Metal-free dihydroxylation of alkenes using cyclobutane malonoyl peroxide

Article abstract of DOI:10.1021/jo202084w

Cyclobutane malonoyl peroxide (7), prepared in a single step from the commercially available diacid 6, is an effective reagent for the dihydroxylation of alkenes. Reaction of a chloroform solution of 7 with an alkene in the presence of 1 equiv of water at 40 °C followed by alkaline hydrolysis leads to the corresponding diol (30-84%). With 1,2-disubstituted alkenes, the reaction proceeds with syn-selectivity (3:1 → 50:1). A mechanism consistent with experimental findings is proposed, which is supported by deuterium and oxygen labeling studies and explains the stereoselectivity observed. Alternative reaction pathways that are dependent on the structure of the starting alkene are also described leading to the synthesis of allylic alcohols and γ-lactones.

Full text of DOI:10.1021/jo202084w

Article
pubs.acs.org/joc
Metal-Free Dihydroxylation of Alkenes using Cyclobutane Malonoyl
Peroxide
Kevin M. Jones† and Nicholas C. O. Tomkinson*,‡
†School of Chemistry, Main Building, Cardiff University, Park Place, Cardiff, CF10 3AT, U. K.
‡WestCHEM, Department of Pure and Applied Chemistry, Thomas Graham Building, University of Strathclyde, 295 Cathedral
Street, Glasgow, G1 1XL, U. K.
S
* Supporting Information
ABSTRACT: Cyclobutane malonoyl peroxide (7), prepared
in a single step from the commercially available diacid 6, is an
effective reagent for the dihydroxylation of alkenes. Reaction of
a chloroform solution of 7 with an alkene in the presence of 1
equiv of water at 40 °C followed by alkaline hydrolysis leads to
the corresponding diol (30−84%). With 1,2-disubstituted
alkenes, the reaction proceeds with syn-selectivity (3:1 →
50:1). A mechanism consistent with experimental findings is
proposed, which is supported by deuterium and oxygen
labeling studies and explains the stereoselectivity observed. Alternative reaction pathways that are dependent on the structure of
the starting alkene are also described leading to the synthesis of allylic alcohols and γ-lactones.
dihydroxylation have been reported; however, this area is
considerably less established than their metal-based counter-
parts.16−18 To date, the development of an asymmetric, metal-
free method for the syn-dihydroxylation of alkenes remains an
elusive and attractive target.
In a series of largely neglected reports, Greene described the
synthesis19 and reactivity20 of phthaloyl peroxide (PPO) 1.
Within these articles, Greene showed that PPO (1) reacts with
trans-stilbene 2 (CCl4, 80 °C) to give two dioxygenated
products 3 and 4 in a 1:3 ratio (Scheme 1).20b Alkaline
INTRODUCTION
■
Over the past decade, metal-free transformations have been
driven to the forefront of chemical research. Transition metals
enjoy widespread use in organic synthesis;1 however, the cost,
toxicity, and environmental impact of many of these reagents/
catalysts have made their use increasingly prohibitive. In
general, metal-free reactions offer a number of notable
advantages, including the fact they are often inexpensive and
the reagents are easy to prepare, bench-stable, tolerant of
moisture and air, and nontoxic. It is for these reasons that the
development of metal-free methods continues to attract
significant research interest.
Scheme 1. Reaction of Phthaloyl Peroxide 1 with trans-
Stilbene 2
Oxidation is central to synthetic chemistry.2 The chemical
industry relies on the selective oxidation of hydrocarbon feed-
stocks in the production of numerous commodity materials,
which find application in all areas of life.3 From a synthetic
standpoint, oxidation is used extensively in the formation of
fine chemicals and natural products.4 Owing to its importance,
a staggering number of reagents and catalytic systems have
been developed to promote oxidation.5 Of the known oxidation
methods, alkene dihydroxylation is particularly important.
Among the reagents available for alkene dihydroxylation,
none have achieved more success than osmium tetroxide.6
For over eighty years, the use of OsO4 has been developed and
refined, forming the basis of one of the most powerful
transformations in synthetic chemistry: the Sharpless asym-
metric dihydroxylation (SAD).7 Despite this reaction's wide-
spread popularity, the toxicity of osmium and high levels of
inorganic waste are commonly cited limitations,8 which has
prompted the development of a number of alternative metal
catalysts,9 including palladium,10 iron,11 ruthenium,12 manga-
nese,13 and copper14 systems.15 Metal-free methods for syn-
hydrolysis of 3 and 4 (either separately or as a mixture) leads to
( )-hydrobenzoin 5.21 Importantly, it was shown that starting
Received: October 7, 2011
Published: December 12, 2011
© 2011 American Chemical Society
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with either trans- or cis-stilbene, the reaction was stereospecific,
formally leading to ( )-hydrobenzoin 5 or meso-hydrobenzoin,
respectively. Although the overall process was low-yielding, this
represents a transition-metal-free syn-dihydroxylation with great
potential. A recent report from Siegel showed improved
reactivity for the derivative 3,4-dichlorophthaloyl peroxide,
albeit with reduced stereoselectivities, showing great capacity
for further development.22
PPO (1) is very sensitive to shock and explodes at 130 °C,
providing an explanation why this interesting transformation
has not been significantly developed further. We reasoned that
stable cyclic acyl peroxides may provide the basis of a metal-free
dihydroxylation procedure, and we have shown that cyclo-
propane malonoyl peroxide is an effective reagent for alkene
syn-dihydroxylation.23 During the development of this reaction,
the reactivity of cyclobutane malonoyl peroxide 7 was
extensively examined. We now wish to provide a more
complete description of the use of 7 for alkene dihydroxylation
and highlight alternative reaction pathways that lead to the
synthesis of allylic alcohol and γ-lactone products, which are
dependent on the structure of the starting alkene.
phthaloyl peroxide with alkenes. Cyclobutane carboxylic acid,
formed during hydrolysis of 9 and 10, was removed by aqueous
workup facilitating isolation of the diol product. The
combination of easily handled reagent and mild conditions
made this reaction extremely simple to perform.
Encouraged by this initial discovery, the reaction conditions
were optimized with respect to peroxide stoichiometry and
solvent (Table 1). Capricious yields were observed using bench
acetonitrile, which suggested that the water content of the
solvent may have an effect on the reactivity (Table 1, entry 1).
Further investigation showed that the use of dry acetonitrile led
to a lower isolated yield over 18 h (20% after hydrolysis),
whereas the addition of 1 equiv of water to the reaction solvent
consistently delivered the diol product in moderate yield (55%)
(Table 1, entries 2 and 3), confirming that the presence of
water was important to the overall reaction.
A screen of common reaction solvents revealed that
chloroform was the most effective, providing the dihydroxy-
lated product 11 in 69% yield (Table 1, entry 4). On the basis
of the water dependency described above, it is interesting that
the heterogeneous reaction mixture of chloroform and water
delivered the product in higher yield than those of water
miscible solvents such as acetonitrile (55%; Table 1, entry 3)
and THF (30%; Table 1, entry 5).
The results in Table 1 revealed a strong trend between
peroxide equivalents and isolated yield of 11. Use of excess
peroxide led to a sharp decrease in the isolated yield of 11
(Table 1, entries 10 and 11). Use of a slight excess of the
reagent (Table 1, entry 9) gave 11 in an excellent 84% yield. A
small of amount of reagent degradation could account for the
need for a slight excess of the peroxide reagent.
RESULTS AND DISCUSSION
Cyclobutane malonoyl peroxide 7 was prepared in one step
from the commercially available diacid 6 (Scheme 2). A series
■
Scheme 2. Synthesis of Cyclobutane Malonoyl Peroxide 7
Following the development of an optimized set of
conditions, we aimed to gain a mechanistic understanding of
the transformation. Two potential pathways are outlined in
Scheme 4. An initial interaction between the peroxide 7 and
alkene 12 forms the first C−O bond and a stabilized benzylic
carbocation 13. Direct cyclization of 13 results in the formation
of dioxonium intermediate 14. Hydrolysis of 14, followed by
decarboxylation, provides the observed products 16 and 17. An
alternative pathway that is also consistent with the products
involves direct decarboxylation and cyclization to give the 2-
cyclobutylidene-1,3-dioxolane 18. Subsequent protonation and
hydrolytic decomposition then leads to 16 and 17. If the
second alternative is operating, 18 would be highly reactive, and
it is not clear why it selectively protonates in preference to
reacting with a second molecule of peroxide 7. Further
investigation is required to deconvolute the subtleties in the
mechanistic pathway.
of peroxide sources were examined for this procedure on the
basis of existing literature methods, which were restricted to
small-scale preparation owing to the use of concentrated
hydrogen peroxide solutions24 or incompatible reagents.25 The
optimized procedure involved treatment of 6 with urea
hydrogen peroxide complex,26 using methane sulfonic acid as
an activator and dehydrating agent.27 Crucially, the reaction
could be performed on a reasonable scale (4 g) and
conveniently purified by aqueous workup and crystallization.
With an efficient route for the preparation of cyclobutane
malonoyl peroxide 7, we turned our attention to examining its
reactivity with alkenes. A set of exploratory investigations
revealed that 7 reacts with 4-methylstyrene (8) to give two
major products 9 and 10 after 18 h (Scheme 3). Treatment of
the crude reaction mixture with aqueous sodium hydroxide
gave diol 11 in low yield (∼30%).
Both of these preliminary mechanisms are supported by
isotopic labeling studies (Scheme 5). The use of 18OH2 results
in exclusive incorporation of the 18O label within the carbonyl
group (22 and 23), consistent with Scheme 4 and previous
observations that water was vital to reaction success. Use of
deuterium oxide as the water source resulted in >80%
Several important features of this reaction require further
discussion. The reaction proceeded under mild conditions in
the presence of air and moisture at a temperature considerably
lower than that reported by Greene for the reactions of
Scheme 3. Reaction of Cyclobutane Malonoyl Peroxide 1 with 4-Methylstyrene 8
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a
Table 1. Optimization of Reaction Conditions for Dihydroxylation of 4-Methyl Styrene 8
b
entry
solvent
H2O equiv
peroxide equiv
yield (%)
1
CH3CN (bench)
CH3CN (dry)
CH3CN
CHCl3
1.5
1.5
1.5
1.5
1.5
1.5
1.5
1.0
1.1
2.0
3.0
20−55
20
2
0
3
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
55
4
69
5
THF
30
6
PhMe
60
7
MeOH
0
8
CHCl3
78
9
CHCl3
84
10
11
CHCl3
44
CHCl3
22
a
b
Reactions performed at 0.8 M on a 1 mmol scale of alkene. Isolated yield after column chromatography.
Scheme 4. Potential Mechanisms for the Cyclobutane
Malonoyl Peroxide 7 Mediated Dihydroxylation
Scheme 5. Labeling Studies for Reaction between Styrene
and 7
deuterium incorporation in the products 24 and 25 as
1
2
confirmed by H, 13C and, D NMR spectroscopy.
Scheme 6. Reaction of 1-Phenyl-2-cyclopropylethylene with
7
It is possible that a radical, single electron transfer (SET), or
ionic mechanism is operating during the reaction of the alkene
and the peroxide. The addition of 0.1 equiv of butylated
hydroxy toluene (BHT), a well-known radical inhibitor,
resulted in minimal change to reaction rate and isolated yield
of 22 and 23. These results suggested that a radical mechanism
was not operating. Reports by Schuster28,29 have shown
malonoyl peroxides to undergo reaction with polyconjugated
aromatics via SET. The possibility exists for the initial C−O
bond-forming event between 7 and the alkene to proceed via
SET. Cyclopropyl carbinyl radicals are known to undergo rapid
ring-opening to give butenyl radicals.30 To probe this
phenomenon further, 1-phenyl-2-cyclopropylethylene 26 was
examined as a substrate in the reaction with 7 (Scheme 6).
Under standard reaction conditions (CHCl3, 1 equiv of H2O,
40 °C, 18 h), the diol 27 was isolated in 83% yield after
hydrolysis. This result does not provide conclusive evidence
against a SET mechanism operating, and further investigation is
required to establish in favor of an ionic or SET pathway.
The substrate scope was examined with a series of
commercially available styrene derivatives (Table 2). It should
be noted that a number of alkene substrates were not
consumed using 1.1 equiv of 7. The use of 1.5 equiv of 7
consistently led to consumption of the alkene starting material
and was used as standard without significantly affecting the
isolated yields. The effect of varying substitution pattern was
examined with 3- and 2-methyl styrene (Table 2, entries 2 and
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an electrophilic reagent, and as a result, dihydroxylation of
electron-deficient alkenes represents a considerable challenge.
In contrast, electron-rich alkenes represent the most likely
substrates to give higher reaction rate. The reaction between
cyclobutane malonoyl peroxide 7 and 3-nitrostyrene was slow
and required the use of excess peroxide (2.0 equiv) and
extended reaction times (68 h) to give the corresponding diol
in a disappointingly low yield of 30% (Table 2, entry 10).
Attention is drawn to the fact that unreacted starting material
Table 2. Substrate Scope for the Cyclobutane Malonoyl
Peroxide (7) Mediated Dihydroxylation
a
1
could be observed in the H NMR of the crude reaction
mixture, indicating that further optimization on this substrate is
possible. As predicted, 4-methoxystyrene was dihydroxylated in
good yield (78%), although no appreciable increase in rate was
noted (Table 2, entry 8). 1,1-Disubstituted alkenes were also
tolerated as exemplified by the dihydroxylation of 1,1-
diphenylethylene in 67% (Table 2, entry 11).
Table 3. Stereoselectivity for the Cyclobutane Malonoyl
a
Peroxide Mediated Dihydroxylation
a
Standard conditions: (i) alkene (1 mmol), 7 (1.5 mmol), H2O (1
equiv), CHCl3 (1.4 mL), 40 °C, 18−24 h; (ii) reduce to dryness, then
a
b
c
1
Standard conditions: (i) alkene (1 mmol), 7 (1.5 mmol), H2O (1
1 M NaOH (10 mL), 60 °C, 4 h. Isolated yield. Determined by H
equiv), CHCl3 (1.4 mL), 40 °C, 18−24 h; (ii) reduce to dryness, then
NMR spectroscopy of crude reaction mixture.
b
c
1 M NaOH (10 mL), 40 °C, 18 h. Isolated yield. 2.0 mmol 7 used
for 68 h.
1,2-Disubstituted alkenes presented an opportunity to
evaluate the stereoselectivity associated with the transformation
(Table 3). The dihydroxylation of trans-stilbene gave a mixture
of ( )- and meso-hydrobenzoin (78%; 28:1), indicating that the
reaction is not stereospecific. The loss of stereochemical
integrity can be attributed to the formation of a benzylic
carbocation (c.f. 13, Scheme 4), at which point free rotation
about the C−C bond is possible, allowing the formation of
both diastereoisomers. Excellent syn-selectivity is observed with
3), which were dihydroxylated in 65 and 80% isolated yield,
respectively. Pleasingly, the sterically demanding mesityl group
was also tolerated (Table 2, entry 4), providing the diol in 65%.
The effect of substitution pattern was further probed with 2-
chlorostyrene, which gave the dihydroxylated product in
significantly lower yield (Table 2, entry 5; 38%). The reaction
was also found to be unaffected by the presence of halogens
(Table 2, entries 6 and 7). Cyclobutane malonoyl peroxide 7 is
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trans-stilbene derivatives with syn:anti ratios >28:1 being
achieved (Table 3, entries 1 and 2). Dihydroxylation of β-
methylstyrene derivatives led to a decrease in the diaster-
eoselectivity with syn:anti ratios ∼5:1 being achieved (Table 3,
entries 3−5). It is interesting to note that substituents that
stabilize (Table 3, entry 4) or destabilize (Table 3, entry 5) a
benzylic carbocation had little effect on the observed
diastereoselectivities as illustrated by 4-methoxy- and 4-
bromo-β-methylstyrene. cis-Stilbene was found to give the
dihydroxylated product with a lower diastereoselectivity (Table
3, entry 6; syn:anti 3:1); however, incorporation of a cis-alkene
within a ring resulted in the exclusive formation of the syn-
dihydroxylated product (Table 3, entry 7; 67%).
A potential explanation for the formation of lactones 33−35
involves the formation of zwitterion 36 following loss of CO2
from 7. Subsequent addition of 36 across the alkene substrate
generates the observed products. Formation of zwitterion 36
has been previously proposed by Adam and co-workers during
their investigation into the formation of α-lactones from
malonoyl peroxides.32 Although providing a plausible mecha-
nism for γ-lactone formation, it is currently unclear how the
alkene substrate brings about such a dramatic change in
reactivity and highlights mechanistic subtleties that are still to
be fully understood (Scheme 8).
Scheme 8. Potential Mechanism for γ-Lactone Formation
Although the majority of the substrates tested gave the
dihydroxylated product exclusively, a number of unexpected
side products were observed throughout reaction development.
Alkenes containing β-hydrogens, such as α-methylstyrene 28,
gave a mixture of dihydroxylated product 29 (50%) and allylic
alcohol 30 (20%) (Scheme 7).
Comparison of cyclopropane malonoyl peroxide 38 and
cyclobutane malonoyl peroxide 7 reveals a series of noteworthy
similarities and differences. Synthesis of each reagent proceeds
in the same yield, and they both lead to the syn-dihydroxylated
product with similar levels of selectivity. As reported
previously,23 reactions of cyclopropyl malonoyl peroxide
proceed at a faster rate, but it is important to note that the
ability to slow down the reaction could have significant
implications in the development of a catalytic procedure. The
major difference between the two reagents resides in the
reaction mechanism. Reaction of 7 with 4-methylstyrene leads
to the intermediates 9 and 10, where decarboxylation has taken
place. Reaction of 38 with 4-methylstyrene leads to the
intermediates 39 and 40, where the carboxylic acid group is still
present (Scheme 9). It is possible that this observation provides
evidence for intermediate 18 (Scheme 4). When using
cyclopropane malonoyl peroxide 38, formation of the
analogous intermediate 41 would be disfavored because of
the formation of an sp2 hybridized center on the cyclopropane
ring. The ability of 7 to decarboxylate allows for different
reactivity, for example, formation of the γ-lactones 33−35.
These products suggest that cyclobutane malonoyl peroxide
may possess unexpected forms of reactivity that are yet to be
fully exploited. Further investigations in this area may reveal
additional synthetically interesting transformations.
Scheme 7. Allylic Alcohol Formation with Alkenes Bearing
Β-Hydrogens
Formation of 30 was attributed to loss of an allylic hydrogen
following the formation of the benzylic carbocation 31.
Subsequent decarboxylation gave the stable allylic ester 32,
which was hydrolyzed without purification to give 30 as a
product. The direct conversion of an alkene to an allylic alcohol
represents a useful transformation,31 and we are currently
investigating the potential of forming the allylic alcohol
exclusively.
An additional set of unusual products were observed
following the attempted dihydroxylation of 4-hydroxystyrene
(Table 4, entry 1). Curiously, the reaction resulted in the
formation of a γ-lactone in low yield (Table 4, entry 1). Further
investigation revealed γ-lactone formation was also observed for
2-hydroxystyrene and 4-N-Boc-aminostyrene (Table 4, entries
2 and 3).
CONCLUSION
■
In summary, we have described an operationally simple method
for the dihydroxylation of alkenes using cyclobutane malonoyl
peroxide 7. The reagent is easily prepared from the
commercially available diacid and can be used to dihydroxylate
a
Table 4. γ-Lactone Formation
b
entry
R1
product
yield (%)
1
2
3
4-OH-C6H4
2-OH-C6H4
33
34
35
19
45
30
4-NHBoc-C6H4
a
b
Reactions performed at 0.8 M on a 1 mmol scale. Isolated yield after column chromatography.
925
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11.5 Hz, 1H), 3.48 (s, 1H), 3.19 (s, 1H), 2.36 (s, 3H); 13C NMR (62.5
MHz, CDCl3) δ 137.5, 137.4, 129.1, 126.0, 74.5, 68.0, 21.1; LRMS
(EI) m/z 152.1 [M]+; HRMS (EI) calculated for C9H12O2 [M]+
152.0837, found 152.0840.
Scheme 9. Comparison of Reactivity of Cyclobutane
Malonoyl Peroxide 7 and Cyclopropane Malonoyl Peroxide
38
1-(O-Oxocyclobutyl)-1-(p-tolyl) Ethane-1,2-diol 9. Colorless
1
oil (0.12 g, 45%): IR (thin film)/cm−1 3480, 3018, 1728, 1252; H
NMR (400 MHz, CDCl3) δ 7.15 (d, J = 8.1 Hz, 2H), 7.09 (d, J = 8.1
Hz, 2H), 5.73 (dd, J = 4.1, 7.7 Hz, 1H), 3.78 (dd, J = 7.7, 12.0 Hz,
1H), 3.70 (dd, J = 4.1, 12.0 Hz, 1H), 3.14 (quin, J = 8.5 Hz, 1H), 2.25
(s, 3H), 2.24−2.11 (m, 4H), 1.91−1.82 (m, 2H); 13C NMR (62.5
MHz, CDCl3) δ 175.1, 138.2, 134.3, 129.3, 126.5, 76.5, 66.1, 38.2,
25.3, 25.1, 21.2, 18.4; LRMS (EI) m/z 216.1 [M − H2O]+; HRMS
(EI) calculated for C14H16O2 [M − H2O]+ 216.1150, found 216.1148.
2-(O-Oxocyclobutyl)-1-(p-tolyl) Ethane-1,2-diol 10. Colorless
oil (0.10 g, 37%): IR (thin film)/cm−1 3471, 3066, 1726, 1252, 1215;
1H NMR (400 MHz, CDCl3) δ 7.20 (d, J = 8.0 Hz, 2H), 7.10 (d, J =
7.9 Hz, 2H), 4.84 (dd, J = 3.2, 8.3 Hz, 1H), 4.19 (dd, J = 3.3, 11.6 Hz,
1H), 4.08 (dd, J = 8.4, 11.6 Hz, 1H), 3.11 (quin, J = 8.5 Hz, 1H), 2.50
(bs, 1H), 2.27 (s, 3H), 2.24−2.11 (m, 4H), 1.91−1.83 (m, 2H); 13C
NMR (62.5 MHz, CDCl3) δ 175.7, 137.9, 137.0, 129.2, 126.1, 72.4,
69.2, 38.0, 25.3, 21.1, 18.4; LRMS (EI) m/z 216.1 [M − H2O]+;
HRMS (EI) calculated for C14H16O2 [M − H2O]+ 216.1150, found
216.1150.
12-Phenylpropane-1,2-diol 29.34 Colorless oil (0.05 g, 50%): IR
1
(thin film)/cm−1 3568, 1449, 1027; H NMR (400 MHz, CDCl3) δ
a range of styrene and stilbene derivatives in good yield, often
without column chromatography. Competitive diastereoselec-
tivities have been achieved for a range of 1,2-disubstituted
alkenes. A plausible mechanism has been proposed, which is
supported by isotopic labeling studies; however, the formation
of side products has been included to illustrate that there are
still mechanistic questions that require further understanding.
Along with developing a more accurate description of the
reaction mechanism, current work is focused on the develop-
ment of a catalytic variant of the reaction.
7.34−7.32 (m, 2H), 7.27−7.24 (m, 2H), 7.19−7.15 (m, 1H), 3.62 (d, J
= 11.2 Hz, 1H), 3.48 (d, J = 11.2 Hz, 1H), 2.90 (s, 2H), 1.39 (s, 3H);
13C NMR (62.5 MHz, CDCl3) δ 144.9, 128.3, 127.0, 125.0, 74.8, 70.8,
25.9; LRMS (EI) m/z 134.1 [M − H2O]+; HRMS (EI) calculated for
C9H10O [M − H2O]+ 134.0732, found 134.0736.
2-Phenylprop-2-en-1-ol 30.35 Colorless oil (0.02 g, 20%): H
1
NMR (400 MHz, CDCl3) δ 7.47−7.44 (m, 2H), 7.38−7.31 (m, 3H),
5.48 (app s, 1H), 5.36 (s, 1H), 4.56 (s, 2H); 13C NMR (125 MHz,
CDCl3) δ 147.3, 138.5, 128.5, 127.9, 126.1, 112.6, 65.1; LRMS (EI)
m/z 134.1 [M]+; HRMS (EI) calculated for C9H10O [M]+ 134.0732,
found 134.0729.
1-Phenylethane-1,2-diol. Table 2, entry 1: mp 61 °C; IR (thin
EXPERIMENTAL SECTION
1
film)/cm−1 3394, 2926, 1613; H NMR (400 MHz, CDCl3) δ 7.37−
■
7.29 (m, 5H), 4.83 (dd, J = 3.6, 8.4 Hz, 1H), 3.76 (dd, J = 3.6, 11.6 Hz,
1H), 3.66 (dd, J = 8.4, 11.2 Hz, 1H), 2.67 (s, 1H), 2.26 (s, 1H); 13C
NMR (100 MHz, CDCl3) δ 140.4, 128.5, 128.0, 126.0, 74.7, 68.1;
LRMS (EI) m/z 138.1 [M]+; HRMS (EI) calculated for C8H10O2
[M]+ 138.0681, found 138.0676.
Caution: Peroxides are particularly dangerous. These procedures
should be carried out only by knowledgeable laboratory workers.
Cyclobutane Malonoyl Peroxide 7.32 Methane sulfonic acid (30
mL) was placed in a round bottomed flask equipped with large
magnetic stirrer bar and immersed in a bath of water at 22 °C. Urea
hydrogen peroxide (9.8 g, 104 mmol) was added in a single portion,
and the mixture was stirred for 30 s. Cyclobutane-1,1-dicarboxylic acid
(5.0 g, 35 mmol) was added in a single portion, and the reaction was
stirred vigorously for 18 h. The reaction mixture was poured into a
mixture of ice (80 g) and ethyl acetate (100 mL), and the layers were
separated. The aqueous layer was washed with ethyl acetate (2 × 100
mL), and the combined organic layers were washed with NaHCO3 (2
× 50 mL) and brine (20 mL) and dried over MgSO4. Removal of the
solvent under reduced pressure gave the title compound 7 as a white
1-m-Tolylethane-1,2-diol. Table 2, entry 2: mp 70−72 °C; IR
1
(thin film)/cm−1 3159, 2924, 1483; H NMR (400 MHz, CDCl3) δ
7.15−7.12 (m, 1H), 7.04−7.00 (m, 3H), 4.65 (dd, J = 3.6, 8.4 Hz,
1H), 3.59 (dd, J = 3.2, 11.6 Hz, 1H), 3.51 (dd, J = 8.4, 11.6 Hz, 1H),
3.44 (bs, 2H), 2.24 (s, 3H); 13C NMR (62.5 MHz, CDCl3) δ 140.4,
138.1, 128.6, 128.3, 126.7, 123.1, 74.7, 68.0, 21.4; LRMS (EI) m/z
152.1 [M]+; HRMS (EI) calculated for C9H12O2 [M]+ 152.0837,
found 152.0836.
1-o-Tolylethane-1,2-diol.36 Table 2, entry 3: mp 104−105 °C;
1
IR (thin film)/cm−1 3258, 2924, 1356, 1066; H NMR (400 MHz,
solid (4.0 g, 80%): mp 63 °C; IR (thin film)/cm−1 1799, 1269; H
1
CDCl3) δ 7.50 (dd, J = 1.6, 7.6 Hz, 1H), 7.24−7.14 (m, 3H), 5.06 (dd,
J = 3.2, 8.4 Hz, 1H), 3.73 (dd, J = 3.2, 11.6 Hz, 1H), 3.61 (dd, J = 8.4,
11.6 Hz, 1H), 2.35 (s, 3H); 13C NMR (125 MHz, CDCl3) δ 138.4,
134.7, 130.4, 127.7, 126.3, 125.6, 71.4, 66.9, 19.0; LRMS (EI) m/z
152.1 [M]+; HRMS (EI) calculated for C9H12O2 [M]+ 152.0837,
found 152.0842.
NMR (250 MHz, CDCl3) δ 2.71 (t, J = 8.0 Hz, 4H), 2.36 (quin, J =
8.0 Hz, 2H); 13C NMR (62.5 MHz, CDCl3) δ 173.9, 40.4, 28.9, 16.3.
General Procedure for the Dihydroxylation of Alkenes with
Cyclobutane Malonoyl Peroxide. 1-p-Tolylethane-1,2-diol
11.33 Alkene (0.7 mmol) was added dropwise to a solution of
cyclobutane malonoyl peroxide (0.15 g, 1.1 mmol) in chloroform (1.4
mL). H2O (13 μL, 0.7 mmol) was added, and the reaction mixture was
heated at 40 °C for 18−24 h. The resulting solution was reduced to
dryness, and 1 M NaOH (10 mL) was added. The reaction mixture
was heated at 40 °C for 18 h. The aqueous layer was extracted with
chloroform (15 mL). The aqueous layer was further extracted with
chloroform (2 × 20 mL), and the combined organic layers were
washed with brine (10 mL) and dried over MgSO4. The solvent was
removed under reduced pressure to give the desired diol: mp 70−72
°C; IR (thin film)/cm−1 3371, 2925, 1647, 1327; 1H NMR (400 MHz,
CDCl3) δ 7.21 (d, J = 8.0 Hz, 2H), 7.14 (d, J = 8.0 Hz, 2H), 4.74 (dd,
J = 3.5, 8.4 Hz, 1H), 3.67 (dd, J = 3.5, 11.5 Hz, 1H), 3.60 (dd, J = 8.4,
1-Mesitylethane-1,2-diol.37 Table 2, entry 4: mp 110−111 °C;
IR (thin film)/cm−1 3365, 2923, 1611; 1H NMR (400 MHz, CDCl3) δ
6.83 (s, 2H), 5.26 (dd, J = 3.6, 10.0 Hz, 1H), 3.96 (dd, J = 10.0, 11.6
Hz, 1H), 3.61 (dd, J = 3.8, 11.6 Hz, 1H), 2.40 (s, 6H), 2.25 (s, 3H);
13C NMR (125 MHz, CDCl3) δ 137.2, 136.6, 132.4, 130.2, 72.6, 64.6,
20.7, 20.7; LRMS (EI) m/z 180.1 [M]+; HRMS (EI) calculated for
C11H16O2 [M]+ 180.1150, found 180.1145.
1-(2-Chlorophenyl)ethane-1,2-diol. Table 2, entry 5: mp 101−
1
104 °C; IR (thin film)/cm−1 3164, 1470, 1361, 1068; H NMR (250
MHz, CDCl3) δ 7.60 (dd, J = 1.9, 7.4 Hz, 1H), 7.35−7.22 (m, 3H),
5.25 (dd, J = 3.0, 8.0 Hz, 1H), 3.91 (dd, J = 2.8, 11.3 Hz, 1H), 3.58
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(dd, J = 8.0, 11.3 Hz, 1H), 2.73 (bs, 1H), 2.18 (bs, 1H); 13C NMR
(125 MHz, CDCl3) δ 137.8, 132.0, 129.4, 129.0, 127.6, 127.1, 71.4,
66.2; LRMS (EI) m/z 172.0 [M]+; HRMS (EI) calculated for
C8H9O2Cl35 [M]+ 172.0291, found 172.0288.
1-(4-Chlorophenyl)ethane-1,2-diol. Table 2, entry 6: mp 76−77
°C; IR (thin film)/cm−1 3612, 3399, 1598, 1077; 1H NMR (400 MHz,
CDCl3) δ 7.35−7.29 (m, 4H), 4.80 (dd, J = 3.6, 8.4 Hz, 1H), 3.74 (dd,
J = 3.6, 11.2 Hz, 1H), 3.61 (dd, J = 8.0, 11.2 Hz, 1H); 13C NMR (125
MHz, CDCl3) δ 138.9, 133.8, 128.7, 127.4, 74.0, 67.9; LRMS (CI) m/
z 190.2 [M + NH4]+; HRMS (ES) calculated for C8H13O2Cl35N [M +
NH4]+ 190.0629, found 190.0626.
1-(4-Bromophenyl)ethane-1,2-diol. Table 2, entry 7: mp 98−99
°C; IR (thin film)/cm−1 3313, 2930, 1590; 1H NMR (400 MHz,
CDCl3) δ 7.49 (d, J = 8.4 Hz, 2H), 7.36 (d, J = 8.4 Hz, 2H), 4.73−4.69
(m, 1H), 4.43 (d, J = 3.6 Hz, 1H), 3.87 (t, J = 6.0 Hz, 1H), 3.65−3.50
(m, 2H); 13C NMR (62.5 MHz, CDCl3) δ 139.4, 131.6, 127.8, 121.8,
74.0, 67.9; LRMS (EI) m/z 216.0 [M]+; HRMS (EI) calculated for
C8H9O2Br79 [M]+ 215.9786, found 215.9790.
rel-(1R,2R)-1-(4-Methoxyphenyl)propane-1,2-diol.40 Table 3,
1
entry 4: IR (thin film)/cm−1 3390, 2979, 2901, 1485, 1397; H NMR
(400 MHz, CDCl3) δ 7.13 (d, J = 8.8 Hz, 2H), 6.78 (d, J = 8.4 Hz,
2H), 4.17 (d, J = 8.0 Hz, 1H), 3.70 (s, 3H), 3.75−3.65 (m, 1H), 0.89
(d, J = 6.4 Hz, 3H); 13C NMR (125 MHz, CDCl3) δ 159.4, 133.2,
128.0, 113.9, 79.1, 72.2, 55.2, 18.7; LRMS (EI) m/z 182.1 [M]+;
HRMS (EI) calculated for C10H14O3 [M]+ 182.0943, found 182.0940.
rel-(1R,2R)-1-(4-Methoxyphenyl)propane-1,2-diol.41 Table 3,
entry 5: IR (thin film)/cm−1 3402, 2896, 1593, 1488, 1400, 1126,
1069, 1040, 1010, 926; 1H NMR (400 MHz, CDCl3) δ 7.47 (d, J = 8.4
Hz, 2H), 7.19 (d, J = 8.4 Hz, 2H), 4.30 (d, J = 7.2 Hz, 1H), 3.80−3.74
(m, 1H), 2.72 (bs, 2H), 1.03 (d, J = 6.4 Hz, 3H); 13C NMR (125
MHz, CDCl3) δ 140.0, 131.6, 128.5, 122.0, 78.8, 72.1, 18.8; LRMS
(EI) m/z 211.9 [M − H2O]+; HRMS (EI) calculated for C9H9OBr79
[M − H2O]+ 211.9837, found 211.9841.
1
meso-Hydrobenzoin. Table 3, entry 6: mp 133 °C; H NMR
(400 MHz, CDCl3) δ 7.26−7.17 (m, 10H), 4.76 (s, 2H), 2.13 (s, 2H);
13C NMR (125 MHz, CDCl3) δ 139.8, 128.2, 128.1, 127.1, 78.1;
LRMS (EI) m/z 196.1 [M − H2O]+; HRMS (EI) calculated for
C14H12O [M − H2O]+ 196.0888, found 196.0886.
rel-(1R,2S)-2,3-Dihydro-1H-indene-1,2-diol. Table 3, entry 7:
mp 88−90 °C; IR (thin film)/cm−1 3395, 2924, 1727, 1610; 1H NMR
(250 MHz, CDCl3) δ 7.36−7.33 (m, 1H), 7.20−7.18 (m, 3H), 4.88
(d, J = 4.8 Hz, 1H), 4.40−4.35 (m, 1H), 3.03 (dd, J = 5.8, 16.3 Hz,
1H), 2.85 (dd, J = 3.6, 16.3 Hz, 1H), 2.50 (bs, 2H); 13C NMR (62.5
MHz, CDCl3) δ 141.9, 140.1, 128.8, 127.2, 125.3, 125.0, 75.9, 73.4,
38.6; LRMS (EI) m/z 150.1 [M]+; HRMS (EI) calculated for
C9H10O2 [M]+ 150.0681, found 150.0684.
General Procedure for the Formation of γ-Lactones. Alkene
(0.7 mmol) was added to a solution of cyclobutane malonoyl peroxide
(0.15 g, 1.0 mmol) in chloroform (2 mL). After ∼5 min, the reaction
mixture turned orange. The reaction mixture was stirred at room
temperature for 1 h. The reaction mixture was reduced to dryness to
give the corresponding γ-lactone, which was purified by column
chromatography.
1-(4-Methoxyphenyl)ethane-1,2-diol. Table 2, entry 8: mp 78−
1
79 °C; IR (thin film)/cm−1 3359, 2935, 2839, 1612, 1246; H NMR
(400 MHz, CDCl3) δ 7.30 (d, J = 8.4 Hz, 2H), 6.90 (d, J = 8.8 Hz,
2H), 4.78 (dd, J = 3.4, 7.8 Hz, 1H), 3.81 (s, 3H), 3.76−3.63 (m, 2H),
2.42 (bs, 1H), 2.03 (bs, 1H); 13C NMR (62.5 MHz, CDCl3) δ 159.3,
132.6, 127.3, 113.9, 74.3, 68.0, 55.3; LRMS (EI) m/z 168.2 [M]+;
HRMS (ES) calculated for C9H12O3Na [M + Na]+ 191.0679, found
191.0676.
tert-Butyl 4-(1,2-Dihydroxyethyl)phenylcarbamate. Table 2,
entry 9: mp 139−141 °C; IR (thin film)/cm−1 3379, 3334, 3281, 2933,
1685, 1525; 1H NMR (400 MHz, CDCl3) δ 7.28 (d, J = 8.4 Hz, 2H),
7.22 (d, J = 8.4 Hz, 2H), 6.43 (bs, 1H), 4.71 (dd, J = 3.6, 8.0 Hz, 1H),
3.66 (dd, J = 3.6, 11.2 Hz, 1H), 3.57 (dd, J = 8.4, 11.2 Hz, 1H) 1.45 (s,
9H); 13C NMR (125 MHz, DMSO) δ 152.7, 138.0, 136.9, 126.3,
117.6, 78.7, 73.3, 67.4, 28.0; LRMS (EI) m/z 253.1 [M]+; HRMS (EI)
calculated for C13H19NO4 [M]+ 253.1314, found 253.1310.
1-(3-Nitrophenyl)ethane-1,2-diol.38 Table 2, entry 10: mp 74−
1
75 °C; H NMR (400 MHz, acetone-d6) δ 8.30 (d, J = 1.6 Hz, 1H),
5-(4-Hydroxyphenyl)-3,3-spirocyclobutylbutyrolactone 33.
Spectral data: mp 140−141 °C; IR (thin film)/cm−1 3369, 2940,
8.13−8.11 (m, 1H), 7.85 (d, J = 7.6 Hz, 1H), 7.62 (t, J = 8.0 Hz, 1H),
4.89 (dd, J = 3.4, 7.9 Hz, 1H), 4.79 (d, J = 4.0 Hz, 1H), 4.08 (t, J = 5.6
Hz, 1H), 3.75−3.61 (m, 2H); 13C NMR (100 MHz, CDCl3) δ 142.7,
132.2, 129.5, 122.9, 121.2, 73.5, 67.7 (one carbon missing); LRMS
(EI) m/z 165.0 [M − H2O]+; HRMS (EI) calculated for C8H7O3N
[M − H2O]+ 165.0426, found 165.0434.
1
1753, 1614, 1517, 1447, 1330, 1172; H NMR (400 MHz, CDCl3) δ
7.17 (d, J = 8.3 Hz, 2H), 6.84 (d, J = 8.8 Hz, 2H), 5.66 (bs, 1H), 5.29
(dd, J = 6.0, 9.3 Hz, 1H), 2.72 (dd, J = 6.0, 13.0 Hz, 1H), 2.62−2.46
(m, 2H), 2.26 (dd, J = 9.0, 13.0 Hz, 1H), 2.19−1.94 (m, 4H); 13C
NMR (125 MHz, CDCl3) δ 181.1, 155.9, 131.0, 127.2, 115.6, 78.2,
44.9, 44.4, 31.6, 29.1, 16.5; LRMS (EI) m/z 218.1 [M]+; HRMS
(MALDI) calculated for C13H14O3 [M]+ 218.0943, found 218.0937.
5-(2-Hydroxyphenyl)-3,3-spirocyclobutylbutyrolactone 34.
Spectral data: mp 169−171 °C; IR (thin film)/cm−1 3365, 2944,
1,1-Diphenylethane-1,2-diol. Table 2, entry 11: mp 110 °C; IR
(thin film)/cm−1 3372, 3303, 1491, 1455, 1384, 1361, 1043; 1H NMR
(400 MHz, CDCl3) δ 7.38−7.36 (m, 4H), 7.29−7.26 (m, 4H), 7.22−
7.18 (m, 2H), 4.10 (d, J = 6.4 Hz, 2H), 3.11 (s, 1H), 1.80 (t, J = 6.4
Hz, 1H); 13C NMR (62.5 MHz, CDCl3) δ 143.7, 128.4, 127.5, 126.4,
78.5, 69.4; LRMS (EI) m/z 196.1 [M − H2O]+; HRMS (EI)
calculated for C14H12O [M − H2O]+ 196.0888, found 196.0887.
( )-Hydrobenzoin. Table 3, entry 1: mp 104−105 °C; IR (thin
1
1749, 1603, 1457, 1333; H NMR (400 MHz, CDCl3) δ 7.26−7.16
(m, 2H), 6.93−6.83 (m, 2H), 6.20 (bs, 1H), 5.64 (dd, J = 6.8, 8.4 Hz,
1H), 2.86 (dd, J = 6.8, 13.0 Hz, 1H), 2.60−2.50 (m, 2H), 2.33 (dd, J =
8.4, 13.0 Hz, 1H), 2.20−1.97 (m, 4H); 13C NMR (62.5 MHz, CDCl3)
δ 181.7, 153.0, 129.2, 125.9, 125.6, 120.6, 115.8, 75.3, 44.5, 42.7, 31.6,
29.5, 16.5; LRMS (EI) m/z 218.1 [M]+; HRMS (EI) calculated for
C13H14O3 [M]+ 218.0943, found 218.0943.
1
film)/cm−1 3389, 2922, 2852, 1645; H NMR (400 MHz, CDCl3) δ
7.19−7.06 (m, 10H), 4.66 (s, 2H), 2.74 (s, 2H); 13C NMR (125 MHz,
CDCl3) δ 139.8, 128.1, 127.9, 126.9, 79.1; LRMS (APCI) m/z 196.1
[M − H2O]+; HRMS (CI) calculated for C14H14O2Na [M + Na]+
237.0886, found 237.0887.
5-(4-N-Boc-Phenyl)-3,3-spirocyclobutylbutyrolactone 35.
Spectral data: mp 115 °C; IR (thin film)/cm−1 3437, 1764, 1725,
1597, 1524; 1H NMR (400 MHz, CDCl3) δ 7.36 (d, J = 8.5 Hz, 2H),
7.21 (d, J = 8.5 Hz, 2H), 6.61 (bs, 1H), 5.29 (dd, J = 6.5, 9.0 Hz, 1H),
2.72 (dd, J = 6.5, 13.0 Hz, 1H), 2.60−2.47 (m, 2H), 2.22 (dd, J = 9.0,
13.0 Hz, 1H), 2.17−1.92 (m, 4H), 1.50 (s, 9H); 13C NMR (125 MHz,
CDCl3) δ 180.7, 152.7, 138.6, 133.7, 126.3, 118.6, 80.7, 77.8, 44.8,
44.5, 31.5, 29.2, 28.3, 16.5; LRMS (EI) m/z 317.2 [M]+; HRMS (EI)
calculated for C18H23O4N [M]+ 317.1627, found 317.1631.
rel-(1R,2R)-1,2-Di-o-tolylethane-1,2-diol. Table 3, entry 2: mp
1
125 °C; IR (thin film)/cm−1 3390, 1604, 1490; H NMR (400 MHz,
CDCl3) δ 7.60 (dd, J = 1.2, 7.6 Hz, 2H), 7.22−7.18 (m, 2H), 7.14−
7.10 (m, 2H), 6.92 (d, J = 7.6 Hz, 2H), 4.93 (s, 2H), 3.22 (s, 2H), 1.64
(s, 6H); 13C NMR (62.5 MHz, CDCl3) δ 137.9, 135.8, 130.0, 127.6,
127.1, 125.8, 74.5, 18.7; LRMS (EI) m/z 224.1 [M − H2O]+; HRMS
(EI) calculated for C16H16O [M − H2O]+ 224.1201, found 224.1203.
rel-(1R,2R)-1-Phenylpropane-1,2-diol.39 Table 3, entry 3: IR
(thin film)/cm−1 3435, 1714, 1520, 1392; 1H NMR (400 MHz,
CDCl3) δ 7.37−7.31 (m, 5H), 4.38 (d, J = 7.6 Hz, 1H), 3.90−3.84 (m,
1H), 2.32 (bs, 2H), 1.07 (d, J = 6.0 Hz, 3H); 13C NMR (125 MHz,
CDCl3) δ 141.0, 128.4, 128.0, 126.8, 79.4, 72.2, 18.7; LRMS (EI) m/z
134.1 [M − H2O]+; HRMS (EI) calculated for C9H10O [M − H2O]+
134.0732, found 134.0730.
ASSOCIATED CONTENT
■
S
* Supporting Information
1H and 13C spectra for all compounds reported. This material is
available free of charge via the Internet at http://pubs.acs.org.
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Article
(20) (a) Greene, F. D. J. Am. Chem. Soc. 1956, 78, 2250. (b) Greene,
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AUTHOR INFORMATION
Corresponding Author
*E-mail: Nicholas.Tomkinson@strath.ac.uk.
■
ACKNOWLEDGMENTS
The authors thank the EPSRC for financial support and the
mass spectrometry service, Swansea for high-resolution spectra.
■
(23) Griffiths, J. C.; Jones, K. M.; Picon, S.; Rawling, M. J.; Kariuki, B.
M.; Campbell, M.; Tomkinson, N. C. O. J. Am. Chem. Soc. 2010, 132,
14409.
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