Enantiospecific total synthesis of (-)-D-noviose

Article abstract of DOI:10.1002/(SICI)1522-2675(19981111)81:11<1997::AID-HLCA1997>3.0.CO;2-V

(-)-D-Noviose ((-)-22), a rare sugar, was synthesized starting from the optically active building block (-)-1 in seven steps. The first step of this route, the introduction of a methyl-ether group under Lewis-acidic conditions, left the acetoxy group unto

Full text of DOI:10.1002/(SICI)1522-2675(19981111)81:11<1997::AID-HLCA1997>3.0.CO;2-V

Helvetica Chimica Acta ± Vol. 81 (1998)
1997
Enantiospecific Total Synthesis of ( )-d-Noviose1)
by Wolf Matthias Pankau and Wolfgang Kreiser*
Naturstoffchemie, Universität Dortmund, Otto-Hahn-Str. 6, D-44221 Dortmund
(
)-d-Noviose (( )-22), a rare sugar, was synthesized starting from the optically active building block ( )-
1 in seven steps. The first step of this route, the introduction of a methyl-ether group under Lewis-acidic
conditions, left the acetoxy group untouched and thereby preserved the absolute configuration in the product 2
(Scheme 2). Next, the double bond of methyl ether 2 was cis-dihydroxylated leading selectively to 3. After
saponification of the acetoxy group of 3 the two vicinal cis OH groups of 17 were selectively protected as the
cyclic carbonate 18 (Scheme 4). This kind of protection was essential to achieve the proper regioselectivity in the
Baeyer-Villiger rearrangement of the cyclopentanone derivative 19 that was obtained after oxidation of the
remaining OH group of 18. Lactone 20 was the major product of this rearrangement. Final reduction to the
corresponding lactol (cyclic hemiacetal) with diisobutylaluminium hydride (DIBAH) at low temperature was
accompanied by reductive cleavage of the protecting cyclic carbonate moiety thereby leading directly to ( )-d-
noviose (( )-22).
Introduction. ± In the work presented here, ( )-d-noviose (( )-22), the unnatural
antipode, was synthesized for the first time de novo from building block ( )-1
(Scheme 1). Both enantiomers of the latter were easily prepared from cheaply
available medion as reported in 1996 [2].
Scheme 1
(‡)-l-Noviose ((‡)-22) has been identified as the sugar moiety of novobiocin, an antibiotic from
Streptomyces spheroides, by Hinman et al. in 1957 [3]. It was first synthesized by Kiss et al. [4] in 1964 starting
from 1,2 :5,6-di-O-isopropylidene-a-d-glucofuranose, which was transformed into a 1,1-dimethyl-d-glucitol
derivative, then oxidized to epi-noviose and isomerized to (‡)-22 in 15 steps. In 1976, Achmatowicz Jr. et al. [5]
published a total synthesis in the racemic series starting from 2-acetylfuran, which, after Grignard reaction,
acetylation, and hydrolysis yielded the keto-sugar derivative; reduction, methylation, and cis-hydroxylation led
to the methyl glycoside of 22. The most recent approach to noviose was reported by Klemer et al. [6] in 1986,
involving a route of seven steps starting from l-rhamnose, which was oxidized after protection, then subjected to
a Grignard reaction, and transformed to pyranose by deprotection; after renewed protection, methylation, and
hydrolysis, (‡)-l-noviose ((‡)-22) was obtained. This short and efficient (overall yield 33%) synthesis, however,
suffers from the high costs of the starting material and the fact that only one antipode is accessible.
1
)
Preliminary communication [1].

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Helvetica Chimica Acta ± Vol. 81 (1998)
Results. ± The first step of our synthesis required the methylation of the free OH
group of ( )-1. This goal was finally achieved by carbene insertion into the O H bond
of the allylic alcohol utilizing diazomethane in Et2O catalyzed by BF3 ´ Et2O. This
somewhat peculiar procedure, being first introduced by Chavis et al. [7], had to be
applied because of the lability of the acetate function towards alkaline conditions which
did not allow a Williamson ether synthesis. Furthermore, migration of the acetate group
could not safely be excluded in that latter synthesis. Thus, reaction of 1 with 5 equiv. of
diazomethane in Et2O and catalytic amounts of BF3 ´ Et2O led to 2 (Scheme 2) which
was obtained as a colorless liquid with a very intense and typical smell in 78% yield
after column chromatography. cis-Hydroxylation of 2 was then performed by catalytic
amounts of OsO4 and 4-methylmorpholine 4-oxide (NMO) as cooxidant in aqueous
acetone, following a method described by Deardorff et al. [8]. These conditions
selectively gave diol 3 in 86% yield due to the directing effect of the substituents on the
b-face of the molecule. Diol 3 was then protected as an acetone ketal 4, before the
acetate function was hydrolyzed and the resulting cyclopentanol derivative 5 oxidized
to ketone 6. With this substrate, surprisingly, the Baeyer-Villiger rearrangement led
selectively to the wrong lactone 7, whereas no trace of the regioisomeric noviono-
lactone derivative 8 could be detected.
The observed abnormal regioselectivity of the Baeyer-Villiger rearrangement of 6
( ! 7) came unexpected to us since it appeared in conflict with well-known rules; but
Scheme 2
a) CH2N2, BF3 ´ Et2O, Et2O, 08. b) OsO4, NMO, acetone/H2O 8 : 1, 08. c) Me2C(OMe)2, TsOH, acetone, r.t.
d) KOH, MeOH/H2O, r.t. e) (COCl)2, DMSO, Et3N, CH2Cl2, 788. f ) 3-Chloroperbenzoic acid, CH2Cl2, r.t.

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similar results have been reported very recently by Chida and Ogawa [9]. To achieve
the desired normal regiochemistry, it was obviously necessary to choose different
protecting groups for the vicinal cis-dihydroxy moiety of 3 which had to display a
stronger electron-withdrawing effect. Thus, the protection by benzoate ester moieties
was examined. Acetate 2 was first hydrolyzed to the alcohol 9 and then transformed to
benzyl ether 10, introducing a stable protective group towards alkaline conditions
(Scheme 3). This material was subjected to cis-hydroxylation with OsO4 and NMO as
cooxidant leading to 11 in 61% yield. Surprisingly, the directing effect of the benzyloxy
group turned out to be weaker than that of the acetoxy group in 2; therefore, partly
dihydroxylation at the b-face was observed too, leading in addition to 11 to the
corresponding all-cis by-product 12 in 12% yield. The isolated diol 11 was then reacted
with benzoyl chloride/pyridine in CH2Cl2 leading to 13, which was transformed to the
free mono-alcohol 14 by hydrogenolytic cleavage of the benzyl-ether group. Oxidation
with pyridinium dichromate (PDC), a very mild method reported by Corey and
Schmidt [10], yielded the cyclopentanone derivative 15 which, however, rapidly
underwent b-elimination to the a,b-unsaturated ketone 16. Such a behavior was not
expected under neutral conditions, but in fact was even observed when 15 was stored
neat at 408. Within a few hours at that temperature, all the material was destroyed,
which possibly may indicate an autocatalytic effect of benzoic acid, released during the
process.
Scheme 3
a) KOH, MeOH, H2O, r.t. b) BnBr, NaH, THF, 08. c) OsO4, NMO, acetone/H2O 8:1, 08. d) BzCl, pyridine,
CH2Cl2, 08. e) H2, Pd/C, MeOH, r.t. f ) PDC, CH2Cl2, r.t.

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Helvetica Chimica Acta ± Vol. 81 (1998)
The benzoyl group having failed as a suitable protective group for the vicinal cis-
dihydroxy moiety of 3 our next choice was a cyclic carbonate as a bidentate protection.
In addition to its electron-withdrawing power and the reduced tendency for b-
elimination, the cyclic carbonate ensures the conservation of the configuration at the
OH-substituted C-atoms. Thus, the acetate function of diol 3 was first hydrolyzed
yielding triol 17 which then was treated with triphosgene (CO(OCCl3)) following a
procedure described by Burk and Roof [11] (Scheme 4). The configuration of triol 17
only allowed for the introduction of the cyclic carbonate moiety at the cis-oriented OH
groups, thereby rendering further protective groups unnecessary. Thus, alcohol 18 was
obtained in 89% yield and easily oxidized by PDC to the cyclopentanone derivative 19
that was not prone to any b-elimination. Baeyer-Villiger oxidation of this new
cyclopentanone derivative 19 was achieved with 3-chloroperbenzoic acid in CH2Cl2 at
room temperature within 3 days and led to the novionolactone derivative 20 as the
major product in 74% yield, whereas the unwanted regioisomeric lactone 21, in this
case, was only produced in 20% yield. The regioisomers could easily be separated by
fractional crystallization from AcOEt. The target ( )-d-noviose (( )-22) was
accessible from the novionolactone derivative 20 in a single step by reduction with
5 equiv. of diisobutylaluminium hydride (DIBAH) at 708 [12] in CH2Cl2. Apart from
the reduction of the lactone to the corresponding lactol (cyclic hemiacetal) under these
conditions, also the protective cyclic carbonate group was cleaved, and ( )-22 was
isolated in 78% yield after recrystallization from cyclohexane/AcOEt, displaying a
melting point of 1288 ([3]: 128 ± 1308).
Scheme 4
a) KOH, H2O, MeOH, r.t. b) CO(OCCl3)2 , pyridine, CH2Cl2 ,
708. c) PDC, CH2Cl2 ; r.t.
d) 3-Chloroperbenzoic acid, CH2Cl2, 3 d, r.t. e) DIBAH, CH2Cl2, 708.
Discussion. ± The synthetic ( )-d-noviose (( )-22) crystallized as almost pure b-d-
anomer out of the equilibrium mixture of anomers, as shown by the 1H-NMR spectrum
measured immediately after dissolution of ( )-22 in CD3OD. After a short while,
1
mutarotation was observed, leading to a double set of H-NMR signals (Fig. 1). Our
1H-NMR data, recorded at 400 MHz, complete those of Angyal et al. [13], measured at

Helvetica Chimica Acta ± Vol. 81 (1998)
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60 MHz. The 13C-NMR spectrum (Table) of ( )-22 showed a double set of signals too,
as reported earlier by Achmatowicz et al. [5].
Most interestingly, the synthetic ( )-d-noviose (( )-22) displayed a surprisingly
high optical rotation of [a]D20
ˆ
29.2 (EtOH/H2O 1 : 1, c ˆ 1.00) (literature values:
Fig. 1. 1H-NMR Spectra (CD3OD) of ( )-22: a) recorded immediately after dissolution in CD3OD and b) after
3 h at room temperature. The insets show regions of most significant change during mutarotation. Besides the
signals of ( )-22, strong signals of CD3OH (via proton exchange) and CHD2OD were registered, the latter one
partially covering the signal of the acetal proton(s).
Table. Chemical Shifts [ppm] and Coupling Constants [Hz] of the a- and b-d-Anomer of ( )-d-Noviose ( )-22
in CD3OD (tentatively assigneda))
H
C(1)
H
C(2)
H
C(3)
H
C(4)
H
C(5) Me
Me
MeO
13C-NMR:
b-d-anomer 91.24
a-d-anomer 95.91
74.09
72.79
70.01
73.57
86.07
85.47
76.02
78.42
29.25
28.83
18.95
25.37
62.50
61.84
1H-NMR:
b-d-anomer 4.90
3.81
3.72
3.21
±
±
1.32 (s) 1.18 (s) 3.60 (s)
1.31 (s) 1.35 (s) 3.57 (s)
(d, J ˆ 1.2) (dd, J ˆ 3.5, 1.2) (dd, J ˆ 9.8, 3.5) (d, J ˆ 9.8)
a-d-anomer 5.03 3.74 4.04 3.24
(d, J ˆ 3.3) (dd, J ˆ 3.5, 3.3) (dd, J ˆ 3.3, 8.0) (d, J ˆ 8.0)
a) Apparently due to different solvents, the 13C-NMR data do not correspond to values reported by
Achmatowicz et al. [5].

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Fig. 2. Mutarotation of ( )-d-noviose ( )-22. Measured at 208 in EtOH/H2O 1 :1 with c ˆ 0.38 g/100 ml.
[a]D ˆ‡ 38 [14] (in 0.5n aq. H2SO4), ‡ 22.6 [15], ‡ 20.8 [6], ‡ 19.9 [3], and ‡ 19.35
[4]). Our value of [a]2D0 is the final value, measured after several hours of equilibration
in EtOH/H2O 1 : 1 at 208. The kinetics of the mutarotation is shown in Fig. 2.
Taking into account the reported cheap availability of both enantiomers of
the building block 1, the synthesis described herein is the most efficient approach
to both enantiomers of noviose (22) which is achieved in 32% overall yield in seven
steps.
Experimental Part
General. All reagents and solvents were commercially available and used without further purification. Abs.
CH2Cl2 was freshly distilled from 4-Š molecular sieve. TLC: Merck silica gel 60 F254 plates (Art. No. 5554);
detection with UV, I2, or phosphomolybdic acid. Column chromatography (CC): silica gel 60 (230 ± 400 mesh) of
Merck Co. M.p.: Büchi-571 instrument; not corrected. Optical rotations: Perkin-Elmer-141 automatic
polarimeter (10-cm, 1-ml cell); at 208. IR Spectra: Schimadzu-470 spectrometer; films or KBr discs; nÄ in
cm 1. NMR Spectra: Bruker-DRX-400 spectrometer (1H, 400.13 MHz; 13C, 100.61 MHz); d in ppm rel. to
internal Me4Si (ˆ 0 ppm); J in Hz. MS: Finnigan Mat-8230 spectrometer. (70 eV); m/z (rel. %).
(1R,4S)-4-Methoxy-5,5-dimethylcyclopent-2-en-1-yl Acetate ( ˆ (1R,4S)-4-Methoxy-5,5-dimethylcyclopent-
2-en-1-ol Acetate; 2). A soln. of 1.525 g (8.96 mmol) of (1R,4S)-4-hydroxy-5,5-dimethylcyclopent-2-en-1-yl
acetate (( )-(1)) in Et2O was cooled to 08, and 10 drops of BF3 ´ Et2O were added. Then an Et2O soln. of
diazomethane was added until the yellow color persisted for 1 min. Then the same amount of BF3 ´ Et2O soln.
was added again, followed by addition of diazomethane soln. These operations were repeated until 50 mmol of
diazomethane soln. had been consumed. Finally, the mixture was stirred for another 30 min, and the solid by-
products were filtered off. The raw material was then purified by distillation under reduced pressure yielding
1.29 g (78%) of 2. Rf 0.77 (cyclohexane/AcOEt 1 : 1). B.p. 388/0.3 mbar. [a]D20
ˆ
21.67 (c ˆ 2.52, CHCl3). IR
(neat): 2822 (MeO), 1735 (CˆO), 1370 (gem. dimethyl), 1363 (C H, acetate), 1240 (C O), 1035 (C O),
716 (H CˆC). 1H-NMR (400 MHz, CDCl3): 0.95 (s, Me C(5)); 1.18 (s, Me C(5)); 2.08 (s, MeCOO); 3.43
(s, MeO); 3.73 (s, H C(4)); 5.22 (s, H C(1)); 5.87 (d, 3J(3,2) ˆ 5.0, H C(3)); 6.11 (d, 3J(2,3) ˆ 5.0, H C(2)).
13C-NMR (100 MHz, CDCl3): 16.70 (q, Me C(5)); 21.00 (q, MeCOO); 27.51 (q, Me C(5)); 46.06 (s, C(5));
58.16 (q, MeO); 83.68 (d, C(1)); 91.37 (d, C(4)); 131.77 (d, C(2)); 134.64 (d, C(3)); 170.79 (s, MeCOO). MS:
‡
184 (3, M ), 153(21), 141(2), 125(35), 95(29), 59(19), 43(100).

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(1S,2S,3R,4R)-2,3-Dihydroxy-4-methoxy-5,5-dimethylcyclopent-1-yl Acetate ( ˆ (1S,2S,3R,4R)-4-Methoxy-
5,5-dimethylcyclopentane-1,2,3-triol 1-Acetate; 3). To a soln. of 2 (12.6 g, 68.4 mmol) and NMO (17.9 g,
151 mmol) in H2O (500 ml) and acetone (60 ml), OsO4 (60 mg) was added and the mixture stirred for 3 days at
r.t. The major part of the solvent was then removed by distillation and the residue extracted with AcOEt (4 Â
200 ml). Usual workup gave 14.2 g of crude yellow oil which was crystallized from AcOEt yielding in several
crops a total of 12.7 g (86%) of pure 3. Rf 0.16 (cyclohexane/AcOEt 1 : 1). M.p. 848 (AcOEt). [a]D20
ˆ
26.09
(c ˆ 2.2, CHCl3). IR (KBr): 3375 (O H), 2945 (C H), 2833 (MeO), 1739 (CˆO), 1376 (gem. dimethyl),
1232 (C O), 1079 (C O), 1058 (C O). 1H-NMR (CDCl3): 0.86 (s, Me C(5)); 1.10 (s, Me C(5)); 2.15
(s, MeCOO); 3.23 (d, 3J(4,3) ˆ 5.0, H C(4)); 3.52 (s, MeO); 3.54 (br. s, OH C(3)*); 4.00 ± 4.02 (m, H C(2),
H
C(3)); 4.08 (br. s, OH C(2)*); 4.58 (d, 3J(1,2) ˆ 5.8, H C(1)). 13C-NMR (100 MHz, CDCl3): 14.06
(q, Me C(5)); 20.88 (q, MeCOO); 25.91 (q, Me C(5)); 40.48 (s, C(5)); 58.85 (q, MeO); 72.14 (d, C(3)); 73.08
(d, C(2)); 85.66 (d, C(1)); 92.11 (d, C(4)); 172.67 (s, MeCOO). MS: 218 (30, M ), 200(5), 186(45), 169(50),
‡
159(5), 43(100).
(1S,2R,3R,4R)-4-Methoxy-5,5-dimethylcyclopentane-1,2,3-triol (17). A soln. of 3 (4.2 g, 19 mmol) in
MeOH (60 ml) was treated with a soln. of KOH (6.0 g) in H2O (10 ml) for 2 h at r.t. MeOH was then removed by
distillation and the residue extracted overnight with Et2O utilizing a perforator apparatus. Usual workup yielded
3.4 g (quant.) of pure 17. Colorless crystals. Rf 0.71 (MeOH/AcOEt 1:1). M.p. 55 ± 568 (Et2O). [a]2D0 ˆ‡ 9.3
(c ˆ 1.72, CHCl3). IR (KBr): 3345 (O H), 2944 (C H), 2832 (MeO), 1367 (gem. dimethyl), 1195 (C O),
1173 (C O), 1134 (C O), 1089 (C O), 1061 (C O). 1H-NMR (400 MHz, CDCl3): 0.79, 1.11 (2s,
2 Me C(5)); 3.14 (d, 3J(4,3) ˆ 4.0,
H
C(4)); 3.46 (d, 3J(1,2) ˆ 7.0,
H C(1)); 3.49 (s, MeO); 3.91
(m, H C(3)*); 4.88 (m, H C(2)*). 13C-NMR (100 MHz, CDCl3): 15.69 (q, 1 Me C(5)); 26.15
(q, 1 Me C(5)); 40.75 (s, C(5)); 58.94 (q, MeO); 72.80 (d, C(3)*); 73.78 (d, C(2)*); 82.2 (d, C(1)); 93.32
(d, C(4)).
(3aR,4S,6R,6aS)-3a,5,6,6a-Tetrahydro-4-hydroxy-6-methoxy-5,5-dimethyl-4H-cyclopenta[d]-1,3-dioxol-2-
one (18). At 708, a soln. of triphosgene (6.6 g, 22.3 mmol) in CH2Cl2 (20 ml) was added dropwise within
20 min to a stirred soln. of 17 (3.93 g, 22.3 mmol) in CH2Cl2 (200 ml). The mixture was stirred for additional
16 h at 708 and then quenched with sat. aq. NH4Cl soln. (100 ml). After warming to r.t. stirring was continued
for another 30 min. The aq. layer was extracted with AcOEt (3Â) and the combined org. phase washed with
HCl and NaHCO3 soln. and worked up as usual: 4.81 g (89%) of 18. Slightly yellow solid. Rf 0.56 (cyclohexane/
AcOEt 1 : 1). M.p. 798 (AcOEt). [a]2D0 ˆ‡ 11.0 (c ˆ 2.6, CHCl3). IR (KBr): 3473 (O H), 2970 (C H), 2938
(C H), 2878 (C H), 2837 (MeO), 1828 (CˆO, carbonate), 1790 (CˆO, carbonate), 1770 (CˆO, carbonate),
1373 (gem. dimethyl), 1267 (C O), 1207 (C O), 1158 (C O), 1108 (C O), 1039 (C O), 1009 (C O).
1H-NMR (400 MHz, CDCl3): 0.84, 1.26 (2s, 2 Me C(5)); 3.37 (d, 3J(6,6a) ˆ 4.3, H C(6)); 3.48 (s, MeO); 3.81
(d, 3J(4,3a) ˆ 4.8,
H
C(4)); 4.80 (m, H C(3a),
H
C(6a)). 13C-NMR (100 MHz, CDCl3): 15.25
(q, 1 Me C(5)); 24.26 (q, 1 Me C(5)); 43.43 (s, C(5)); 58.58 (q, MeO); 81.49 (d, C(4)); 82.50 (d, C(6a)*);
‡
83.84 (d, C(3a)*); 90.44 (d, C(6)); 154.96 (s, C(2)). MS: 202 (2, M ), 170(41), 101(11), 98(23), 84(56),
43(100).
(3aS,6R,6aS)-3a,5,6,6a-Tetrahydro-6-methoxy-5,5-dimethyl-4H-cyclopenta[d]-1,3-dioxole-2,4-dione (19).
PDC (30.0 g, 40 mmol) was added to a soln. of 18 (4.01 g, 20 mmol) in CH2Cl2 (200 ml) and the resulting
suspension stirred for 3 d at r.t. Thereafter, it was filtrated through a plug of ca. 2 cm of silica gel and washed with
more CH2Cl2 (500 ml). Evaporation yielded 3.7 g (92%) of almost pure 19 which was recrystallized from
AcOEt. Rf 0.61 (cyclohexane/AcOEt 1 :1). M.p. 728 (AcOEt). [a]2D0 ˆ‡ 32.13 (c ˆ 2.68, CHCl3). IR (KBr):
2984 (C H), 2962 (C H), 2842 (C H, MeO), 1861, 1844, 1834, 1824, 1810, 1791, 1784, 1768, 1759 (all CˆO),
1
1376 (gem. dimethyl), 1262, 1112, 1102, 1091, 1079, 1063 (all C O). H-NMR (400 MHz, CDCl3): 0.99, 1.16
(2s, 2 Me C(5)); 3.48 (s, MeO); 3.55 (d, 3J(6,6a) ˆ 3.5, H C(6)); 4.97 (dd, 3J(6a,6) ˆ 3.5, 3J(6a,3a) ˆ 9.0,
H
C(6a)); 5.03 (d, 3J(3a,6a) ˆ 9.0, H C(3a)). 13C-NMR (100 MHz, CDCl3): 20.44 (q, 1 Me C(5)); 23.14
(q, 1 Me C(5)); 51.90 (s, C(5)); 60.57 (q, MeO); 78.33 (d, C(3a)); 81.20 (d, C(6a)); 90.80 (d, C(6)); 155.14
(s, C(2)); 209.68 (s, C(4)). MS: 200 (70, M ), 149(5), 97(14), 86(100), 71(71).
‡
2,3-O-Carbonyl-d-noviono-1,5-lactone ( ˆ (3aS,7S,7aS)-3a,6,7,7a-Tetrahydro-7-methoxy-6,6-dimethyl-4H-
1,3-dioxolo[4,5-c]pyran-2,4-dione; 20). A soln. of 19 (3.3 g, 16.5 mmol) and 3-chloroperbenzoic acid (14.16 g,
65.5 mmol) in CH2Cl2 (250 ml) was stirred for 3 d at r.t. Then more CH2Cl2 (200 ml) was added and the mixture
washed with 100 ml of aq. Na2S2O3 and NaHCO3 soln. (100 ml each), dried (MgSO4), and evaporated. The
crude yellowish oil was crystallized from AcOEt: 2.64 g (74%) of pure 20. Colorless crystals. Rf 0.53
(cyclohexane/AcOEt 1 : 1). M.p. 1078 (AcOEt). [a]2D0 ˆ‡ 12.36 (c ˆ 1.44, CHCl3). IR (KBr): 2982 (C H), 2966
(C H), 1835, 1818, 1806, 1793 (all CˆO), 1748 (CˆO, lactone), 1393, 1377 (gem. dimethyl), 1261, 1106, 1098,
1087 (all C O). 1H-NMR (400 MHz, CDCl3): 1.39, 1.52 (2s, 2 Me C(6)); 3.46 (d, 3J(7,7a) ˆ 5.3, H C(7));

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Helvetica Chimica Acta ± Vol. 81 (1998)
3.61 (s, MeO); 5.16 (dd, J(7a,7) ˆ 5.3, 3J(7a,3a) ˆ 7.3, H C(7a)); 5.29 (d, 3J(3a,7a) ˆ 7.3, H C(3a)). 13C-NMR
(100 MHz, CDCl3): 22.27 (q, 1 Me C(6)); 26.97 (q, 1 Me C(6)); 59.6 (q, MeO); 70.27 (d, C(3a)); 77.99
‡
(d, C(7a)); 82.26 (s, C(6)); 82.85 (d, C(7)); 152.28 (s, C(2)); 163.39 (s, C(4)). MS: 216 (2, M ), 201(6),
128(10), 99(19), 86(100), 71(92).
(
)-d-Noviose ( ˆ ( )-6-Deoxy-5-C,4-O-dimethyl-d-lyxo-hexopyranose; ( )-22). Within 30 min, 1m DIBAH
in hexane (25 ml, 25 mmol) was added dropwise at 708 to a soln. of 20 (1.1 g, 5.09 mmol) in abs. CH2Cl2
(50 ml). The mixture was stirred for another 3.5 h, then quenched with sat. aq. Na2SO4 soln. (25 ml), and allowed
to warm up to r.t. After evaporation, the residue was dried in vacuo leading to a white powder which was
submitted to Soxhlet extraction with CH2Cl2 (14 h). This yielded a slightly yellow solid which was recrystallized
from cyclohexane/AcOEt: 764 mg (78%) of pure ( )-22. Rf 0.18 (CH2Cl2/AcOEt/EtOH 6 : 3). M.p. 1288.
[a]2D0
ˆ
29.2 (c ˆ 1.0, EtOH/H2O 1 : 1). IR (KBr): 3418 (O H), 2981 (C H), 1385, 1371 (gem. dimethyl),
1198, 1164, 1112, 1070, 1023 (all C O). H- and 13C-NMR: Table. MS: 192 (1, M ), 145(9), 99(2), 87(52),
1
‡
74(100), 71(26).
Compounds 4 ± 16 are described in [16].
REFERENCES
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Received June 22, 1998