Enantioselective synthesis of deoxymannojirimycin based on sharpless asymmetric epoxidation of a highly functionalized allylic alcohol

Article abstract of DOI:10.1002/ejoc.201100102

An efficient enantioselective synthesis of deoxymannojirimicin is reported. It is based on the unusual Sharpless asymmetric epoxidation of a silyl-substituted allylic 1,4-amino alcohol coupled with a further highly stereoselective intramolecular aldolizat

Full text of DOI:10.1002/ejoc.201100102

SHORT COMMUNICATION
DOI: 10.1002/ejoc.201100102
Enantioselective Synthesis of Deoxymannojirimycin Based on Sharpless
Asymmetric Epoxidation of a Highly Functionalized Allylic Alcohol
Marie-Céline Lamas,[a] Max Malacria,[a] and Serge Thorimbert*[a]
Keywords: Asymmetric synthesis / Nitrogen heterocycles / Aldol reactions / Epoxidation / Total synthesis
An efficient enantioselective synthesis of deoxymannojirim-
icin is reported. It is based on the unusual Sharpless asym-
metric epoxidation of a silyl-substituted allylic 1,4-amino
alcohol coupled with a further highly stereoselective intra-
molecular aldolization. Both enantiomers of deoxymannojiri-
micin are available. An orthogonally protected polyhy-
droxylated piperidine was prepared, which could formally
lead to other members of this piperidine family.
depicts the selected synthetic pathway based on an enantio-
selective Sharpless asymmetric epoxidation to control the
first two stereogenic centers. Polyhydroxylated piperidine 1
could be obtained from previously functionalized silylpiper-
idine 4. The piperidine ring is expected to be formed during
stereoselective intramolecular aldol condensation of acyclic
precursor 5. The oxirane of 5 would be formed by enantio-
selective Sharpless epoxidation of silylated allylic alcohol
6.[10] The introduction of the overall chirality being con-
trolled at that stage of the synthesis. Chemo- and stereose-
lective palladium-catalyzed amination of bis-allylic deriva-
tives 7 gives target precursor 6 with the required double
bond configuration.
Introduction
Since the isolation of deoxynojirimicin in the 1970s, gly-
cosidase inhibitors have become the subject of intense scru-
tiny. Besides their influences on cell–cell and cell–virus re-
cognition processes, they present marked effects on glyco-
protein processing and oligosaccharide metabolism.[1,2]
Polyhydroxylated piperidines are one class of nitrogen het-
erocycles that can be used as potential drugs to treat diabe-
tes, hepatitis, and several type of cancer.[3,4] 1-Deoxyman-
nojirimycin (1), 1-deoxynojirimycin (2), and fagomine (3)
(Figure 1) and also their N-alkylated derivatives have been
well studied for their biological properties.[5] Due to their
potential as therapeutic agents and in order to develop bio-
logically active analogues, a large number of synthetic ap-
proaches toward piperidines have been developed.[6,7] The
growing need of efficient and short access to polyhy-
droxylated piperidines prompted us to propose a general
stereoselective synthesis to this class of molecules.[8]
Scheme 1. Retrosynthesis towards (–)-deoxymannojirimycin (1).
Figure 1. Structure of 1-deoxymannojirimycin (DMJ, 1), 1-deoxy-
nojirimycin (DNJ, 2), and fagomine (3).
As depicted in Scheme 2, the reaction of bis-allylic dicar-
bonate 7[11] with N-tosylglycine methyl ester in the presence
of palladium(0) results in a highly regio- and stereoselective
substitution of only one carbonate. Interestingly, performed
Results and Discussion
This communication deals with the de novo enantioselec-
tive synthesis of (–)-deoxymannojirimycin (1).[9] Scheme 1
[a] UMPC Univ Paris 06, Institut Parisien de Chimie Moléculaire
(UMR CNRS 7201),
4 place Jussieu, C43, 75005 Paris, France
Fax: +33-1-44273056
E-mail: serge.thorimbert@upmc.fr
Supporting information for this article is available on the
WWW under http://dx.doi.org/10.1002/ejoc.201100102.
Scheme 2. Preparation of (E)-allylic alcohol 6.
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M.-C. Lamas, M. Malacria, S. Thorimbert
SHORT COMMUNICATION
in THF, the reaction does not deliver the expected product, its trans/cis diastereomer 11 as a minor product (10/11 =
but instead degradation occurred.[12] In iPrOH, allylic 82:18). In both cases, the relative configuration between the
amine 8 was isolated in 75% yield. Treatment of 8 with a oxiranyl and the hydroxy functions was totally controlled
catalytic amount of K2CO3 in MeOH gave corresponding to be trans.[17] Attempts to improve the diastereoselectivity
allylic alcohol 6 in excellent yield.
by lowering the temperature with or without Lewis acids
Starting from compounds 6, a study of the enantio- [Yb(OTf)3, Mg(ClO4)2] were unsuccessful. However, dia-
selectivity of the epoxidation step was performed. We first stereoisomers 10 and 11 could be separated by careful SiO2
turned our attention toward the Sharpless conditions.[13] flash chromatography.
Surprisingly, only few examples have been reported con-
cerning the Sharpless asymmetric epoxidation of alkenes
bearing both amine and alcohol functions in the allylic po-
sitions.[14] These kinds of compounds seem to be challeng-
ing substrates, and a stoichiometric amount of Ti(OiPr)4
coupled with long reaction times have been mainly re-
ported.[15] More challenging is the reactivity of precursor 6,
because the double bond bears three substituents and re-
mains relatively hindered (Scheme 3).
Scheme 4. Preparation of piperidine 4.
At that point of the synthesis, 10 could be converted into
the corresponding silylated ether. HPLC analysis confirmed
the high enantiomeric purity of piperidines (+)-12 and (–)-
Scheme 3. Sharpless enantioselective epoxidation of 6.
12. For that purpose, a racemic mixture of 10 and 11 was
As expected, the reaction takes place with stoichiometric
quantities of Ti(OiPr)4 as the metal source, diisopropyl-
tryptamine (DIPT) as the chiral inductor, and tert-butyl hy-
droperoxide (TBHP) as the co-oxidant. We observed total
conversion of the starting material after 7 d in DCM at
–25 °C. The optimum balance between conversion and en-
antiomeric excess allowed us to isolate expected epoxide 9
in an average yield of 80% after purification. The reaction
was performed on various scales (0.5 to 5 g scale) and even
with a large quantity of substrate, no decrease in the con-
version or selectivity was observed. Under the best condi-
tions, using (+)-DIPT, an enantiomeric ratio (er) of 98:2
was obtained for (+)-9 (determined by chiral HPLC, Chira-
cel OD-H column; hexane/iPrOH, 0.45:0.05 mL). A dra-
matic influence of the temperature on the enantioselectivity
was observed when the reaction was by performed at –20 °C
with (–)-DIPT as the chiral source.[16] Epoxide (–)-9 was
isolated after 5 d in 75% yield and with a 85:15er. We have
no explanation for such sensitivity to the temperature. Even
if stoichiometric quantities of reagent are required, this re-
action using Ti(OiPr)4 and tartrate is not expensive and al-
lowed the preparation of both enantiomers of precursor 6
in high yields and gram quantities.
also converted into corresponding TBDS ethers 12 and 13
(see Supporting Information). We pursued the synthesis
with enantiomer (–)-12. Having the correctly functionalized
piperidine core in hand, we reduced both the ester and the
epoxide functions with LiAlH4. As expected, the opening
of the oxiranyl ring is totally chemoselective and proceeds
through attack of the hydride onto the carbon bearing the
silicon group. The N-tosyl protecting group could be re-
moved during the reduction by prolonging the reaction time
to 48 h. To facilitate the purification, the acylation of the
crude mixture with Ac2O was carried out to give expected
piperidine 4 in 78% yield after chromatography.
The oxidation of the C–Si bond of 4 to a C–O bond
with overall retention of configuration could be conducted
according
to
the
Tamao–Fleming
procedure
(Scheme 5).[18,19] Upon treatment with Hg(OAc)2
(1.6 equiv.) in a AcOOH/AcOH solution, 4 was oxidized
into 14 in 78% yield. The use of the Fleming’s buffered
conditions (AcOOH, AcOH, KBr) led to only moderate
On both enantiomers of 9, the primary alcohol function
was oxidized into an aldehyde group in 70% yield by treat-
ment with iodoxybenzoic acid. Resulting acyclic epoxy al-
dehyde 5 cyclized smoothly in the presence of DBU to give
the desired piperidine ring in 98% yield (Scheme 4). This
highly stereoselective intramolecular aldolization gave
mainly one out of four possible stereoisomers. Expected
trans/trans diastereomer 10 was the major compound with Scheme 5. Tamao–Fleming oxidation: preparation of (–)-DMJ (1).
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Enantioselective Synthesis of Deoxymannojirimycin
136.0 (Cq), 143.6 (Cq), 168.9 (Cq) ppm. HRMS: calcd. for
C22H29NO6SSiNa 486.1383; found 486.1373.
conversion and the starting material was recovered in 50%
yield after 15 h.
After selective removal of the TBS protecting group of
14, the intermediate diol was acetylated to isolate penta-
acetylated (–)-DMJ 15. Finally, total deprotection with a
6 n HCl gave expected d-DMJ salt 1·HCl after simple evap-
oration of the volatiles. The spectral data of this compound
are in total accord with the literature data.[20] This validates
our enantioselective approach for the synthesis of both
enantiomers of DMJ (1).
Supporting Information (see footnote on the first page of this arti-
cle): HPLC data and/or optical rotation for compounds 4, 5, 9, 12,
and 1.
Acknowledgments
We gratefully acknowledge financial support from the University
Pierre et Marie Curie (UPMC), Centre National de la Recherche
Scientifique (CNRS), and Institut Universitaire de France (IUF).
We thank A. Dos Santos, H. Said Hamed, and R. Ngo for initial
technical assistance.
Conclusions
In conclusion, we reported an alternative enantioselective
synthesis of deoxymannojirimycin that rivals previously
published preparations. (–)-Deoxymannojirimycin was ob-
tained in seven steps from acyclic precursor 6 (34% yield,
Ͼ96%ee). This approach allows differentiation of all the
hydroxy groups, which we believe offers great potential for
the elaboration of more complex molecules. This work illus-
trates that a strategy based on the Sharpless epoxidation of
functionalized trisubstituted alkenes is a viable and useful
synthetic approach for the enantioselective construction of
polyhydroxylated heterocycles.
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Experimental Section
Molecular sieves (4 Å, 5.7 g) were heated at 250 °C and dried in
vacuo overnight before use. Under an atmosphere of argon, a solu-
tion of Ti(OiPr)4 (4.4 mL, 15 mmol, 1.2 equiv.) in CH2Cl2 (93 mL)
was added to the molecular sieves. The heterogeneous solution was
stirred at –23 °C for 15 min. A solution of (+)-DIPT (4.32 g,
14.8 mmol, 1.2 equiv.) in CH2Cl2 (93 mL) was added by cannula to
the cold mixture under an atmosphere of argon, and the flask was
washed with CH2Cl2 (27 mL) The resulting mixture was stirred at
–23 °C for 25 min. A solution of allylic alcohol 6 (5.5 g, 12 mmol,
1 equiv.) in CH2Cl2 (93 mL + 27 mL to rinse) was then added by
cannula to the precedent cold mixture, followed by a solution of
TBHP (6 m in octane, 6.2 mL, 37 mmol, 3 equiv.). After stirring at
–23 °C for 7 d, the mixture was hydrolyzed with a saturated solu-
tion of Na2SO4 (30 mL) and stirred for 30 min to warm to room
temperature. The thick solution was filtered through Celite. The
filtrate was dried with MgSO4, filtered, and concentrated in vacuo.
After purification by flash chromatography (cyclohexane/EtOAc,
7:3 to 5:5), epoxy alcohol 9 (4.1 g, 8.8 mmol, 75%) was obtained
as a colorless oil. [α]2D0 = +15.9 (c = 0.9, CHCl3). HPLC (Chiracel
column OD-H, hexane/iPrOH = 0.45:0.05, flow rate = 0.5 mL/min,
r.t.): tR = 36.3 min, 96%ee. Rf = 0.25 (petroleum ether/EtOAc =
7:3). IR: ν = 3538, 2953, 1746, 1598, 1428, 1338, 1250, 1213, 1156,
˜
1097, 837, 735, 701 cm–1. 1H NMR (400 MHz, CDCl3): δ = 0.48
(s, 3 H SiMe3), 0.54 (s, 3 H, SiMe3), 2.42 (s, 3 H, TsMe), 2.97 (t, J
= 5.5 Hz, 1 H, 3-H), 3.38 (s, 3 H, CO2Me), 3.41 (d, J = 14 Hz, 1
H, 1-H), 3.66 (d, J = 18.5 Hz, 1 H, CO2Me), 3.71 (d, J = 5.5 Hz,
2 H, CH2OH), 3.92 (d, J = 18.5 Hz, 1 H, CH2CO2Me), 3.93 (d, J
= 15 Hz, 1 H, 1-H), 7.26 (d, J = 8 Hz, 2 H, Har), 7.34 to 7.41 (m,
3 H, Har), 7.54 to 7.62 (m, 4 H, Har) ppm. 13C NMR (100 MHz,
CDCl3): δ = –5.0 (CH3), –4.9 (CH3), 21.5 (CH3), 47.2 (CH2), 47.6
(CH2), 51.7 (CH3), 55.8 (Cq), 58.9 (CH), 60.2 (CH2), 127.4 (2 CH),
127.9 (2 CH), 129.5 (2 CH), 129.7 (CH), 134.4 (2 CH), 135.1 (Cq),
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Received: January 24, 2011
Published Online: March 23, 2011
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Eur. J. Org. Chem. 2011, 2777–2780