High-Yielding Diastereoselective syn-Dihydroxylation of Protected HBO: An Access to D-(+)-Ribono-1,4-lactone and 5-O-Protected Analogues

Article abstract of DOI:10.1002/ejoc.201801780

A diastereoselective chemoenzymatic synthetic pathway to D-(+)-ribono-1,4-lactone, a versatile chiral sugar derivative widely used for the synthesis of various natural products, has been designed from cellulose-based levoglucosenone (LGO). This route involves a sustainable Baeyer-Villiger oxidation of LGO to produce enantiopure (S)-γ-hydroxymethyl-α,β-butenolide (HBO) that is further functionalized with various protecting groups to provide 5-O-protected γ-hydroxymethyl-α,β-butenolides. The latter then undergo a diastereoselective and high-yielding syn-dihydroxylation of the α,β-unsaturated lactone moiety followed by a deprotection step to give D-(+)-ribono-1,4-lactone. Through this 4-step synthetic route from LGO, D-(+)-ribono-1,4-lactone is obtained with d.r. varying from 82:18 to 97:3 and in overall yields between 32 and 41 % depending on the protecting group used. Moreover, valuable synthetic intermediates 5-O-tert-butyldimethylsilyl-, 5-O-tert-butyldiphenylsilyl- as well as 5-O-benzyl-ribono-1,4-lactones are obtained in 3 steps from LGO in 58, 61 and 40 %, respectively.

Full text of DOI:10.1002/ejoc.201801780

A Journal of
Accepted Article
Title: High yielding diastereoselective syn-dihydroxylation of protected
HBO: an access to D-(+)-ribono-1,4-lactone and 5-O-protected
analogues
Authors: Maxime Moreaux, Guillaume Bonneau, Aurélien Peru, Fanny
Brunissen, Marine Janvier, Arnaud Haudrechy, and Florent
Allais
This manuscript has been accepted after peer review and appears as an
Accepted Article online prior to editing, proofing, and formal publication
of the final Version of Record (VoR). This work is currently citable by
using the Digital Object Identifier (DOI) given below. The VoR will be
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to this Accepted Article as a result of editing. Readers should obtain
the VoR from the journal website shown below when it is published
to ensure accuracy of information. The authors are responsible for the
content of this Accepted Article.
To be cited as: Eur. J. Org. Chem. 10.1002/ejoc.201801780
Link to VoR: http://dx.doi.org/10.1002/ejoc.201801780
Supported by

10.1002/ejoc.201801780
European Journal of Organic Chemistry
COMMUNICATION
High yielding diastereoselective syn-dihydroxylation of protected
HBO: an access to D-(+)-ribono-1,4-lactone and 5-O-protected
analogues
Maxime Moreaux,[a,b] Guillaume Bonneau,[a,b] Aurélien Peru,[a] Fanny Brunissen,[a] Marine Janvier,[a]
Arnaud Haudrechy*[b] and Florent Allais*[a]
Abstract: A diastereoselective chemo-enzymatic synthetic pathway
to D-(+)-ribono-1,4-lactone, a versatile chiral sugar derivative widely
used for the synthesis of various natural products, has been
designed from cellulose-based levoglucosenone (LGO). This route
involves a sustainable Baeyer-Villiger oxidation of LGO to produce
enantiopure (S)-γ-hydroxymethyl-α,β-butenolide (HBO) that is further
functionalized with various protecting groups to provide 5-O-
protected D-(+)-ribono-1,4-lactones. The resulting 5-O-protected
lactones then undergo a diastereoselective and high yielding syn-
dihydroxylation of the α,β-unsaturated lactone moiety followed by a
deprotection step to give D-(+)-ribono-1,4-lactone. Through this 4-
step synthetic route from LGO, D-(+)-ribono-1,4-lactone is obtained
with d.r. varying from 82:18 to 97:3 and in overall yields between 32
and 41% depending on the protecting group used. Moreover,
valuable synthetic intermediates 5-O-tert-butyldimethylsilyl-, 5-O-tert-
butyldiphenylsilyl- as well as 5-O-benzyl-ribono-1,4-lactones are
obtained in 3 steps from LGO in 58, 61 and 40%, respectively.
constituted a synthon of choice for the production of several
valuable products such as natural products, nucleosides,
anticancer drugs and building blocks.4-8
Among the compounds obtained from LGO, the unsaturated
chiral γ-lactone (S)-γ-hydroxymethyl-α,β-butenolide (HBO,
Scheme 1) has found numerous applications as
a key
intermediate for the synthesis of drugs (such as Burseran or
Isostegane),9,10 flavors11,12 and antiviral agents against HIV or
hepatitis B virus.13-15 Our team recently developed cost-efficient,
low toxicity and green syntheses of optically pure HBO from
LGO using Baeyer-Villiger oxidations.16-19 Dedicated to the
development of valuable applications of this platform molecule,
our team then designed and optimized the chemo-enzymatic
synthesis of (S)-dairy lactone,12
applications for its fruity odor and creamy dairy-like taste.
a flavor used in food
HO
O
Furacell(R)
Baeyer-Villiger
oxidation
Introduction
O
O
O
O
O
O
HO
O
OH
HO
In a context of increasing scarcity and price of fossil resources,
and also more drastic regulations such as the REACH regulation,
the use of alternative renewable resources has raised a growing
interest in the scientific community. The production of valuable
chemicals from renewable biomass has been largely developed
in the last decades, with the aim of offering new sustainable
efficient procedures as alternative routes to traditional synthetic
pathways.1 In this context, an interesting alternative is the
valorization of lignocellulose, which is the most abundant and
bio-renewable biomass on earth.2 The catalytic fast pyrolysis
(CFP) of lignocelluloses has already been deeply studied for the
production of target products in high yields.3 Levoglucosenone
(LGO) is one of the products that can be produced from
lignocellulose CFP (Scheme 1). The structure of this synthon is
particularly interesting, due to the presence of one natural chiral
center preserved from cellulose, and the presence of two
functionalisable moieties (α,β-unsaturated ketone and protected
aldehyde functionality). According to these properties, LGO
n
LGO
HBO
Scheme 1. Synthesis16-19 of HBO from cellulose-based levoglucosenone
(LGO).
D-(+)-ribono-1,4-lactone, a rather costly rare sugar (ca. 50€/g)
present in leaves of Listea japonica, displays an interesting
vicinal 1,2-cis-diol and has been used for the synthesis of
various natural or synthetic bioactive molecules20 - such as
Herbarumin I21 or (+)-Varitriol22 (Scheme 2).
NH
O
O
O
HO
HO
MeO
HO
NH
N
HO
OH
OH
O
HO
HO
(+)-Varitriol
4-Deazaformycin B
O
(antitumor)
(antibiotic)
OH
D-(+)-Ribono-1,4-lactone
H
N
H
N
O
O
HO
HO
R
O
OH
HO
[a]
M. Moreaux, G. Bonneau, A. A. M. Peru, F. Brunissen, Dr. M.
Janvier and Prof. F. Allais*
NH2
HO
OH
O
Chaire Agro-Biotechnologies Industrielles (ABI)
AgroParisTech
CEBB 3 rue des Rouges Terres 51110 Pomacle, France
E-mail: florent.allais@agroparistech.fr
M. Moreaux, G. Bonneau, Prof. A. Haudrechy*
Institut de Chimie Moléculaire de Reims, UMR CNRS 7312, SFR
Condorcet FR CNRS 3417
R = H, Herbarumin I
R = OH, Herbarumin II
(herbicide)
R
Siastatin B
(sialidase inhibitor)
HO
OH
R = MeS, Mannostatin A
R = MeSO, Mannostatin B
(antiviral)
[b]
Scheme 2. Some molecules of interest accessible from D-(+)-ribono-1,4-
lactone
Université de Reims Champagne-Ardenne
BP 1039 51687 Reims Cedex 2, France
E-mail: arnaud.haudrechy@univ-reims.fr
D-(+)-ribono-1,4-lactone can be prepared in ca. 65% yield
through the molecular bromine-mediated oxidation of D-ribose,23
Supporting information for this article is given via a link at the end of
the document.
This article is protected by copyright. All rights reserved.

10.1002/ejoc.201801780
European Journal of Organic Chemistry
COMMUNICATION
a costly sugar (ca. 400€/kg). Another route consists in first
protecting the primary alcohol of HBO with bulky groups to
hinder the upper face of the molecule, then performing the
asymmetric syn-dihydroxylation of the α,β-unsaturation in
presence of KMnO4 (1.25 eq) and dicyclohexano-18-crown-6
ether (10 mol%) in CH2Cl2 at -42 °C.24 Although this procedure
provides 5-O-protected D-(+)-ribono-1,4-lactone in d.r. between
12:1 and 50:1 depending on the protecting group used, the
oxidizing agent is used in stoichiometric amount, the yields
remain low to average (<66%) - due to overoxidation of the
resulting diol - and energy-demanding low temperature control is
required. In this paper, we will describe a high yielding syn-
dihydroxylation of 5-O-protected HBO, and discuss the influence
of the protecting group on its diastereoselectivity, as well as the
final deprotection steps required to access D-(+)-ribono-1,4-
lactone (Scheme 3).
asymmetric dihydroxylation,26,27 involving osmium catalyst, has
been widely used due to its high stereospecificity and
enantioselectivity.
Dihydroxylation conditions
A: Sharpless
B: Ruthenium catalysis
C: Upjohn
D: modified-Upjohn
O
O
O
O
RO
RO
HO
OH
HBO-R
HBO-R-2OH
Table 1. syn-Dihydroxylation using Sharpless conditions, RuCl3 catalysis,
Upjohn and modified-Upjohn conditions.
Substrate
(HBO-R)
d.r. (%)
NMR[c,d]
d.r. (%)
Entry
Meth.[b]
Yield (%)[b]
HPLC[c,e]
O
O
Syn-dihydroxylation
O
Protection
O
O
O
RO
HO
HBO-TBDMS
A
B
C
D
A
B
C
D
A
B
C
D
0
-
-
RO
1
2
HO
OH
60
50
88
0
94:6
91:9
93:7
-
97:3
91:9
95:5
-
HBO
HBO-R
HBO-R-2OH
3
4
Deprotection
O
O
O
O
HO
HO
+
5
HBO-TBDPS
HO
OH
HO
OH
D-(+)-ribono-1,4-lactone
D-(-)-lyxono-1,4-lactone
6
62
55
89
0
94:6
95:5
97:3
-
94:6
92:8
94:6
-
(major)
(minor)
7
Scheme 3. Synthetic strategy to convert HBO into (+)-D-ribono-1,4-lactone
8
Results and Discussion
9
HBO-Bn
The first step of the synthetic route to D-(+)-ribono-1,4-lactone
consisted in the efficient and straightforward H2O2-mediated
Baeyer-Villiger oxidation of LGO into HBO (Scheme 4).19
Validated at the kilo scale, this sustainable synthetic procedure
provides HBO in 84% yield. Protection of HBO was performed
using benzyl (Bn), tert-butyldimethylsilyl (TBDMS), as well as
tert-butyldiphenylsilyl (TBDPS) protecting groups. Silyl ethers
HBO-TBDMS and HBO-TBDPS were obtained under classical
conditions (silyl chloride, imidazole, DMF) in 78 and 82% yields,
respectively. For the benzyl ether HBO-Bn, acidic conditions
using benzyl 2,2,2-trichloroacetimidate as benzyl donor25 were
applied and lead to HBO-Bn in 53% yield.
10
11
12
60
12
75
80:20
78:22
82:18
88:12
86:14
83:17
A: AD-mix-β (K2OsO4 or OsO4, K3Fe(CN)6, chiral ligand (DHQD)2PHAL) and
basic buffer K2CO3. B: RuCl3 (5 mol%), NaIO4 (1.5 eq), CeCl3 (10 mol%),
CH3CN/AcOEt/water (3/3/1), rt, 30 min. C: K2OsO4 (5 mol%), NMO (1.28 eq),
acetone/water (4/1), rt, 18h. D: K2OsO4 (0.6 mol%), NMO (1.1 eq), EtOH/H2O
(1/1), citric acid (0.75 eq), rt, 18h.
[a] Determined by 1H NMR of crude reaction mixture. [b] Isolated as a pure
mixture of diastereomers. [c] Major diastereomer being the D-ribono-1,4-
lactone derivative. [d] Determined by 1H NMR of crude reaction mixture. [e]
Determined by HPLC of crude reaction mixture.
O
Classical Sharpless conditions were first applied (Table 1,
entries 1, 5 and 9) with the commercially available AD-mix β
(K2OsO4 or OsO4, K3Fe(CN)6, chiral ligand (DHQD)2PHAL) and
basic buffer K2CO3. Nevertheless, under such conditions no
dihydroxylation was observed. Ruthenium-catalyzed syn-
a
O
O
b or c or d
O
O
O
O
HO
RO
LGO
HBO
HBO-TBDMS (R = TBDMS)
HBO-TBDPS (R = TBDPS)
HBO-Bn (R = Bn)
dihydroxylation using an in situ generation of the oxidant specie
a: 30% aqu. H2O2, H2O, 84%; b: (HBO-TBDMS): imidazole, TBDMSCl, Et3N,
DMAP, DCM, 78%; c: (HBO-TBDPS): imidazole, TBDPSCl, DMF, rt, 82%; d:
28
RuO4
(RuCl3.5H2O, NaIO4, CeCl3, CH3CN-AcOEt-water
(HBO-Bn)
: benzyl 2,2,2-trichloroacetimidate, TfOH, DCM-cyclohexane, 0 °C,
53%
(3/3/1)) was also investigated (Table 1, entries 2, 6 and 10).
Under these conditions, HBO-TBDMS-2OH, HBO-TBDPS-2OH
and HBO-Bn-2OH were obtained in 60, 62 and 60% yields,
Scheme 4. Protection of HBO with TBDMS, TBDPS and Bn protecting groups
respectively,
comparable
to
that
obtained
with
Upjohn
Olefin dihydroxylation is a common reaction in the synthesis of
pharmaceuticals and natural products. The Sharpless
KMnO4/dicyclohexano-18-crown-6
ether24.
dihydroxylation conditions,29-31 involving osmium tetroxide as
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10.1002/ejoc.201801780
European Journal of Organic Chemistry
COMMUNICATION
catalyst and N-methylmorpholine-N-oxide (NMO) as oxidant,
were then investigated (Table 1, entries 3, 7 and 11). Among the
different solvent mixtures tested (i.e., methanol, acetone-water
and acetone-water-butanol), acetone/water proved the most
relevant one and gave access to dihydroxylated derivatives of
HBO-TBDMS (HBO-TBDMS-2OH), HBO-TBDPS (HBO-
TBDPS-2OH), and HBO-Bn (HBO-Bn-2OH) in moderate yields,
50, 55 and 12% respectively. As classical Upjohn conditions did
not lead to higher yields, modified-Upjohn conditions were
applied as the addition of citric acid had been proven
beneficial.31 After being optimized, this room temperature
yield for ribono-1,4-lactone and 37% for lyxono-1,4-lactone)
(Scheme 5). The same strategy was applied for the synthesis of
the TBDPS derivatives and provided 5-O-tert-butyldiphenylsilyl-
D-ribonolactone and 5-O-tert-butyldiphenylsilyl-D-lyxono-1,4-
lactone in 76 and 74% yield, respectively. The synthesis of the
benzylated standards proved less straightforward and required
multi-step pathways. The three-step preparation of 5-O-benzyl-
D-ribono-1,4-lactone started with the selective acetalization of D-
ribono-1,4-lactone
into
2,3-O-isopropylidene-D-ribono-1,4-
lactone (HCl, acetone, 75%) (Scheme 6). The latter was then
benzylated (BnBr, NaH, DMF, 34%)32 and the resulting
intermediate was hydrolyzed (Montmorillonite K10, EtOH, 86%)
to provide 5-O-benzyl-D-ribonolactone. The preparation of 5-O-
benzyl-D-lyxono-1,4-lactone was even more tedious and
required a six-step pathway. L-gulonolactone was first bis-
acetalized (acetone, p-TsOH, 2,2-DMP) to provide crude 2,3-
5,6-di-O-isopropylidene-L-gulonolactone which then underwent
procedure
provided
the
corresponding
5-O-protected
dihydroxylactones in excellent yields (HBO-TBDMS-2OH: 88%,
overall yield from LGO: 58%; HBO-TBDPS-2OH: 89%, overall
yield from LGO: 61%; HBO-Bn-2OH: 89%, overall yield from
LGO: 40%) (Table 2, entries 4, 8 and 12). The diastereomeric
excesses were first evaluated by performing 1H NMR
spectroscopy of the crude reaction mixtures by looking at the
signal of the protons of the CH2 at the γ position. Calculations
showed that the syn-dihydroxylation proceeds with d.r. between
82:18 and 97:3 depending on the protecting group used,
demonstrating the average to high diastereoselectivity of the
syn-dihydroxylation. As expected, the higher steric hindrance of
tert-butyldimethyl silyl and tert-butyldiphenyl silyl groups
provides the highest d.r. compared to the less bulky “flat” benzyl
group. Nevertheless, because of partial overlapping of signals in
1H NMR spectroscopy, d.r. needed to be confirmed by another
technique.
a
selective hydrolysis of the ketal at the 5,6-positions
(AcOH/water) giving access to 2,3-O-isopropylidene-L-
gulonolactone (61% from L-gulonolactone). The 5,6-diol moiety
of the latter was then submitted to an oxidative cleavage
(periodic acid, THF)33 and the resulting crude aldehyde was
readily reduced (NaBH3CN, AcOH) to provide 2,3-O-
isopropylidene-D-lyxono-1,4-lactone (64% over the two steps).
Finally, the benzylation of the primary alcohol at C-6 (BnBr, NaH,
DMF, 24%) followed by the hydrolysis of the ketal (AcOH, water,
73%) led to 5-O-benzyl-D-lyxono-1,4-lactone (7% overall yield
from L-gulonolactone).
To confirm the diastereoisomeric ratios measured by 1H NMR
spectroscopy, HPLC analysis of the crude dihydroxylation
mixtures was carried out. To do so, the two pure diastereomers
(i.e., protected D-ribono-1,4-lactone and D-lyxono-1,4-lactone)
were required for every single protected HBO-R. As these
compounds were not commercially available, we first dedicated
ourselves to their synthesis starting from readily available
commercial D-ribono-1,4-lactone, D-lyxono-1,4-lactone and D-
gulonolactone.
With all the standards in hand, HPLC analyses of the crude
reaction mixture were performed. The d.r. calculated from the
chromatograms and reported in Table 1 were similar to those
obtained by 1H NMR spectroscopy with values between 82:18
and 97:3, thus undoubtedly confirming the protecting group-
dependency of the syn-dihydroxylation diastereoselectivity
toward D-ribono-1,4-lactone scaffold. When compared to the
previously reported procedure involving K2OsO4 and DCH-18-
crown-6 ether,24 RuO4-catalyzed and modified-Upjohn syn-
dihydroxylations prove as diastereoselective, the latter is
nevertheless more efficient with regards to yields.
O
O
O
O
TBDMSCl or TBDPSCl, imidazole, DMF
HO
RO
HO
OH
HO
OH
The fourth and final step of this novel chemo-enzymatic route to
D-(+)-ribono-1,4-lactone from LGO consisted in the removal of
the protecting groups at the 5-O position of the HBO-R-2OH
compounds. It is noteworthy to mention that the cleavage
procedures have been performed on the mixtures of
diastereomers and not on isolated protected D-ribono-1,4-
lactones. Deprotection of the benzyl group of HBO-Bn-2OH was
readily performed using palladium-catalyzed hydrogenation
providing HBO-2OH in 92% yield (Table 2, entry 1). Silyl ethers
cleavage was first attempted under classical deprotection
conditions in presence of fluoride anions. Among the various
reagents used, KF proved efficient on HBO-TBDPS-2OH,
providing D-(+)-ribono-1,4-lactone in 52% yield (Table 2, entry 2),
while tetra-n-butylammonium fluoride (TBAF) allowed the
deprotection of HBO-TBDMS-2OH in 68% yield (Table 2, entry
6).
D-(+)-ribono-1,4-lactone
5-O-R D-(+)-ribono-1,4-lactone
R = TBDMS, 25%
R = TBDPS, 76%
O
O
O
O
TBDMSCl or TBDPSCl, imidazole, DMF
HO
RO
HO
OH
HO
OH
D-(+)-lyxono-1,4-lactone
5-O-R D-(+)-lyxono-1,4-lactone
R = TBDMS, 37%
R = TBDPS, 74%
Scheme 5. Preparation of the silylated standards for HPLC
5-O-tert-butyldimethylsilyl-D-ribonolactone
and
5-O-tert-
butyldimethylsilyl-D-lyxono-1,4-lactone were readily obtained in
one step through the silylation of D-ribono-1,4-lactone and D-
lyxono-1,4-lactone, respectively (TDMSCl, imidazole, DMF, 25%
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10.1002/ejoc.201801780
European Journal of Organic Chemistry
COMMUNICATION
O
O
O
O
O
O
HCl, acetone
BnBr, NaH, DMF
34%
BnBr, NaH, DMF
86%
BnO
O
O
HO
BnO
HO
75%
O
O
O
O
HO
HO
OH
OH
D-(+)-ribono-1,4-lactone
5-O-benzyl-D-(+)-ribono-1,4-lactone
HO
HO
O
1) p-TsOH, acetone, 2,2-DMP
1) periodic acid, THF
2) NaBH3CN, AcOH
1) BnBr, NaH, DMF, 24%
2) NaBH3CN, AcOH, 73%
O
O
O
O
O
O
HO
HO
O
2) AcOH, water
HO
BnO
O
O
61%
64%
O
HO
D-gulonolactone
O
OH
HO
OH
5-O-benzyl-D-(+)-lyxono-1,4-lactone
Scheme 6. Preparation of the benzylated standards for HPLC
TBDMS towards acidic hydrolysis, its removal requires harsher
acidic conditions.37
Deprotection
O
O
O
O
RO
HO
HO
OH
HO
OH
HBO-R-2OH
D-(+)-ribono-1,4-lactone
Conclusion
This
four-step
synthetic
route
from
cellulose-based
Table 2. Deprotection of HBO-R-2OH
levoglucosenone (LGO) involving (i) H2O2-mediated Baeyer-
Villiger oxidation and (ii) diastereoselective and high yielding
modified-Upjohn syn-dihydroxylation as key steps allows to
access D-(+)-ribono-1,4-lactone with good to excellent
diastereoselectivity and in good overall yields using TBDMS
(44% yield, d.r. ca. 94:6), TBDPS (38%, d.r. ca. 94:6) and Bn
(31%, d.r. ca. 80:20) protecting group, respectively. Although
this new route does not compete with the one-step oxidation of
D-ribose into D-(+)-ribono-1,4-lactone (ca. 65%) in terms of yield,
diastereoselectivity and number of steps, not only it uses LGO, a
cheaper renewable starting material, but it also allows the
straightforward synthesis of 5-O-silylated and benzylated ribono-
1,4-lactones which are valuable intermediates for the synthesis
of high value added chemicals such as bioactive compounds
and functional additives for drugs, food, feed or cosmetics.
Substrate
(HBO-R-2OH)
Yield
(%)[a]
Overall yield
from LGO
(%)
Entry
Procedure
HBO-Bn-2OH
1
H2, Pd/C, EtOH
92
31
2
3
4
HBO-TBDPS-2OH
KF, DMF
52
51
62
32
31
38
CH3COCl, MeOH
TfOH-SiO2, MeCN
Montmorillonite
K10, MeOH/water
5
<10
-
TBAF, THF,
DOWEX 50W
HBO-TBDMS-2OH
6
7
8
68
37
77
39
21
44
CH3COCl, MeOH
Acknowledgements
Montmorillonite
K10, MeOH/water
The authors are grateful to the Circa Group for providing them
with industrial grade levoglucosenone, and to the Région Grand
Est, the Conseil Départemental de la Marne, and Grand Reims
for their financial support.
[a] Isolated
In the latter case, it is worth noting that the resulting D-ribono-
1,4-lactone being highly water-soluble, resin-based post-
treatment was used instead of classical aqueous treatment to
remove the excess of reagent. Assays using acetyl chloride34
and triflic acid supported on silica35 as acid catalyst on HBO-
TBDPS-2OH resulted in 51 and 62% yields, respectively (Table
2, entry 3). Successful deprotection of HBO-TBDMS-2OH in
37% was also observed with acetyl chloride (Table 2, entry 7).
Keywords: Chiral pool • Oxidation • Asymmetric synthesis •
Dihydroxylation • Substituent effects
[1]
[2]
A. Corma, S. Iborra, A. Velty, Chem. Rev. 2007, 107 (6), 2411-2502.
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[3]
[4]
[5]
[6]
G. W. Huber, S. Iborra, A. Corma, Chem. Rev. 2006, 106 (9), 4044-
4098.
Finally, we were pleased to observe that the use of
a
sustainable and mild procedure36 involving Montmorillonite K10
in a methanol/water mixture allowed the deprotection of HBO-
TBDMS-2OH in 77% (Table 2, entry 8). Unfortunately, the
implementation of this procedure on HBO-TBDPS-2OH did not
prove successful with only <10% yield (Table 2, entry 5). Indeed,
TBDPS being considerably more stable (ca. 100 times) than
M. S. Miftakhov, F. A. Valeev, I. N. Gaisina, Russ. Chem. Rev. 1994,
63 (10), 869-882.
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10.1002/ejoc.201801780
European Journal of Organic Chemistry
COMMUNICATION
Entry for the Table of Contents
Key topic: Ribonolactone synthesis
COMMUNICATION
M. Moreaux, G. Bonneau, A. A. M. Peru,
F. Brunissen, M. Janvier, A. Haudrechy*
and F. Allais*
O
O
O
Baeyer-Villiger
O
O
Deprotection
1) Protection
O
O
O
RO
HO
O
HO
2) syn-Dihydroxylation
HO
OH
HO
OH
D-(+)-ribono-1,4-lactone
5-O-protected D-ribono-1,4-lactone
LGO
HBO
Page No. – Page No.
d.r. 82:18-97:3
d.r. 82:18–97:3
High yielding diastereoselective syn-
dihydroxylation of protected HBO: an
access to D-(+)-ribono-1,4-lactone
and 5-O-protected analogues
A diastereoselective synthetic pathway leads to valuable D-(+)-ribono-1,4-lactone
and its 5-O-protected derivatives starting from cellulose-derived levoglucosenone.
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