EtOAc
used (eq 13). Reaction of (12) with m-CPBA furnishes a 55:45
(17)
NH
88% NH
mixture of (13) and (14) in 81% yield. O
O
MeO H2O2, MeCO3H MeO MeO
NaOAc O
36 h, rt
O
O
O
+ (13) Other Applications. Peracetic acid has been used to (a) ox-
O
72%
idize primary amines to nitroso compounds,30 (b) oxidize sec-
OCH2Ph OCH2Ph OCH2Ph
ondary alcohols to ketones in the presence of a CrVI ester catalyst
(12) (13) 92:8 (14)
(eq 18)31 or sodium bromide,32 (c) oxidize sulfenamides to sul-
fonamides (eq 19),33 (d) oxidize iodobenzene to iodosobenzene
Position-specific Baeyer Villiger rearrangement has been diacetate34 and iodoxybenzene,35 and (e) oxidize N-heterocycles
observed in the reaction of peracetic acid with some polycyclic such as pyridine to N-oxides.36 Ä…,²-Unsaturated aldehydes (and
ketones.22,23 An µ-lactone, required for the synthesis of erythrono- Ä…,²-unsaturated ketones) do not undergo facile epoxidation with
lide B, was synthesized in 70% yield through position-specific peracetic acid since the double bond is not electron rich. However,
Baeyer Villiger rearrangement of a cyclohexanone having sub- the acetals of Ä…,²-unsaturated aldehydes can be oxidized readily
stituents on all the ring carbons;24 the ketone was treated with (eq 20).37 For the epoxidation of Ä…,²-unsaturated aldehydes with
ć%
excess 25% peracetic acid in ethyl acetate for 6 days at 55 58 C. H2O2/base see Hydrogen Peroxide.
Peracetic acid oxidation of the keto ²-lactam (15) furnishes stereo-
selectively the interesting ²-lactam (16) (eq 14);25 the initially
MeCO3H
formed Baeyer Villiger reaction product undergoes further reac- OH O O O
Cr 0 °C, CH2Cl2
tion. Ketone (15) has also been reacted with m-CPBA in acetic
CCl4, 30 min
O O
(18)
acid but the selectivity is slightly less, forming (16):(17) in 10:1
96%
( )3 ( )3
ratio.
MeCO3H
O
N
K2CO3, EtOH, H2O
OCHO OCHO
MeCO3H, NaOAc
O
SNH2
H H
AcOH
88%
O
OAc OAc S
+ EtO
H H
83% (14)
H H
NH NH
N
NH
O O
O SO2NH2 (19)
S
(15) (16) 11:1 (17)
EtO
Avoid Skin Contact with All Reagents
4 PERACETIC ACID
20 (0.1 mol %)
O
OAc
OAc (21)
MeCO3H
32% CH3CO3H (in AcOH, 2 equiv)
O O
EtOAc
CH3CN, rt, 5 min
O O (20)
H H
89%
40 °C, 7 h
45%
Ph H Ph O H
Me Me
For industrial applications, peracetic acid is the most widely
N N
used organic peracid since it is inexpensive. It is the only com-
(R,R-mcp) =
monly used peracid which can be prepared in situ for epoxida-
N N
tion reactions, since the acid catalyst (1% H2SO4; eq 1), which
can facilitate epoxide ring opening, is used in low concentrations;
the accompanying acetic acid, being a weak acid, is not very ef-
O
ficient in epoxide opening. The in situ method is not hazardous.
20 (0.5 mol %)
Although the reagent is available commercially, it is also prepared CH3CO3H (1 equiv)
in the laboratory since its preparation is easy, fairly fast, and no
-20 °C, CH3CN
O
solvent is required for isolation. Epoxidation reactions and sub- 91%
O
sequent workup can be performed with no solvent, or only small
(22)
quantities of solvent since the peracid and accompanying acetic
O
acid are both water soluble and volatile. It is not essential that
20 (0.5 mol %)
the substrate should dissolve in the reagent (peracetic acid acetic
CH3CO3H (3 equiv)
O
acid).
0 °C, CH3CN
88%
O
O
[MnII(bipy)2(CF3SO3)2] (0.1 mol %)
First Update
(23)
5
5
CH3CO3H, rt, CH3CN, 5 min
94%
John E. Hofferberth
Kenyon College, Gambier, OH, USA
Oxidation of Saturated Hydrocarbons. The oxidation of
unactivated C H bonds to alcohols, acetylated alcohols, and
General Considerations. Peracetic acid has recently found
ketones by peracetic acid has been observed in the presence
utility as a primary oxidant in catalytic oxidations. To avoid
of a number of transition metal catalysts including: Ru/C,40
the degradation of certain catalysts, a convenient preparation
RuCl3,40,41 Cu(MeCN)4BF4,42 Cu(OAc)2,42 Cu(ClO4)2,42 and
of the reagent devoid of the sulfuric acid found in commercial
n-Bu4NVO3.43 Consistent with the putative-free radical mecha-
peracetic acid has been employed. The preparation involves treat-
nism of this reaction, selectivity and degree of oxidation depends
ment of acetic acid with 50% hydrogen peroxide in the pres-
on the substrate, the catalyst, and the specific reaction conditions
ence of the acidic resin Amberlite IR-120. Removal of the resin
employed. A wide range of alkanes are competent substrates, how-
yields solutions containing 8 10% peracetic acid (in acetic acid)
ever, most yield a mixture of oxidized products. The relative reac-
with pH <" 4 and <1% residual hydrogen peroxide.38 Appropriate
tivity of C H bonds in this type of oxidation follows the empirical
caution should be exercised during the preparation of this
trend: tertiary > secondary primary. Oxidation of adamantane
reagent as concentrated solutions of hydrogen peroxide in organic
highlights the synthetic potential of this technique when thought-
solvents are potentially explosive.
ful selection of alkane and reaction conditions is made (eq 24).41
Epoxidation of Electron-deficient Alkenes. Electron-rich
RuCl3 (1 mol %)
CH3CO3H (30% in EtOAc)
olefins are readily epoxidized by peracetic acid while terminal
and electron-deficient olefins exhibit only sluggish reactivity. A
TFA/CH2Cl2 (5:1)
70% conversion
number of manganese complexes have been identified as effi-
cient catalysts for the peracetic acid epoxidation of electron-
deficient olefins.38,39 The complex [MnII(R,R-mcp)(CF3SO3)2]
+ (24)
OH
OH
(20) is sufficiently robust to tolerate commercial preparations of
peracetic acid as a primary oxidant and has been shown effective
89% 9%
in the epoxidation of a broad scope of electronically and streri-
cally distinct alkenes (eq 21). The electrophilic character of the
active oxidant allows for regioselective epoxidation of electron- Catalytic Oxidation of Primary Alcohols to Carboxy-
rich double bonds at reduced temperature (eq 22). The simple com- lates. Nitroxyl-radical-mediated oxidation is a selective and mild
plex [MnII(bipy)2(CF3SO3)2] is an exceptionally active catalyst, approach to oxidize primary alcohols to their corresponding car-
which benefits from the commercially available bipy ligand, how- boxylate salts in the presence of unprotected secondary alcohols.
ever, requires peracetic acid devoid of sulfuric acid as the primary It has recently been reported that peracetic acid is an effective
oxidant (eq 23). Only modest enantio- and diastereoselectivites regenerating oxidant for the nitroxyl-radical catalyst 4-AcNH-
have been observed for peracetic acid epoxidations catalyzed by TEMPO (4-acetamido-2,2,6,6-tetramethylpiperidine-1-oxyl) in
this class of manganese complexes. the presence of cocatalytic sodium bromide (eq 25).44 Other
A list of General Abbreviations appears on the front Endpapers
PERACETIC ACID 5
common primary oxidants for TEMPO-catalyzed oxidations 2. Vogel, E.; Klug, W.; Breuer, A., Org. Synth. 1976, 55, 86.
include NaOCl, m-CPBA, KHSO5, NaClO2, and t-BuOCl. 3. Cooper, M. S.; Heaney, H.; Newbold, A. J.; Sanderson, W. R., Synlett
1990, 533.
OH ONa
4. Pandell, A. J., J. Org. Chem. 1983, 48, 3908.
4-AcNH-TEMPO (cat)
O
NaBr (cat), NaOH 5. Hazards in the Chemical Laboratory; Luxon, S. G., Ed.; Royal Society
O O
(25)
of Chemistry: Cambridge, 1992.
HO CH3CO3H (2 equiv) HO
HO HO 6. Kirmse, W.; Kornrumpf, B., Angew. Chem., Int. Ed. Engl. 1969, 8, 75.
5 °C, 10 h, pH 8.2
O O
n
n 85%
7. MacPeek, D. L.; Starcher, P. S.; Phillips, B., J. Am. Chem. Soc. 1959,
81, 680.
8. Emmons, W. D.; Pagano, A. S., J. Am. Chem. Soc. 1955, 77, 89.
Oxidation of Catechols. Muconic acids (2,4-hexadienedioic
9. Crandall, J. K.; Banks, D. B.; Colyer, R. A.; Watkins, R. J.; Arrington,
acids) are readily prepared by treatment of catechols with 4 equiv
J. P., J. Org. Chem. 1968, 33, 423.
of peracetic acid (32% solution in acetic acid) (eq 26).45 The
10. Shani, A.; Sondheimer, F., J. Am. Chem. Soc. 1967, 89, 6310.
ć%
reaction mixture is allowed to warm from 0 C to rt and stir for
11. Corey, E. J.; Myers, A. G., J. Am. Chem. Soc. 1985, 107, 5574.
2 3 d. The scope of the reaction has been demonstrated to include
12. Corey, E. J.; Noyori, R., Tetrahedron Lett. 1970, 311.
alkyl- and chloro-substituted catechols in addition to a number of
13. Halterman, R. L.; McEvoy, M. A., Tetrahedron Lett. 1992, 33, 753.
dimeric catechols. Products commonly include geometric isomers
14. Back, T. G.; Blazecka, P. G.; Vijaya Krishna, M. V., Tetrahedron Lett.
and lactonized isomers of the target muconic acid.
1991, 32, 4817.
15. Kaneda, K.; Haruna, S.; Imanaka, T.; Hamamoto, M.; Nishiyama, Y.;
OH
Ishii, Y., Tetrahedron Lett. 1992, 33, 6827.
32% CH3CO3H (in AcOH, 4 equiv)
OH
16. Kobayashi, Y.; Katsuno, H.; Sato, F., Chem. Lett. 1983, 1771.
0 °C to rt, 48 h
70% 17. Kuwajima, I.; Urabe, H., Tetrahedron Lett. 1981, 22, 5191.
18. Tanis, S. P.; Robinson, E. D.; McMills, M. C.; Watt, W., J. Am. Chem.
CO2H HO2C
Soc. 1992, 114, 8349.
19. Cava, M. P.; Shirley, R. L., J. Org. Chem. 1961, 26, 2212.
(26)
+
20. Grundmann, C., Synthesis 1977, 644.
21. Grudzinski, Z.; Roberts, S. M.; Howard, C.; Newton, R. F., J. Chem.
HO2C HO2C
Soc., Perkin Trans. 1 1978, 1182.
5:2
22. Salomon, R. G.; Sachinvala, N. D.; Roy, S.; Basu, B.; Raychaudhuri,
S. R.; Miller, D. B.; Sharma, R. B., J. Am. Chem. Soc. 1991, 113,
3085.
Oxidation of Phosphites. The need to synthesize phospho-
23. Corey, E. J.; Srinivas Rao, K., Tetrahedron Lett. 1991, 32, 4623.
rylated organic molecules for biological evaluation has led to the
24. Corey, E. J.; Kim, S.; Yoo, S.; Nicolaou, K. C.; Melvin, Jr., L. S.; Brunelle,
development of a one-pot chemical phosphorylation protocol.46
D. J.; Falck, J. R.; Trybulski, E. J.; Lett, R.; Sheldrake, P. W., J. Am. Chem.
Soc. 1978, 100, 4620.
An organic alcohol is first treated with dibenzyl N,N-diisopropyl
phosphoramidite in the presence of 1H-tetrazole and the result- 25. Kobayashi, Y.; Ito, Y.; Terashima, S., Tetrahedron 1992, 48, 55.
ing phosphite intermediate is oxidized with peracetic acid or 26. Murahashi, S.-I.; Saito, T.; Hanaoka, H.; Murakami, Y.; Naota,
T.; Kumobayashi, H.; Akutagawa, S., J. Org. Chem. 1993, 58,
m-CPBA to form the corresponding dibenzyl phosphates
2929.
(eq 27).47 This protocol has become a standard method for the syn-
27. Murahashi, S.-I.; Naota, T.; Kuwabara, T.; Saito, T.; Kumobayashi, H.;
thesis of phosphorylated inositols due to the ease of purification
Akutagawa, S., J. Am. Chem. Soc. 1990, 112, 7820.
of dibenzyl phosphates by column chromatography or preparative
28. Murahashi, S.-I.; Saito, T.; Naota, T.; Kumobayashi, H.; Akutagawa, S.,
HPLC. Deprotection of purified dibenzyl phosphates by catalytic
Tetrahedron Lett. 1991, 32, 2145.
hydrogenation often yields target organophosphates of sufficient
29. Murahashi, S.-I.; Saito, T.; Naota, T.; Kumobayashi, H.; Akutagawa, S.,
purity for direct analysis or functionalization.48,49
Tetrahedron Lett. 1991, 32, 5991.
30. Corey, E. J.; Gross, A. W., Tetrahedron Lett. 1984, 25, 491.
HOOMEM
(BnO)2PNi-Pr2, tetrazole, CH3CN
31. Corey, E. J.; Barrette, E.-P.; Magriotis, P. A., Tetrahedron Lett. 1985, 26,
HO
HO CH3CO3H (32% in AcOH)
5855.
O
HO
32. Morimoto, T.; Hirano, M.; Ashiya, H.; Egashira, H.; Zhuang, X., Bull.
Chem. Soc. Jpn. 1987, 60, 4143.
OMEM
(BnO)2OPO
33. Larsen, R. D.; Roberts, F. E., Synth. Commun. 1986, 16, 899.
(BnO)2OPO
(27)
(BnO)2OPO
34. Sharefkin, J. G.; Saltzman, H., Org. Synth. 1963, 43, 62.
O
(BnO)2OPO
35. Sharefkin, J. G.; Saltzman, H., Org. Synth. 1963, 43, 65.
36. Mosher, H. S.; Turner, L.; Carlsmith, A., Org. Synth., Coll. Vol. 1963, 4,
Related Reagents. m-Chloroperbenzoic Acid; Perbenzoic
828.
Acid.
37. Heywood, D. L.; Phillips, B., J. Org. Chem. 1960, 25, 1699.
38. Murphy, A.; Pace, A.; Stack, T. D. P., Org. Lett. 2004, 6, 3119.
39. Murphy, A.; Dubois, G.; Stack, T. D. P., J. Am. Chem. Soc. 2003, 125,
5250.
1. (a) Swern, D. Organic Peroxides; Wiley: New York, 1971; Vol. II, p 355.
(b) Plesnicar, B. Organic Chemistry; Academic: New York, 1978; Vol. 40. Murahashi, S.-I.; Oda, Y.; Komiya, N.; Naota, T., Tetrahedron Lett. 1994,
5C, p 211. 35, 7953.
Avoid Skin Contact with All Reagents
6 PERACETIC ACID
41. Komiya, N.; Noji, S.; Murahashi, S.-I., J. Chem. Soc., Chem. Commun. 45. McKague, A. B., Synth. Commun. 1999, 29, 1463.
2001, 65.
46. Yu, K.-L.; Fraser-Reid, B., Tetrahedron Lett. 1988, 29, 979.
42. Shul pin, G. B.; Gradinaru, J.; Kozlov, Y. N., Org. Biomol. Chem. 2003,
47. Schnaars, A.; Schultz, C., Tetrahedron 2001, 57, 519.
1, 3611.
48. Dinkel, C.; Moody, M.; Traynor-Kaplan, A.; Schultz, C., Angew. Chem.,
43. Cuervo, L. G.; Kozlov, Y. N.; Süss-Fink, G.; Shul pin, G. B., J. Mol.
Int. Ed. 2001, 40, 3004.
Catal. A: Chem. 2004, 218, 171.
49. Roemer, S.; Rudolf, M. T.; Stadler, C.; Schultz, C., J. Chem. Soc., Chem.
44. Bragd, P. L.; Besemer, A. C.; van Bekkum, H., Carbohydr. Polym. 2002,
Commun. 1995, 411.
49, 397.
A list of General Abbreviations appears on the front Endpapers