Practical one-pot synthesis of protected l-glyceraldehyde derivatives

Article abstract of DOI:10.1055/s-0031-1291136

A large-scale, simple, economic, and safe procedure for the preparation of l-glyceraldehyde acetonide under conditions, which allow its direct transformation (one-pot) into the desired products (acetylene, imine, nitrone, unsaturated ester) is reported. l-Glyceraldehyde acetonide is obtained from the corresponding ester, which is readily available from l-serine. Georg Thieme Verlag Stuttgart New York.

Full text of DOI:10.1055/s-0031-1291136

PRACTICAL SYNTHETIC PROCEDURES
▌2695
practical synthetic procedures
Practical One-Pot Synthesis of Protected L-Glyceraldehyde Derivatives
One-Pot Synthesis of Protected L-Glyceraldehydes
Sebastian Stecko, Michał Michalak, Maciej Stodulski, Łukasz Mucha, Kamil Parda, Bartłomiej Furman,
Marek Chmielewski*
Institute of Organic Chemistry, Polish Academy of Sciences, Kasprzaka 44/52, 01-224 Warsaw, Poland
Fax +48(22)6326681; E-mail: chmiel@icho.edu.pl
PSP
Received: 17.01.2012; Accepted after revision: 09.03.2012
No230
Abstract: A large-scale, simple, economic, and safe procedure for the preparation of L-glyceraldehyde acetonide under conditions, which
allow its direct transformation (one-pot) into the desired products (acetylene, imine, nitrone, unsaturated ester) is reported. L-Glyceralde-
hyde acetonide is obtained from the corresponding ester, which is readily available from L-serine.
Key words: L-glyceraldehyde acetonide, L-glyceraldehyde derivatives, aldehydes, nitrones, acetylenes
3 steps
O
O
O
DIBAL-H
O
O
O
L-serine
O
O
R
H
OMe
6
1
CH
7
8
9
R = C
not isolated
R = C=N(O)Bn
R = C=NCHPh2
10 R = (E)-C=CHCOOEt
Scheme 1
O,O-Ketals of L-glyceraldehyde, particularly the isopro- chain hydroxyl groups protected with isopropylidene
pylidene derivative 1 (Figure 1), represent valuable sub- group, and then the 5,6-O,O-isopropylidene derivative
strates in target-oriented synthesis.1–12 There are several subjected to NaIO4 degradation to provide 1.15
well-known methods for its preparation. Aldehyde 1 can
The 5,6-O,O-isopropylidene group can be introduced into
ascorbic acid (2) prior to hydrogenation of the double
bond. Subsequently, compound 4 is reduced with NaBH4,
be obtained, by analogy to its D-enantiomer,13 from L-
mannitol following a two-step procedure involving for-
mation of diacetal followed by a glycolic cleavage.6 Con-
hydrolyzed, and oxidized with lead tetraacetate,3,16 or al-
sidering the high price of the substrate, such a method
ternatively, the product is reduced with LiAlH4 and then
certainly has only a limited value.
oxidized with NaIO4.16,17 Compound 4 can be also sub-
Other methods use inexpensive and readily available jected to oxidative degradation (30% H2O2) to afford 3,4-
ascorbic acid (2) as the substrate. There are several ways O-isopropylidene-L-threonic acid (5) (Figure 1), which
of its transformation into 1. Substrate 2 can be hydroge- subsequently is subjected to hypochloric acid promoted
nated to L-gulono-1,4-lactone (3)14 (Figure 1), the side decarbonylation to provide 1.18,19
O
O
HO
HO
O
O
O
O
O
O
O
O
O
HO
HO
OH
O
O
(S)
1
HO
HO
OH
OH
OH
HO
COOH
2
3
4
5
O
O
O
O
Ph
O
N
N
O
O
O
O
O
O
COOMe
Bn
Ph
COOEt
6
7
8
9
10
Figure 1 Structures of compounds 1–10
SYNTHESIS 2012, 44, 2695–2698
Advanced online publication: 26.06.2012
0
0
3
9
-
7
8
8
1
1
4
3
7
-
2
1
0
X
DOI: 10.1055/s-0031-1291136; Art ID: SS-2012-T0054-PSP
© Georg Thieme Verlag Stuttgart · New York

2696
S. Stecko et al.
PRACTICAL SYNTHETIC PROCEDURES
The major drawback of all methods based on ascorbic large-scale preparation.15b,18,19 Moreover, compound 6
acid is related to the formation of the final acetonide of L- seems to be the most suitable starting material from the
glyceraldehyde 1 in dilute water solution. The numerous point of view of the atom economy. If one calculates the
applications of 1 in target-oriented synthesis usually re- mass balance of substrates and product 1, in the case of
quire an anhydrous product. To obtain such a product, la- compound 6, only ~18% of material is transformed into
borious extraction of 1 is necessary reducing substantially useless by-products whereas in the cases of 4 and 5 (for
the overall yield of the procedure. Generally, it is strongly calcium salt), ~40% and ~33% of material is wasted, re-
recommended to avoid any aqueous workup during the spectively.
glyceraldehyde synthesis due to the fact that it is able to
form a stable hydrate. Moreover, the reactions must be
The general suitability of the proposed procedure is fur-
ther demonstrated by the direct formation of acetylene 7,
carried out under restricted pH conditions because 1 is
nitrone 8, imine 9, and α,β-unsaturated ester 10 (Figure 1)
prone to racemization or deprotection under basic or acid-
from compound 1. These compounds 7–10 were selected
considering their usefulness in target-oriented synthesis.
ic condition, respectively.
Herein, we report a practical method for the synthesis of In particular, the acetylene 7, substrate for the synthesis of
crude 1 based on the transformation of relatively cheap L- ezetimibe, a powerful cholesterol inhibitor,23 can be ob-
serine. The key advantage of the proposed procedure is tained by treatment of 1 in dichloromethane solution with
the ability to use directly the solution of the freshly the Bestmann–Ohira reagent (dimethyl 1-diazo-2-oxopro-
formed aldehyde 1 without its prior isolation and purifica- pylphosphonate)24,25 in the presence of anhydrous metha-
tion (one-pot approach for synthesis).
nol and anhydrous potassium carbonate. The N-benzyl
nitrone 826,27 can be prepared by treatment of a solution of
1 with N-benzylhydroxylamine, whereas the imine 928 can
be obtained by reacting 1 with diphenylmethylamine,
while the ester 10 can be obtained by treatment of 1 with
ethyl triphenylphosphorylideneacetate29 or triethyl phos-
phonoacetate.15
Following known procedures,20–22 L-serine can be trans-
formed into the acetonide of methyl dihydroxypropanoate
6 (Scheme 1) in a three-step sequence that involves the
displacement of the amino group to form a hydroxyl
group (with retention of configuration, through the re-
spective diazonium intermediate) followed by the esterifi-
cation and acetal formation.
To conclude, we have described a large-scale, simple,
economic, and safe procedure for the preparation of L-
glyceraldehyde acetonide (1) under conditions which al-
low for its direct transformation (one-pot) into desired
products (acetylene, imine, nitrone, unsaturated ester).
Aldehyde 1 is obtained from ester 6, which is readily
available from L-serine.
According to our protocol, compound 6 can be reduced
with DIBAL-H, or other modified hydrides to provide 1.
This procedure provides ketals of L-glyceraldehyde in an
organic solvent, usually in dichloromethane, toluene, or
hexane, in good yield and ready to be used in subsequent
transformations without purification. The yield of crude
aldehyde 1 is ca. 90% (based on GC). For comparison,
procedures based on ascorbic acid derivative 4 provide
crude product 1 in 95%,15b whereas, the transformation of
L-threonic acid salts 5 give only 60–75% of crude 1.18,19
Although reported yields of aldehyde 1 are high, the effi-
ciency of isolation of the product from a solution is rather
moderate, ca. 50–55%. This is because all of the known
syntheses of L-glyceraldehyde are performed in aqueous
or aqueous/organic solution, which makes isolation of the
product from the post-reaction mixture troublesome.
There are two factors responsible for that. As mentioned
in the introduction, the product 1 forms a stable hydrate,
which increases its solubility in water and, in conse-
quence, complicates extractive workup. Additionally, L-
glyceraldehyde acetonide is a relatively volatile com-
pound, so removal of organic solvent(s) from the solution
must be performed under restricted pressure condi-
tions.15b,18,19 On the other hand, conducting the synthesis
in an anhydrous organic solvent enables to overcome the
above-mentioned difficulties and simplifies handling of
the aldehyde 1; moreover, the procedure allows to use a
solution of 1 directly for further transformations, which is
the key advantage of the described method.
All reagents were used as purchased from commercial suppliers
without further purification. Anhydrous CH2Cl2 was obtained by
distillation over CaH2 and anhydrous MeOH was purchased from
Aldrich. NMR spectra were recorded on Varian 200 and 400 MHz
spectrometers using CDCl3 with TMS as the internal standard.
Chemical shifts are reported as δ values in ppm and coupling con-
stants are in hertz. Infrared spectra were obtained on an FT-IR-1600
Perkin-Elmer spectrophotometer. The optical rotations were mea-
sured with a JASCO J-2000 digital polarimeter. Mass spectra were
recorded on ESI-TOF Mariner (Perspective Biosystem; ESI ioniza-
tion) and AMD-604 (AMD Intectra GmbH; EI ionization) spec-
trometers. Elementary analysis was recorded on a Perkin-Elmer 240
Elemental Analyzer.
Methyl (S)-2,3-O-Isopropylidenepropionate (6)
Step 1, (S)-2,3-Dihydroxypropionate:20 To a solution of L-serine (50
g, 0.47 mol) in H2O (100 mL) at 0 °C were added aq H2SO4 (5 M,
150 mL) and aq NaNO2 (6 M, 85 mL). After stirring the reaction
mixture for 5 h at r.t., an additional portion of aq NaNO2 (6 M, 85
mL) was added at 0 °C. The reaction mixture was stirred for 3 d at
r.t. and then aq H2SO4 (5 M, 150 mL) and aq NaNO2 (6 M, 85 mL)
were added at 0 °C. After stirring the reaction mixture for 2 d at r.t.,
H2O (ca. 500 mL) was distilled out under reduced pressure. The re-
sulting residue was treated with a solution of NaOH (20 g) in H2O
(50 mL) at 0 °C. Then, a mixture of MeOH–acetone (3:1, 200 mL)
was added to the resulting mixture and it was filtered through a short
pad of Celite. After removal of the solvent, a mixture of MeOH–
acetone (3:1, 200 mL) was added again. The above operation was
repeated 7 times. After partial evaporation of the solvent, toluene
Additionally, our method does not require restricted pH
control that usually creates a problem, especially during
Synthesis 2012, 44, 2695–2698
© Georg Thieme Verlag Stuttgart · New York

PRACTICAL SYNTHETIC PROCEDURES
One-Pot Synthesis of Protected L-Glyceraldehydes
IR (film): 2120, 1068 cm–1.
1H NMR (200 MHz, CDCl3): δ = 4.67 (ddd, J = 6.4, 6.2, 2.3 Hz, 1
H, H-3), 4.14 (dd, J = 8.1, 6.4 Hz, 1 H, H-4a), 3.92 (dd, J = 8.1, 6.2
Hz, 1 H, H-4b), 2.47 (d, J = 2.3 Hz, 1 H, H-1), 1.47 (s, 3 H, CH3),
1.35 (s, 3 H, CH3).
2697
(100 mL) was added to the residue, and the solvent was removed by
distillation under reduced pressure. Additional portion of toluene
(100 mL) was added to the residue and then the above operation was
repeated twice. The residue was dissolved in MeOH (200 mL) and
acidified with concd H2SO4, and then trimethyl orthoformate (50
mL) was added to the mixture. The mixture was stirred for 30 min
at 60 °C and then neutralized with NaOMe at 0 °C. After filtration
of the mixture and evaporation of the solvent, the crude product was
distilled under diminished pressure (bp 65–70 °C/0.5 Torr) to afford
methyl (S)-2,3-dihydroxypropionate (42 g, 75%) as a colorless oil;
[α]D20 –7.1 (c 0.94, CH2Cl2) {Lit.20 [α]D25 –6.11 (c 5, CHCl3)}.
13C NMR (50 MHz, CDCl3): δ = 110.7, 81.6, 74.3, 70.0, 65.5, 26.4,
26.3.
Anal. Calcd for C7H10O2: C, 66.65; H, 7.99. Found: C, 66.59; H,
8.02.
(R,Z)-[(2,2-Dimethyl-1,3-dioxolan-4-yl)methylene]-N-benzyl-
amine N-Oxide (8)
IR (neat): 3471, 1741 cm–1.
1H NMR (400 MHz, CDCl3): δ = 4.16 (m, 1 H), 3.85–3.71 (m, 2 H),
3.70 (s, 3 H), 3.39 (br s, 1 H, OH), 2.55 (br s, 1 H, OH).
13C NMR (100 MHz, CDCl3): δ = 174.0, 72.2, 64.0, 53.5.
A solution containing crude 1 (7.3 g, 325 mL) at r.t. was diluted
with CH2Cl2 (200 mL) and treated with anhyd MgSO4 (14 g, 112
mmol) and BnNHOH (7.4 g, 60 mmol) in CH2Cl2 (40 mL). After 5
h, the suspension was filtered and the solvent was evaporated. To
the oily residue was added cold Et2O (75 mL) and the crude nitrone
was separated by filtration to afford 10 g of 8 (72%, 2 steps from 6)
MS (EI) m/z = 120.0 [M].
Anal. Calcd for C4H8O4: C, 40.00; H, 6.71. Found: C, 39.90; H,
6.67.
20
as a colorless solid; mp 90–91 °C (Lit.26 mp 90 °C); [α]D –96 (c
25
0.50, CH2Cl2) {Lit.26 for the D-enantiomer [α]D +96.8 (c 0.5,
Step 2, Methyl (S)-2,3-O-Isopropylidenepropionate (6):22 To a solu-
tion of methyl (S)-2,3-dihydroxypropionate (30 g, 0.25 mol) in 2,2-
dimethoxypropane (500 mL) was added p-TsOH (1.43 g, 7.5
mmol). After stirring at r.t. for 3 h, NaHCO3 (3 g) was added, and
the mixture was stirred for 1 h. Then solid was filtered off, washed
with Et2O (3 × 100 mL), and solvents were removed under dimin-
ished pressure. The residue was distilled under reduced pressure (bp
115–118 °C/20 Torr) to afford compound 6 (35.2 g, 88%) as a col-
CHCl3)}.
IR (film): 1599 cm–1.
1H NMR (400 MHz, CDCl3): δ = 7.37 (m, 5 H), 6.78 (d, J = 4.6 Hz,
1 H), 5.08 (ddd, J = 7.1, 5.9, 4.6 Hz, 1 H), 4.80 (br s, 2 H), 4.35 (dd,
J = 8.7, 7.1 Hz, 1 H), 3.82 (dd, J = 8.7, 5.9 Hz, 1 H), 1.37 (s, 3 H),
1.34 (s, 3 H).
13C NMR (100 MHz, CDCl3): δ = 139.1, 132.1, 129.4, 129.2, 109.8,
72.0, 67.0, 67.8, 26.2, 24.9.
20
20
orless oil; [α]D –19.9 (c 1.5, CHCl3) {Lit.22 [α]D –17.4 (c 3,
CHCl3)}.
Anal. Calcd for C13H17NO3: C, 66.36; H, 7.28; N, 5.96. Found: C,
66.40; H, 7.25; N, 5.99.
IR (neat): 1760 cm–1.
1H NMR (500 MHz, CDCl3): δ = 4.56 (dd, J = 7.2, 5.2 Hz, 1 H),
4.20 (dd, J = 8.7, 7.2 Hz, 1 H), 4.07 (dd, J = 8.7, 5.2 Hz, 1 H), 3.74
(s, 3 H), 1.45 (s, 3 H), 1.36 (s, 3 H).
(S)-2,2-Dimethyl-1,3-dioxolan-4-ylmethylene-1,1-diphenyl-
methylamine (9)
A solution containing crude 1 (7.3 g, 325 mL) at r.t. was diluted
with CH2Cl2 (150 mL) and treated with Ph2CHNH2 (62 mmol, 11.3
g) and anhyd MgSO4 (112 mmol, 13.4 g). After 2 h, the mixture was
filtered and the solid was washed with anhyd CH2Cl2 (3 × 50 mL).
The solvent was evaporated from the combined organic layers un-
der diminished pressure to afford 16.6 g (90%, 2 steps from 6) of
imine 9 as a colorless syrup; [α]D20 –35 (c 1, CH2Cl2).
1H NMR (400 MHz, CDCl3): δ = 7.72 (d, J = 4.8 Hz, 1 H, CH=N),
7.10–7.23 (m, 10 H, ArH), 5.34 (s, 1 H, CHPh), 4.62 (td, J = 6.8,
6.0, 4.8 Hz, 1 H, CHCH2O), 4.12 (dd, J = 8.4, 6.8 Hz, 1 H, OCH2),
3.91 (dd, J = 8.4, 6.0 Hz, 1 H, OCH2), 1.33 (s, 3 H, CH3), 1.30 (s, 3
H, CH3).
13C NMR (125 MHz, CDCl3): δ = 171.5, 111.3, 73.9, 52.2, 25.7,
25.4.
HRMS (ESI): m/z [M + Na+] calcd for C7H12O4 + Na: 183.0633;
found: 183.0629.
Anal. Calcd for C7H12O4: C, 52.49; H, 7.55. Found: C, 52.33; H,
7.65.
2,3-O-Isopropylidene-L-glyceraldehyde (1)
To a solution of ester 6 (10 g, 62.4 mmol) in anhyd CH2Cl2 (250
mL) cooled to –78 °C was slowly added a 1 M solution of DIBAL-
H in CH2Cl2 (75 mL) over 1 h. The reaction progress was monitored
by GC. After disappearance of the substrate (ca. 5–6 h), the crude
acetonide of L-glyceraldehyde 1 (7.3 g, yield 90%, calculated by
GC with an internal standard) was ready for further transformations
without isolation and purification. An analytical sample was ob-
tained by extraction and distillation under diminished pressure; bp
13C NMR (100 MHz, CDCl3): δ = 163.6, 143.0, 142.9, 128.5, 127.6,
127.5, 127.14, 127.11, 110.2, 67.4, 26.5, 25.4.
MS (EI): m/z = 295.4 [M].
Anal. Calcd for C19H21NO2: C, 77.26; H, 7.17; N, 4.74. Found: C,
77.25; H, 7.15; N, 4.75.
20
68–75 °C/30 Torr [Lit.15 bp 67–73 °C/30 Torr]; [α]D −72 (c 6,
CH2Cl2) {Lit.15 [α]D20 –75.4 (c 8, C6H6)}.
1H NMR (400 MHz, CDCl3): δ = 9.72 (d, J = 2.0 Hz, 1 H), 4.08–
4.21 (m, 2 H), 4.38 (m, 1 H), 1.49 (s, 3 H), 1.44 (s, 3 H).
E/Z-Mixture of Ethyl (R)-3-(2,2-Dimethyl-1,3-dioxolan-4-yl)ac-
rylate (10)
Ethyl triphenylphosphorylideneacetate (84 mmol, 29.3 g) was add-
ed to a solution containing crude aldehyde 1 (7.3 g, 325 mL) and the
mixture was stirred for 16 h at r.t. Subsequently, the mixture was fil-
tered and the solid was washed with CH2Cl2 (3 × 100 mL). The sol-
vent from the combined washings was evaporated under diminished
pressure. The residue was purified on a silica gel column using hex-
ane–EtOAc (9:1) as an eluent to afford 10.1 g of the E-isomer 10
(81%, 2 steps from 6) as a colorless syrup and 0.9 g of the Z-isomer.
(S)-4-Ethynyl-2,2-dimethyl-1,3-dioxolane (7)
Anhyd MeOH (150 mL) was added to a solution of crude 1 (7.3 g,
325 mL) and the mixture was cooled to –10 °C. Subsequently, an-
hyd K2CO3 (112 mmol, 15.6 g), and Bestmann–Ohira reagent (84
mmol, 16.1 g) were added. After 12 h, the mixture was treated with
sat. aq NH4Cl (200 mL) and stirred for additional 1 h. Subsequently,
the mixture was extracted with pentane (2 × 100 mL) and the com-
bined extracts were dried (MgSO4). The solvent was evaporated un-
der diminished pressure (40° C/650 mbar) and the residue distilled
at 110–112 °C/250 Torr to afford 6.3 g (80%, 2 steps from 6) of
acetylene 7 as a colorless syrup; [α]D20 –40 (c 1.0, CH2Cl2) {Lit.30
for the D-enantiomer [α]D20 +40.6 (c 1.1, CHCl3)}.
E-Isomer 10
[α]D20 –40.1 (c 1, CH2Cl2) {Lit.29 [α]D20 –40 (c 1.1, CHCl3)}.
1H NMR (400 MHz, CDCl3): δ = 6.79 (dd, J = 16.0, 5.3 Hz, 1 H),
6.01 (dd, J = 16.0, 0.9 Hz, 1 H ), 4.58 (q, J = 6.0 Hz, 1 H), 4.16–4.06
© Georg Thieme Verlag Stuttgart · New York
Synthesis 2012, 44, 2695–2698

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S. Stecko et al.
PRACTICAL SYNTHETIC PROCEDURES
(m, 3 H), 3.58 (t, J = 7.6 Hz, 1 H), 1.35 (s, 3 H), 1.31 (s, 3 H), 1.20
(t, J = 7.0 Hz, 3 H).
13C NMR (100 MHz, CDCl3): δ = 166.0, 144.7, 122.4, 110.2, 75.0,
68.8, 60.6, 26.5, 25.8, 14.2.
HRMS (ESI): m/z calcd for C10H17O4 [M + H+]: 201.1127; found:
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Anal. Calcd for C10H16O4: C, 59.98; H, 8.05. Found: C, 59.96; H,
8.03.
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Acknowledgment
Financial support for this work was provided through the Polish Mi-
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