Preparation of chiral cyclopropanecarboxylic acids and 3-oxabicyclo[3.1.0]hexane-2-ones from levoglucosenone

Article abstract of DOI:10.1016/j.tetasy.2008.02.016

Levoglucosenone (a chiral α,β-unsaturated ketone derivative of cellulose) serves as a starting compound in 2 and 3 step syntheses of chiral cyclopropanecarboxylic acids and 3-oxabicyclo[3.1.0]hexane-2-ones, respectively.

Full text of DOI:10.1016/j.tetasy.2008.02.016

Available online at www.sciencedirect.com
Tetrahedron: Asymmetry 19 (2008) 691–694
Preparation of chiral cyclopropanecarboxylic acids and
3-oxabicyclo[3.1.0]hexane-2-ones from levoglucosenone
Alexander V. Samet,* Dmitriy N. Lutov, Leonid D. Konyushkin, Yuri A. Strelenko and
Victor V. Semenov
N. D. Zelinsky Institute of Organic Chemistry RAS, Leninsky Pr., 47 Moscow 119991, Russia
Received 15 January 2008; accepted 13 February 2008
Abstract—Levoglucosenone (a chiral a,b-unsaturated ketone derivative of cellulose) serves as a starting compound in 2 and 3 step
syntheses of chiral cyclopropanecarboxylic acids and 3-oxabicyclo[3.1.0]hexane-2-ones, respectively.
Ó 2008 Elsevier Ltd. All rights reserved.
O
1. Introduction
O
O
O
O
O
RCO3H
Chiral molecules with a cyclopropane motif are of major
interest as biologically active natural and synthetic prod-
ucts1,2 and as intermediates in organic synthesis.3 In partic-
ular, chiral 3-oxabicyclo[3.1.0]hexane-2-ones A can serve as
valuable starting compounds in the preparation of chiral
cyclopropanecarboxylic acid derivatives,4–6 chiral butano-
lides,7 and nucleoside analogues.8 Compounds A are, in
turn, prepared either by intramolecular cyclization of allyl
diazoacetates in the presence of chiral catalysts9–11 or from
various chiral precursors.12–16
H
O
O
O
R1
H
R2
H
R1
R2
1
O
H
2
H+
O
HCO
O
O
H
H
R1 R2
O
O
3
Scheme 1.
A
subsequent acid-catalyzed recyclization, although the
mechanism involved was never investigated in detail).
Levoglucosenone 1 [(1S,5R)-6,8-dioxabicyclo[3.2.1]oct-2-
ene-4-one]—an unsaturated ketone prepared by acid-cata-
lyzed pyrolysis of cellulose—is known to undergo stereo-
selective Michael addition of nucleophiles and cycloaddi-
tion to the C@C bond on the side opposite to the 1,6-anhy-
dro bridge.17–19 With peracids, these addition products 2
(as well as compound 1 itself) undergo an unusual transfor-
mation to butanolides 3 (Scheme 1) with retention of con-
figuration of the asymmetric centers20–23 (evidently, this is
an interesting case of a Baeyer–Villiger rearrangement with
By cyclopropanation of levoglucosenone 1 with sulfur
ylides, we have recently prepared chiral cyclopropanes 4,24
(Scheme 2), which may be able to undergo a similar conver-
sion to the target chiral 3-oxabicyclo[3.1.0]hexane-2-ones.
O
O
R2S=CHCOR'
A
1
H
H
R'OC
O
H
4
*
Corresponding author. Tel.: +7 495 7161418; e-mail addresses:
sametav@yahoo.com; sametav@server.ioc.ac.ru
Scheme 2.
0957-4166/$ - see front matter Ó 2008 Elsevier Ltd. All rights reserved.
doi:10.1016/j.tetasy.2008.02.016

692
A. V. Samet et al. / Tetrahedron: Asymmetry 19 (2008) 691–694
2. Results and discussion
O
HO
H
HCO 2'
O
OH
3
We have found that annulated cyclopropanes 4 can be
converted by 30% aq H2O2 in AcOH to cyclopropanecarb-
oxylic acids 5; heating of the latter in MeOH/HCl pro-
duces 4-hydroxymethyl-3-oxabicyclo[3.1.0]hexane-2-ones
6 (Scheme 3, Table 1).
O
1'
H
H
COOH
H
4
1
5
1
H
H
2
6
H
H
Cl
Cl
O
O
5b
6b
Figure 1. Key cross-peaks in 2D 1H NOESY spectra of 5b and 6b.
O
O
30% H2O2 (1.2 eq.)
O
4
AcOH
H
The structures of compounds 5 and 6 are confirmed by
1
OH
NOE spectra of 5b and 6b (Fig. 1). The 2D H NOESY
H
R'OC
spectrum of 6b features a strong cross-peak between the
signals of H-1 (d 2.65) and H-5 (d 2.71) protons and weak
cross-peaks between these two signals and the signal of the
H-6 proton (d 3.42), thus indicating that the H-6 proton is
trans- to the protons H-1 and H-5. This is consistent with
O
B
H
H
HO
H
the coupling constants values J1,6 = 2.4–2.6 Hz, J5,6
=
HCO
O
OH
1
O
3.2–3.4 Hz, J1,5 = 6.1–6.2 Hz in H NMR spectra of 6a–
g, considering that cis-constants in cyclopropanes are lar-
ger than trans-. The configurations of the C-6 (and C-4)
centers are further confirmed by a strong cross-peak be-
tween the signals of H-6 and H-4 (d 4.63) protons (any
other configuration of these centers would increase the dis-
tance between the H-6 and H-4 protons and thus render
such a cross-peak impossible, cf. NOE experiments with
similar structures15,26).
MeOH, H+
O
COOH
H
H
H
H
H
H
H
COR'
COR'
5
6
Scheme 3.
Table 1. Preparation of compounds 5a–d, 6a–g
Starting
compound
R0
Product 5
(yield)
Product
6 (yield)
1
Similarly, in the 2D H NOESY spectrum of 5b, strong
cross-peaks between the signals of H-1 (d 2.29) and H-3
(d 1.94) protons and between the signals of H-2 (d 3.30)
and H-10 (d 3.93) protons, together with weak cross-peaks
H-1–H-2, H-2–H-3 and the coupling constant values
J1,2 = 4.5–4.6 Hz, J2,3 = 5.7–5.8 Hz, J1,3 = 9.4–9.5 Hz in
1H NMR spectra of 5a–d, indicate that the stereochemistry
of 5 is the same as that of 6. In addition, the formyl proton
(d 8.20) shows a cross-peak with CH2-protons (d 4.12 and
4.18) rather than with H-10 proton, thus supporting the
proposed 2-formyloxy-1-hydroxyethyl side chain structure
against a 1-formyloxy-2-hydroxyethyl structure, which ini-
tially seemed possible as well.
4a
4b
4c
Ph
4-ClC6H4
4-BrC6H4
5a (79)
5b (83)
5c (82)
6a (81)
6b (84)
6c (79)
4d
4e
5d (79)
6d (80)
S
Me
a
6e (79b)
N
N
O
a
a
4f
4g
1-Adamantyl
OEt
6f (63b)
6gc (67b)
a Not isolated in pure form.
b Yield in two steps from 4.
These data are in agreement with the previously reported
retention of the configuration of the stereocenters in the
process of the rearrangement (Scheme 1).20–23
c For 6g, R0 = OMe due to transesterification.
It should be noted that there is no need to use hazardous
peracetic acid or a large excess of H2O2 (cf. lit.20–23). The
transformation of 4e–g to 5e–g is accompanied by partial
hydrolysis of the formyl group in the products, so the cor-
responding crude 5 was converted to 6 without isolation.
At the same time, oxidation of 4a–d (R0 = Ar or 2-thienyl)
affords pure acids 5a–d in high yields. Most likely, the acids
5 result from the acid-catalyzed hydrolysis of the intermedi-
ate lactones B (Scheme 3) Interestingly, the rearrangement
selectively affects a cyclic keto group in molecules 4a–f,
while the acyl substituents (COR0) in the cyclopropane ring
are left intact. This is, probably, due to the remarkably high
reactivity of the cyclic keto group adjacent to an acetal frag-
ment (thus, it is known to readily add water and MeOH
yielding gem-diols and ketals, respectively).17,24,25
3. Conclusion
Thus, levoglucosenone proved to be a suitable chiral tem-
plate for the convenient and straightforward synthesis of
optically active substituted cyclopropanecarboxylic acids
and 3-oxabicyclo[3.1.0]hexane-2-ones.
The assignments of H-1 and H-5 protons are also based on the 2D 1H
NOESY spectrum of 6b. The signal at d 2.71, in contrast to the one at d
2.65, shows cross-peaks with the signals of H-4 (d 4.63) and CH2-protons
(d 3.62), thus indicating the former to be the H-5 proton, and the latter
to be H-1.

A. V. Samet et al. / Tetrahedron: Asymmetry 19 (2008) 691–694
693
4. Experimental
H-3); 2.26 (dd, J = 9.4, 4.5 Hz, 1H, H-1); 3.22 (t,
J = 5.2 Hz, 1H, H-2); 3.93 (m, 1H, H-10); 4.14 (m, 2H,
CH2); 5.27 (br s, 1H, OH); 7.29 (dd, J = 4.9, 3.8 Hz, 1H);
8.08 (dd, J = 4.9, 1.6 Hz, 1H); 8.19 (m, 1H, HCOO);
12.63 (br s, 1H, COOH). Anal. Calcd for C12H12O6S: C,
50.70; H, 4.25; S, 11.28. Found: C, 50.61; H, 4.40; S, 10.93.
4.1. General
NMR spectra were recorded on a Bruker-DRX500 spec-
1
1
trometer (500.13 MHz for H NMR and 2D H NOESY,
125.75 MHz for 13C). Optical rotations were measured on
a Jasco-340 polarimeter. Compounds 4 were prepared by
a known procedure.24 Levoglucosenone 1 was supplied
by Chemical Block Ltd (www.chemblock.com).
4.2.2. Preparation of 6a–d (general procedure). To a solu-
tion of 5a–d (2 mmol) in MeOH (3 ml), concd HCl (0.1 ml)
was added and the mixture was refluxed for 3 h. Then, the
solvent was distilled off at atmospheric pressure, the residue
was kept for 30 min at 80 °C and recrystallized from a suit-
able solvent.
4.2. Synthetic procedures
4.2.1. Preparation of 5a–d (general procedure). To a solu-
tion of 30% aq H2O2 (0.27 g, 2.4 mmol) in glacial AcOH
(2 ml), 4a–d (2 mmol) was added in portions with stirring.
The resulting suspension was gently heated at 30–40 °C
until a clear solution was formed and left for 5 h at rt.
The resulting precipitate of 5a–d was filtered off, washed
thoroughly with water, and dried.
4.2.3. Preparation of 6e–g (‘one-pot’, general proce-
dure). To a solution of 30% aq H2O2 (0.27 g, 2.4 mmol)
in glacial AcOH (2 ml), 4e–g (2 mmol) was added in por-
tions with stirring. The resulting suspension was gently
heated at 30–40 °C, until a clear solution was formed (ca.
20 min) and then left for 5 h at rt. The solvent was removed
in vacuo, and the residue was dissolved in MeOH (3 ml)
with the resulting solution treated as specified above for
the preparation of 6a–d.
4.2.1.1.
(1S,2S,3S)-2-Benzoyl-3-((S)-2-formyloxy-1-
hydroxyethyl)cyclopropanecarboxylic acid 5a. Mp 186–
20
189 °C (EtOH) (decomp.). ½aꢀD ¼ þ112:4 (c 1.0, DMSO).
1H NMR (DMSO-d6): 1.95 (td, J = 9.5, 5.7 Hz, 1H,
H-3); 2.27 (dd, J = 9.3, 4.6 Hz, 1H, H-1); 3.29 (t,
J = 5.2 Hz, 1H, H-2); 3.95 (m, 1H, H-10); 4.16 (m, 2H,
CH2); 5.25 (br s, 1H, OH); 7.57 (t, J = 8.4 Hz, 2H); 7.68
(t, J = 8.4 Hz, 1H); 8.03 (d, J = 8.3 Hz, 2H); 8.20 (s, 1H,
HCOO); 12.61 (br s, 1H, COOH). Anal. Calcd for
C14H14O6: C, 60.43; H, 5.07. Found: C, 60.05; H, 5.32.
4.2.3.1.
(1S,4S,5S,6S)-6-Benzoyl-4-hydroxymethyl-3-
6a. Mp 127–128 °C
oxabicyclo[3.1.0]hexane-2-one
20
(MeOH). ½aꢀD ¼ þ112:8 (c 1.0, DMSO). 1H NMR
(DMSO-d6): 2.64 (dd, J = 6.1, 2.4 Hz, 1H, H-1); 2.70 (dd,
J = 6.1, 3.3 Hz, 1H, H-5); 3.41 (t, J = 3.0 Hz, 1H, H-6);
3.62 (m, 2H, CH2); 4.64 (t, J = 3.6 Hz, 1H, H-4); 5.14 (t,
J = 5.7 Hz, 1H, OH); 7.57 (t, J = 7.6 Hz, 2H); 7.71 (t,
J = 7.3 Hz, 1H); 8.13 (d, J = 7.9 Hz, 2H). 13C NMR
(DMSO-d6): 26.83, 27.33, 29.96, 62.44, 81.03, 128.52,
128.91, 133.92, 136.18, 173.65, 194.99. Anal. Calcd for
C13H12O4: C, 67.23; H, 5.21. Found: C, 67.00; H, 5.33.
4.2.1.2. (1S,2S,3S)-2-(4-Chlorobenzoyl)-3-((S)-2-formyl-
oxy-1-hydroxyethyl)cyclopropanecarboxylic acid 5b. Mp
20
188–190 °C (EtOH) (decomp.). ½aꢀD ¼ þ98:0 (c 1.0,
1
DMSO). H NMR (DMSO-d6): 1.94 (m, 1H, H-3); 2.29
(dd, J = 9.3, 4.6 Hz, 1H, H-1); 3.30 (t, J = 5.3 Hz, 1H,
H-2); 3.93 (m, 1H, H-10); 4.12 (dd, J = 11.0, 4.3 Hz, 1H,
CH2); 4.18 (dd, J = 11.0, 5.8 Hz, 1H, CH2); 5.24 (br s,
1H, OH); 7.64 (d, J = 8.5 Hz, 2H); 8.07 (d, J = 8.5 Hz,
2H); 8.20 (s, 1H, HCOO); 12.63 (br s, 1H, COOH). 13C
NMR (DMSO-d6): 27.90, 28.98, 33.77, 64.91, 67.28,
129.07, 130.12, 135.08, 138.65, 162.17, 170.81, 195.09.
Anal. Calcd for C14H13ClO6: C, 53.77; H, 4.19; Cl, 11.34.
Found: C, 54.08; H, 3.96; Cl, 11.10.
4.2.3.2. (1S,4S,5S,6S)-6-(4-Chlorobenzoyl)-4-hydroxy-
methyl-3-oxabicyclo[3.1.0]hexane-2-one 6b. Mp 184–
20
1
185 °C (EtOH). ½aꢀD ¼ þ88:1 (c 1.0, DMSO). H NMR
(DMSO-d6): 2.65 (dd, J = 6.1, 2.5 Hz, 1H, H-1); 2.71 (dd,
J = 6.1, 3.2 Hz, 1H, H-5); 3.42 (t, J = 3.0 Hz, 1H, H-6);
3.62 (m, 2H); 4.63 (t, J = 3.6 Hz, 1H, H-4); 5.12 (br s,
1H, OH); 7.64 (d, J = 8.5 Hz, 2H); 8.16 (d, J = 8.5 Hz,
2H). Anal. Calcd for C13H11ClO4: C, 58.55; H, 4.16; Cl,
13.29. Found: C, 58.81; H, 3.99; Cl, 13.42.
4.2.1.3. (1S,2S,3S)-2-(4-Bromobenzoyl)-3-((S)-2-formyl-
oxy-1-hydroxyethyl)cyclopropanecarboxylic acid 5c. Mp
4.2.3.3. (1S,4S,5S,6S)-6-(4-Bromobenzoyl)-4-hydroxy-
methyl-3-oxabicyclo[3.1.0]hexane-2-one 6c. Mp 195–
20
20
1
190–193 °C (EtOH) (decomp.). ½aꢀD ¼ þ89:6 (c 0.5, DMSO).
197 °C (EtOH). ½aꢀD ¼ þ79:7 (c 1.0, DMSO). H NMR
(DMSO-d6): 2.63 (dd, J = 6.1, 2.5 Hz, 1H, H-1); 2.69 (dd,
J = 6.2, 3.4 Hz, 1H, H-5); 3.41 (t, J = 3.0 Hz, 1H, H-6);
3.61 (m, 2H); 4.62 (t, J = 3.6 Hz, 1H, H-4); 5.13 (br s,
1H, OH); 7.78 (d, J = 8.5 Hz, 2H); 8.07 (d, J = 8.5 Hz,
2H). Anal. Calcd for C13H11BrO4: C, 50.18; H, 3.56; Br,
25.68. Found: C, 49.89; H, 3.60; Br, 26.00.
1H NMR (DMSO-d6): 1.94 (td, J = 9.5, 5.8 Hz, 1H, H-3);
2.29 (dd, J = 9.5, 4.6 Hz, 1H, H-1); 3.30 (t, J = 5.2 Hz, 1H,
H-2); 3.93 (m, 1H, H-10); 4.12 (dd, J = 11.1, 4.6 Hz, 1H,
CH2); 4.18 (dd, J = 11.1, 5.7 Hz, 1H, CH2); 5.25 (br s, 1H,
OH); 7.79 (d, J = 8.5 Hz, 2H); 7.97 (d, J = 8.5 Hz, 2H);
8.20 (s, 1H, HCOO); 12.63 (br s, 1H, COOH). Anal. Calcd
for C14H13BrO6: C, 47.08; H, 3.67; Br, 22.37. Found: C,
46.78; H, 3.60; Br, 22.60.
4.2.3.4. (1S,4S,5S,6S)-4-Hydroxymethyl-6-(2-thienoyl)-
3-oxabicyclo[3.1.0]hexane-2-one
6d. Mp
202–203 °C
20
4.2.1.4. (1S,2S,3S)-2-((S)-2-Formyloxy-1-hydroxyethyl)-
3-(2-thienoyl)cyclopropanecarboxylic acid 5d. Mp 192–
(MeOH). ½aꢀD ¼ þ112:4 (c 1.0, DMSO). 1H NMR
(DMSO-d6): 2.75 (dd, J = 6.2, 2.6 Hz, 1H, H-1); 2.89 (dd,
J = 6.2, 3.3 Hz, 1H, H-5); 3.42 (t, J = 3.0 Hz, 1H, H-6);
3.63 (m, 2H); 4.60 (t, J = 3.6 Hz, 1H, H-4); 5.16 (t,
20
195 °C (EtOH) (decomp.). ½aꢀD ¼ þ140:0 (c 0.8, DMSO).
1H NMR (DMSO-d6): 1.91 (td, J = 9.5, 5.8 Hz, 1H,

694
A. V. Samet et al. / Tetrahedron: Asymmetry 19 (2008) 691–694
4. Martin, S. F.; Dwyer, M. P.; Hartmann, B.; Knight, K. S. J.
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J = 5.7 Hz, 1H, OH); 7.32 (dd, J = 4.9, 3.9 Hz, 1H); 8.12
(d, J = 4.9 Hz, 1H); 8.37 (d, J = 3.9 Hz, 1H). Anal. Calcd
for C12H12O6S: C, 55.45; H, 4.23; S, 13.46. Found: C,
55.51; H, 4.35; S, 13.13.
6. Reichelt, A.; Martin, S. F. Acc. Chem. Res. 2006, 39, 433–
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Jawalkar, D. G.; Mahajan, S. W.; Ratnam, K. R.; Goghare,
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4.2.3.5. (1S,4S,5S,6S)-4-Hydroxymethyl-6-(4-methyl-
furazane-3-yl)carbonyl-3-oxabicyclo[3.1.0]hexane-2-one 6e.
24
Mp 125–126 °C (benzene). ½aꢀD ¼ þ97:2 (c 1.0, DMSO).
1H NMR (DMSO-d6): 2.52 (s, 3H); 2.80 (dd, J = 6.2,
2.5 Hz, 1H, H-1); 2.87 (dd, J = 6.2, 3.3 Hz, 1H, H-5);
3.19 (t, J = 2.9 Hz, 1H, H-6); 3.63 (m, 2H, CH2); 4.63 (t,
J = 3.5 Hz, 1H, H-4); 5.19 (t, J = 5.7 Hz, 1H, OH). Anal.
Calcd for C10H10N2O5: C, 50.42; H, 4.23; N, 11.76. Found:
C, 50.65; H, 4.10; N, 12.11.
4.2.3.6.
(1S,4S,5S,6S)-6-(1-Adamantoyl)-4-hydroxy-
methyl-3-oxabicyclo[3.1.0]hexane-2-one 6f. Mp 112–
20
1
114 °C (MeOH). ½aꢀD ¼ þ84:1 (c 1.0, DMSO). H NMR
(DMSO-d6): 1.69 (m, 6H); 1.81 (m, 6H); 2.00 (m, 3H);
2.30 (dd, J = 6.1, 2.6 Hz, 1H, H-1); 2.40 (dd, J = 6.1,
3.3 Hz, 1H, H-5); 2.84 (t, J = 3.0 Hz, 1H, H-6); 3.58 (m,
2H); 4.50 (t, J = 3.7 Hz, 1H, H-4); 5.09 (br s, 1H, OH).
Anal. Calcd for C17H22O4: C, 70.32; H, 7.64. Found: C,
70.04; H, 7.79.
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4.2.3.7. (1S,4S,5S,6S)-Methyl-4-hydroxymethyl-2-oxo-3-
oxabicyclo[3.1.0]hexane-6-carboxylate 6g. Mp 115–116 °C
20
(MeOH). ½aꢀD ¼ þ98:8 (c 1.0, DMSO). 1H NMR (DMSO-
d6): 2.18 (t, J = 3.0 Hz, 1H, H-6); 2.53 (dd, J = 6.1, 2.4 Hz,
1H, H-1); 2.63 (dd, J = 6.1, 3.3 Hz, 1H, H-5); 3.60 (m, 2H,
CH2); 3.69 (s, 3H); 4.50 (t, J = 3.5 Hz, 1H, H-4); 5.13 (br
s, 1H, OH). 13C NMR (DMSO-d6): 23.22, 25.38, 27.25,
52.29, 62.30, 80.64, 169.90, 172.98. Anal. Calcd for
C8H10O5: C, 51.61; H, 5.41. Found: C, 51.85; H, 5.19.
Acknowledgment
This research was supported by a grant from Chemical
Block Ltd (www.chemblock.com).
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