An original on-column oxidative cleavage of vicinal diols using alumina/potassium periodate: Application to sequential oxidation/Horner-Emmons reactions

Article abstract of DOI:10.1002/ejoc.201100396

An unprecedented simple on-column solvent-free oxidative cleavage of vicinal diols in the solid phase using alumina/potassium metaperiodate is described herein. It permits preparation of the corresponding carbonyl compounds with high purity and good to excellent yields requiring only short reaction times. This methodology is then employed in on-column sequential oxidation/Horner-Emmons reactions for the preparation of selected stilbenes in good yields where both reaction and purification are integrated in a single unit or occur simultaneously permitting the rapid and easy preparation of small samples of pure stilbenes. The on-column oxidative cleavage of vicinal diols using alumina/potassium periodate is investigated. This approach is then applied to sequential oxidation/Horner-Emmons reactions for the simultaneous preparation and purification of stilbenes in good yields and requiring short reaction times.

Full text of DOI:10.1002/ejoc.201100396

FULL PAPER
DOI: 10.1002/ejoc.201100396
An Original On-Column Oxidative Cleavage of Vicinal Diols Using Alumina/
Potassium Periodate: Application to Sequential Oxidation/Horner–Emmons
Reactions
Saada C. Dakdouki,[a] Didier Villemin,*[a] and Nathalie Bar[a]
Keywords: Solid-phase synthesis / Reactive chromatography / Oxidation / Alcohols / Microwave chemistry
An unprecedented simple on-column solvent-free oxidative
cleavage of vicinal diols in the solid phase using alumina/
potassium metaperiodate is described herein. It permits
preparation of the corresponding carbonyl compounds with
high purity and good to excellent yields requiring only short
reaction times. This methodology is then employed in on-col-
umn sequential oxidation/Horner–Emmons reactions for the
preparation of selected stilbenes in good yields where both
reaction and purification are integrated in a single unit or
occur simultaneously permitting the rapid and easy prepara-
tion of small samples of pure stilbenes.
Introduction
On-column organic synthesis is one of the innovative
strategies that are gaining considerable importance in
modern chemistry.[1] In the course of our ongoing research
on reactive chromatography and solid-phase synthesis, we
were interested in performing on-column sequential reac-
tions, and more precisely, the oxidative cleavage of 1,2-diols/
Horner–Emmons sequence. In previous work,[2] we showed
that it is possible to prepare high purity methoxylated ana-
logues of resveratrol by Horner–Emmons reaction directly
in a column of alumina-KF with good to excellent yields.
In the present work, some stilbene derivatives, including a
methoxylated analogue of resveratrol, are prepared in a So-
lid Phase Extraction (SPE) column, starting from the suit-
able 1,2-diol which is cleaved into the corresponding alde-
hyde on an oxidative support already packed in a column.
The aldehyde produced is then engaged in a Horner–Em-
mons reaction over a basic support loaded in the same col-
umn below the oxidative support (Figure 1). This approach
permits the preparation of the target stilbenes with high
purity and good yields in short reaction times.
Figure 1. On-column sequential oxidative cleavage of vicinal diols/
Horner–Emmons reactions.
oxidants used for this purpose are periodic acid[3] and lead
tetraacetate.[4] Other oxidants employed for the cleavage of
α-glycols include sodium bismuthate,[5] pyridinium chloro-
chromate,[6] N-iodosuccinimide,[7] calcium hypochlorite[8]
and many others.[9] However, many of these oxidants suffer
drawbacks in terms of toxicity and issues related to storage,
handling, cost and solubility. For instance, periodic acid
and its related salts remain attractive reagents due to their
low toxicity, specificity and their rapid and clean reactivity
under mild conditions.[3] Yet, glycol cleavage reactions,
using sodium and potassium periodate, are often done in
water or aqueous organic solvents due to their solubility
properties. This solubility limitation has been overcome
using quaternary ammonium periodate;[10] potassium per-
iodate under phase-transfer catalysis conditions;[11] poly-
mer-supported periodates,[12] silica gel-supported sodium
periodate[13] and alumina-supported potassium dimeso-
periodate.[14]
Initially, the nature of the oxidative support as well as
the experimental conditions for the oxidation step was
studied. In organic synthesis, the oxidative cleavage of vici-
nal diols is a widely employed transformation. The classical
[a] Laboratoire de Chimie Moléculaire et Thioorganique, UMR
CNRS 6507, INC3M, FR 3038, ENSICAEN & Université de
Caen,
14050 Caen, France
Fax: +33-2-31452877
E-mail: didier.villemin@ensicaen.fr
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On-Column Reactions of Vicinal Diols
ethane-1,2-diol (1b), 1,2-bis(benzo[d]dioxol-6-yl)ethane-1,2-
diol (1c) and 1,2-bis(3,4,5-trimethoxyphenyl)ethane-1,2-diol
(1d) yielded 4-methoxybenzaldehyde, piperonal and 3,4,5-
trimethoxybenzaldehyde in 92, 65 and 40% yields, respec-
tively (Table 1, Entries 2–4).
In some cases, subsequent reactions occurred after the
cleavage reactions shown in (Table 1, Entries 5–8). Thus,
1,2-dihydroacenaphthylene-1,2-diol (1e) was cleaved into
the corresponding dialdehyde which was immediately en-
gaged in a Cannizzaro reaction affording intramolecular cy-
clization product (2e) in 22% yield (Scheme 1).
Under the same experimental conditions, cis-cyclohex-
ane-1,2-diol (1f) and 3,7,7-trimethylbicyclo[4.1.0]heptane-
3,4-diol (1g) were cleaved respectively into adipaldehyde
and 2-[2,2-dimethyl-3-(2-oxopropyl)cyclopropyl]acetalde-
hyde which immediately underwent intramolecular aldol
condensations giving the corresponding enal and enone de-
rivatives in 63 and 82% yields, respectively (Table 1, Entries
6 and 7). Similarly, cis-octane-1,2-diol (1h) gave the intra-
molecular aldol condensation product following microwave
irradiation but in low yield (Table 1, Entry 8).
Moreover, the microwave irradiation of diethyltartrate
for 10 min in the presence of the alumina/potassium meta-
periodate did not lead to complete conversion of the start-
ing diol. Instead, 92% of the starting diethyl tartrate was
collected at the end of the reaction.
In an attempt to avoid the intramolecular aldol conden-
sations and to isolate the dialdehydes in the case of cy-
cloalkyl-1,2-diols, milder conditions were applied where the
cleavage reactions were conducted at room temperature and
in the absence of microwave irradiation. In these cases, the
diol, alumina and potassium metaperiodate were well
ground together and the scission reactions were allowed to
proceed in a SPE column at room temperature in the ab-
sence of solvent. These conditions gave rise to the corre-
sponding dialdehydes without any further cyclizations in
the cases of, cyclohexane-1,2-diol (1f), 3,7,7-trimethylbicy-
clo[4.1.0]heptane-3,4-diol (1g) and cyclooctane-1,2-diol (1h)
(Table 2, Entries 1–3). However, this protocol did not lead
to complete conversion of the starting diol in all cases
(Table 2), and even a substantial increase in reaction time
(6 h) did not improve yields.
Results and Discussion
Oxidative Cleavage of Vicinal Diols
In this work, we report an original and efficient on-col-
umn solvent free oxidative cleavage of 1,2-diols to afford the
corresponding carbonyl compounds using alumina/potas-
sium metaperiodate. Our new protocol does not require the
pre-preparation of the supported reagent and, unlike pre-
viously reported protocols, there is no need for the dissol-
ution of periodate. Also, no vigorous stirring in an organic
solvent is needed and no filtration workup is done since the
reaction takes place in the column. Instead, the glycol scis-
sion reaction takes place readily in the commercially avail-
able SPE column (Varian Bond Elut, 6 mL) packed with a
well-ground mixture of diol, alumina and potassium metap-
eriodate either at room temperature or with microwave irra-
diation. The scission products are collected by simple elu-
tion using dichloromethane and their nature depends on the
precise reaction conditions used.
Initially, a control experiment was done using potassium
metaperiodate without any support and the scission reac-
tion of 1,2-diphenylethane-1,2-diol (1a) was carried out in
a SPE column packed with a well-ground mixture of potas-
sium metaperiodate and diol. Unfortunately, microwave ir-
radiation of the column for 10 min afforded only the start-
ing diol indicative of an unsuccessful cleavage reaction. Al-
ternatively, the oxidation reaction was done using alumina/
potassium metaperiodate. Gratifyingly, the microwave irra-
diation of a well-ground mixture of 1,2-diphenylethane-1,2-
diol, alumina and KIO4 already loaded onto a SPE column
in the absence of any solvent gave the corresponding benz-
aldehyde in pure form in 99% yield; see Equation (1). It is
noteworthy that the replacement of alumina with silica lead
to only a 60% conversion of the starting diol under the
same experimental conditions.
In brief, the alumina/potassium metaperiodate permitted
only incomplete conversion of the starting diols (cyclo-
alkane-1,2-diols) at room temperature under solvent-free
(1)
The feasibility of this method for the oxidative cleavage conditions. Based on these results, we assumed that this
of other α-glycols under solvent-free microwave chemistry might be attributable to poor diffusion resulting in weak
conditions has been investigated. Under the above-men- interactions of starting diols with the oxidative support.
tioned experimental conditions, 1,2-bis(4-methoxyphenyl)- Thus, we decided to dissolve the diols in a minimal volume
Scheme 1. Tandem glycolic cleavage/intramolecular Cannizzaro reactions.
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S. C. Dakdouki, D. Villemin, N. Bar
FULL PAPER
Table 1. On-column oxidative cleavage of substituted α,αЈ-diphenylethane-1,2-diols using microwave irradation.
of solvent. In this case, the potassium metaperiodate and 1f–h can be attributed to the use of solvent which permits
alumina were well ground together and the obtained pow- a better diffusion of the diols and consequently improves
der was loaded to the SPE column. The diol was then dis- their interactions with the oxidative support.
solved in a minimum volume of dichloromethane (0.2 mL)
and adsorbed onto the oxidative support in the column.
The cleavage reactions were allowed to proceed at room
temperature. Surprisingly, the starting diols were completely
converted into the corresponding carbonyl compounds.
On-Column Sequential Oxidative Cleavage/Horner–
Emmons Reactions
Thus, the cis-cyclohexane-1,2-diol (1f), 3,7,7-trimethylbicy-
The on-column oxidative cleavage of vicinal diols ap-
clo[4.1.0]heptane-3,4-diol (1g) and cis-cyclooctane-1,2-diol pears to be promising for performing on-column sequential
(1h) gave adipaldehyde (3a), 2-[2,2-dimethyl-3-(2-oxopro- reactions, namely, the sequence of oxidative diol cleavage
pyl)]acetaldehyde (3b) and octanedial (3c) in 92, 70 and and subsequent Horner–Emmons reaction. This methodol-
98% yields, respectively (Table 3). Complete conversions of ogy is illustrated in the synthesis of some stilbenes, includ-
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On-Column Reactions of Vicinal Diols
Table 2. On-column oxidative cleavage of vicinal diols using alumina/potassium metaperiodate at room temperature under solvent free
conditions.
1
[a] Conversions were determined by H NMR.
Table 3. On-column oxidative cleavage of vicinal diols at room temperature.
ing a methoxylated analogue of resveratrol. In this case, a column Horner–Emmons reaction whose products were
vicinal diol was cleaved in the alumina/potassium meta- collected by simple elution with dichloromethane.
periodate layer affording the corresponding aldehyde which
Several benzylic phosphonates were used in these reac-
was then eluted with tetrahydrofuran into the alumina/KF tions and their corresponding stilbenes successfully synthe-
layer containing an adsorbed benzylic phosphonate. Micro- sized (Table 4). In all examples of the oxidative cleavage/
wave irradiation of the adsorbed aldehyde permitted the on- Horner–Emmons sequence, the scission reactions pro-
Eur. J. Org. Chem. 2011, 4448–4454
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S. C. Dakdouki, D. Villemin, N. Bar
FULL PAPER
Table 4. On-column sequential oxidative cleavage of vicinal diol/Horner–Emmons reactions.
[a] Isolated yields; % conversion of diol in the oxidative cleavage reaction: 100%; % conversion of phosphonates in Horner reaction:
100%.
ceeded to completion and the starting diol was totally con-
verted into the corresponding aldehyde which was then
driven into the basic support with THF. For instance, the
volume of THF used to impregnate the alumina-KF was
not necessarily sufficient to elute all aldehyde intermediate
from the diol cleavage reaction from the alumina/KIO4
layer. Consequently, an excess of diol was used in order to
ensure consumption of the starting phosphonate in the
Horner–Emmons reaction. Column elution with dichloro-
methane afforded the expected stilbenes along with unre-
acted aldehydes. To obtain these stilbenes in pure form, the
reaction column was eluted with a less polar solvent (cyclo-
hexane or mixtures of cyclohexane and ethyl acetate), and
the eluent was allowed to pass directly through another
SPE column loaded with silica permitting the direct purifi-
cation of stilbenes in 60–75% overall yield (Figure 2, a).
Alternatively, the sequence of reactions (oxidation/
Horner–Emmons) as well as the purification step can be
integrated into a single unit. Thus, a SPE column was
Figure 2. Simultaneous on-column sequential oxidation/Horner–
Emmons reaction and purification.
Conclusions
In conclusion, we have developed a rapid, simple and
loaded with 3 consecutive layers of: (1) silica, (2) Al2O3-KF efficient procedure for the oxidative cleavage of vicinal diols
and (3) Al2O3/KIO4 (Figure 2, b). In this case, the oxidative in the solid state using alumina/potassium metaperiodate
cleavage, Horner–Emmons reaction and purification are all in a SPE column. This protocol does not require the pre-
done in a single column. This methodology was applied to preparation of the supported oxidant nor the dissolution of
the preparation of stilbene 5a which was obtained in pure the periodate or diol and no organic solvent was necessary
form in the same yield (60%) as previously noted using two to perform the oxidation reaction. It enabled facile cleavage
separate columns (Table 4, Entry 1).
of substituted 1,2-diphenylethane-1,2-diols as well as cyclo-
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On-Column Reactions of Vicinal Diols
10 min. The reaction products were then eluted with dichlorometh-
ane (~ 15 mL). The solvent was then evaporated to afford the corre-
sponding scission product. In most cases, the cleavage products
were found to be pure.
alkane-1,2-diols requiring only short reaction times. Also,
this on-column oxidation of vicinal diols was used to carry
out on-column sequential oxidation/Horner–Emmons reac-
tions for the preparation of selected stilbenes. This method-
ology integrates both reaction and purification steps into a
single unit and circumvents long aqueous workups.
General Procedure for the On-Column Oxidative Cleavage of Vicinal
Diols Using Alumina/Potassium Metaperiodate at Room Tempera-
ture: A well-ground mixture of alumina (1 g) and potassium meta-
periodate (2 g) is loaded in a SPE column. The diol (1.0 mmol)
was dissolved in dichloromethane (0.2 mL) and adsorbed on the
oxidative support in the column. The reaction was then allowed to
proceed at room temperature for 1–2 h. The reaction products were
eluted with dichloromethane (ca. 15 mL) and the solvent then evap-
orated to afford the corresponding carbonyl product.
Experimental Section
General Methods: All commercial reagents were purchased from
Acros, Aldrich, and Sigma and were used as received without fur-
ther purification. Reactions were monitored by TLC until no start-
ing material remained. TLC was performed using Silica gel 60 F254
precoated aluminium sheets. Column chromatography was per-
formed using Silica gel Si 60 (40–63 μm). Microwave irradiation
was executed using a mono-mode Prolabo Synthewave 402 cavity.
1H, 31P and 13C NMR spectra were recorded with Bruker AC 250
or AC 400 spectrometers. Chemical shifts (δ) are expressed in parts
per million [ppm] and are referenced to the internal deuterated sol-
vents with tetramethylsilane as the internal standard. Data are re-
ported as follows: multiplicity (s = singlet, d = doublet, t = triplet,
q = quartet, dd = doublet of doublet, dt = doublet of triplet, m =
multiplet, br. = broad). Coupling constants are given in Hertz (Hz).
Mass spectra were recorded with a QTOF Micro (Waters) spec-
trometer with electrospray ionization (ESI, positive mode), lock-
spray orthophosphoric acid, infusion introduction at 10 μL/min, a
source temperature of 80 °C and desolvation temperature of
120 °C.
General Procedure for On-Column Sequential Oxidation/Horner–
Emmons Reactions (Method A): A polypropylene SPE column (Var-
ian Bond Elut®, 6 mL), equipped with a frit at its lower end, was
charged with a layer of alumina-KF (3.0 g) over which was ad-
sorbed the benzylphosphonate (0.5 mmol). This column was then
loaded with another layer of a well-ground mixture of diol (1–2 mol
equivalents), alumina (1.0 g) and potassium metaperiodate (2.0 g).
It was then placed in a quartz reactor and exposed to microwave
irradiation (120 W) in a resonance cavity for 10 min. The formed
aldehyde was eluted with an adequate volume of tetrahydrofuran
(ca. 1.2 mL) so as to reach the alumina-KF layer. The column was
then microwave irradiated for 12 min. The stilbene produced was
then eluted from the column with cyclohexane or cyclohexane/ethyl
acetate (95:5, 20 mL) and the mobile phase then allowed to pass
directly through another SPE column packed with silica (2.0 g) to
ultimately afford purified stilbene following solvent removal.
All the compounds synthesized in this work are known and their
spectroscopic data were found to be in agreement with those re-
ported in literature. References are cited either in the text or in
relevant tables.
General Procedure for On-Column Sequential Oxidation/Horner–
Emmons Reactions (Method B): The same procedure employed in
method A was used except that the SPE column was loaded with:
(1) a layer of silica (1.5 g), (2) a layer of alumina-KF (1.8 g), (3) a
layer of a well-ground mixture of diol, potassium metaperiodate
(1.0 g) and alumina (0.5 g).
Preparation of the Substituted 1,2-Diphenylethane-1,2-diols 1b–d:
These diols were prepared as a mixture of cis and trans isomers
using a pinacol coupling procedure described by Zhang and Li.[25]
The mixtures of cis/trans isomers are subjected to glycolic cleavage
reactions without separation.
Acknowledgments
Synthesis of Diol 1e:[26] To a stirred suspension of acenaphthylene-
1,2-dione (3.0 g, 16.5 mmoL) in methanol (50 mL), was added so-
dium borohydride (1.25 g, 32.9 mmol) in small portions at 0 °C.
When the addition was complete, the reaction mixture was allowed
to stir at room temp. for 90 min. The solvent was then evaporated
under reduced pressure and the resulting residue was washed with
water to afford the corresponding vicinal diol (2.0 g, 65%). 1H
NMR (400 MHz, CDCl3): δ = 7.80 (d, J = 8.0 Hz, 2 H, ArH),
7.61–7.53 (m, 4 H, ArH), 5.49 (d, J = 6.5 Hz, 2 H, CH-O), 2.35
(d, J = 6.5 Hz, 2 H, OH) ppm. 13C NMR (100.6 MHz, CDCl3): δ
= 141.6, 136.0, 131.0 (2C), 128.5 (2C), 125.2 (2C), 120.6 (2C), 84.1
We gratefully acknowledge financial support from the Ministère de
la Recherche et des Nouvelles Technologies, Centre National de la
Recherche Scientifique (CNRS), the Région Basse-Normandie and
the European Union (FEDER funding) for financial support. Also,
we would like to thank Miss Eléonore Payen de la Garanderie for
her contribution to this work.
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Eur. J. Org. Chem. 2011, 4448–4454