Novel bicyclisation of unsaturated polyols in PdCl2-CuCl 2-AcOH catalytic system

Article abstract of DOI:10.1016/j.jorganchem.2005.10.036

Novel type of Pd(II)-catalysed transformation of sugar-derived alkenitols furnishing 7-benzyloxy-2,5-dioxabicyclo[2.2.1]heptanes was discovered. The investigated bicyclisation displays an exceptional substrate selectivity towards xylo-configured unsaturat

Full text of DOI:10.1016/j.jorganchem.2005.10.036

Journal of Organometallic Chemistry 691 (2006) 928–940
www.elsevier.com/locate/jorganchem
Novel bicyclisation of unsaturated polyols in
PdCl2–CuCl2–AcOH catalytic system
a
a
a
ˇ
ˇ
´
Matej Babjak , Lꢀubos Remen , Peter Szolcsanyi ,
a
b
a,
*
´
´
ˇ
ˇ
Peter Zalupsky , Dusan Miklos , Tibor Gracza
a
Department of Organic Chemistry, Slovak University of Technology, Radlinske´ho 9, SK-812 37 Bratislava, Slovak Republic
Department of Inorganic Chemistry, Slovak University of Technology, Radlinske´ho 9, SK-812 37 Bratislava, Slovak Republic
b
Received 28 September 2005; received in revised form 21 October 2005; accepted 21 October 2005
Available online 5 December 2005
Abstract
Novel type of Pd(II)-catalysed transformation of sugar-derived alkenitols furnishing 7-benzyloxy-2,5-dioxabicyclo[2.2.1]heptanes was
discovered. The investigated bicyclisation displays an exceptional substrate selectivity towards xylo-configured unsaturated polyols.
Moreover, a newly build stereogenic centre is formed in a diastereospecific cis-manner. The observed stereochemical preference was cor-
roborated by modelling of pertinent transition states at the semiempirical level of theory (PM5). In addition, the single crystal X-ray
analysis of an acylated analogue D-glycero-L-gulo-21 was done in order to establish the relative configuration of related bicyclic products.
ꢀ 2005 Elsevier B.V. All rights reserved.
Keywords: Palladium(II)-catalysis; Diastereoselectivity; Substrate selectivity; Bicyclisation; Semiempirical calculations
1. Introduction
In this account, we will discuss the new type of bicycli-
sation of unsaturated polyols with this particular catalytic
system.
The Wacker process for the palladium-catalysed oxida-
tion of ethylene to acetaldehyde was developed forty-three
years ago [1]. Since the development of this process a mul-
titude of transformations mediated by palladium(II) com-
pounds has been described. These comprise two major
reaction types, a nucleophilic attack on Pd(II)-complexed
olefin, and an insertion of olefins into r-alkyl palladium(II)
species [2]. Intramolecular versions of these processes are
very useful in the synthesis of oxygen and nitrogen-contain-
ing heterocycles [3]. A catalytic system that is mostly effi-
cient for oxidations, carbonylations, cycloacetalisations
and the other type of such reactions contains both palla-
dium(II) chloride and copper(II) chloride in acetic acid
with sodium acetate as a buffer [3,4].
2. Results and discussion
Our entry into this research area was initiated by
isolation of an unexpected side product, namely L-gly-
cero-D-gulo-2 formed in 9% yield in the Pd(II)-catalysed
oxycarbonylation of L-ido-1 [5] along with the desired
(+)-7-epi-goniofufurone as a major product, a naturally
occurring cytotoxic styryl-lactone [6]. The bicyclic struc-
ture of L-glycero-D-gulo-2 lacking C@O moiety was deter-
mined using single crystal X-ray structure analysis [7].
Our suspicion, that compound L-glycero-D-gulo-2 was
formed via competitive bicyclisation of 1, was proved
by an experiment with exclusion of carbon monoxide
from the reaction mixture. Indeed, using palladium(II)
chloride as catalyst (0.1 equiv.), copper(II) chloride as
oxidant (3 equiv.) and sodium acetate (3 equiv.) in glacial
acetic acid as buffer at room temperature [3,4,8] led to
*
Corresponding author. Tel.: +421 2 593 25 167; fax: +421 2 529 68
560.
E-mail address: tibor.gracza@stuba.sk (T. Gracza).
0022-328X/$ - see front matter ꢀ 2005 Elsevier B.V. All rights reserved.
doi:10.1016/j.jorganchem.2005.10.036

M. Babjak et al. / Journal of Organometallic Chemistry 691 (2006) 928–940
929
the formation of bicycle 2 as a sole product in 73% yield
(Scheme 1).
starting polyol. This indicates that the chemoselectivity of
reaction is directly correlated with the relative configura-
tion of substrates 1 and 6. It is noteworthy that from
diastereomeric mixtures of starting polyols, those with
all-syn (xylo) configuration on C3,C4,C5-atoms, i.e.,
D-gluco-6b (Entry 2) and D-ido-6c (Entry 3), led to corre-
sponding bicycles of the type I. On the other hand, bicyclic
acetals of types II and/or III were formed from all other
diastereomers of substrates. As a proof of stereochemical
dependence for necessary xylo-configuration, enantiomeri-
cally pure substrates L-ido-1 (Entry 6) and D-gluco-1 (Entry
7) furnished products L-glycero-D-gulo-2 and/or D-glycero-
D-gulo-2 exclusively, while the non-xylo configured D-
manno-6b [17,10b] (Entry 5) gave only acetals 16 and 17.
The only exception to this rule was the reaction of diaste-
reomeric mixture D-erythro-6a/D-threo-6a (Entry 1), which
afforded a single product D-lyxo-13 due to its C-2 symmetry
[18]. An important point to note is that xylo-configured
diastereoisomers provide the desired bicyclic products of
type I in synthetically useful yields (Entries 1–3, 6, 7). This
certainly makes our novel transformation well suited for
utilisation in total syntheses of tetrahydrofuran-containing
natural products (Table 1).
The determination of chemical and relative configura-
tion of bicycles of type I was done by single-crystal X-ray
analysis of bis-acylated analogue D-glycero-L-gulo-21
(Fig. 1). The structure exhibits considerable disorder at
one of terminal phenyl groups, which obviously tends to
rotate around the C–C bond connecting two phenyl rings.
This fact has been approximated by two orientations of the
corresponding aromatic substituent represented by atoms
C26–C271–C281–C29–C301–C311 with occupancy of
59.5% and C26–C272–C282–C29–C302–C312 with occu-
pancy of 40.5%, respectively, wherein the angle between
the two ring planes is 65.9(5)ꢁ. Crystal data and selected
bond lengths and angles are given in Tables 2 and 3,
respectively.
The formation of 1,4:2,5-dianhydro-heptitols I repre-
sents a new type of PdCl2/CuCl2-catalysed bicyclisation
of alkenitols and can be mechanistically rationalised as fol-
lows: intramolecular nucleophilic attack of (C-5)OH to
Pd(II)-activated terminal C@C bond of D-ido-6c in p-com-
plex A leads to r-palladium intermediate B. The advanta-
geous coplanar spatial arrangement of (C-1)C-2 and
(C-4)OPd bonds of B is now ideally set for subsequent
reductive elimination affording the bicyclic D-glycero-D-
gulo-20. The required catalytic cycle is closed by reoxidation
of Pd(0) with CuCl2. Moreover, we have found copper(II)
chloride to be an indispensable reagent for this particular
transformation as its replacement for other oxidant (benzo-
quinone) has a detrimental effect on the bicyclisation
(Scheme 5).
From the synthetic point of view, the aforementioned
transformation represents a new type of functionalisation
of terminal alkene moiety. Formally, two nucleophilic sub-
stituents are attached to both ends of C@C double bond.
Thus, we decided to study this rather unusual reactivity
pattern in a more detail.
2.1. Preparation of unsaturated polyols as substrates
Firstly, easily accessible C5–C8 alkenitols were chosen as
suitable substrates for screening the optimal reaction con-
ditions of key bicyclisation. Diastereomeric mixtures of
various a-O-benzyl-alkenitols
6 were prepared from
aldoses 3a [9], 3b [10], 3c [11], 3d [12] according to common
synthetic sequence comprising the following steps: vinyl-
magnesium bromide addition to aldehydes 3 furnished cor-
responding allylalcohols 4, followed by benzylation to fully
protected alkenitols 5. Final hydrolysis of acetonides 5
afforded the desired key substrates 6 as nearly equimolar
diastereomeric mixtures (Scheme 2).
In addition, enantiomerically pure substrates L-ido-1
and D-gluco-1 were synthetised from the commercially
available D-gluconolactone in 10 steps. Mesylation of the
known triol 7 [15] followed by nucleophilic displacement
of 8 furnished iodide 9 that subsequently underwent Zn–
Cu promoted elimination to provide alkene 10. Selective
hydrolysis of the terminal acetonide followed by oxidative
cleavage of triol 11 gave a crude aldehyde that was sub-
jected, without any purification, to the phenylmagnesium
bromide addition yielding the corresponding adducts
L-ido-12 and D-gluco-12 as a diastereomeric mixture in
the ratio 7:3. The highly regioselective reduction of benzyl-
idene ring of pure L-ido-12 and D-gluco-12 diols (separated
by flash column chromatography) was accomplished with
the NaBH3CN/TiCl4 system, furnishing the required a-O-
Bn-protected tetraols L-ido-1 and D-gluco-1 (Scheme 3).
2.2. Palladium(II)-catalysed bicyclisation of unsaturated
polyols
With all prepared substrates on our hands, we subjected
them to the key PdCl2/CuCl2-catalysed transformation
under standard reaction conditions [16] (Scheme 4). There
are two different modes of transformation, yielding three
types of bicyclic products I, II and III, depending on a
On the other hand, the formation of bicyclic acetals II
and/or III can be easily explained by a known Pd(II)-catal-
ysed cascade process [20] involving two steps: the first being
the formation of a common intermediate E via complexes
C and D, which subsequently undergoes an acid catalysed
Scheme 1.

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M. Babjak et al. / Journal of Organometallic Chemistry 691 (2006) 928–940
Scheme 2.
Scheme 3.
Scheme 4.
1,5- and/or 1,6-acetalisation to produce compounds 19
and/or 18 (Scheme 6).
alkene. This leads to the formation of 2,3-trans-r-Pd-com-
plex F thermodynamically more favoured due to the dimin-
ished sterical hindrance in comparison to its diastereomeric
2,3-cis-r-Pd-complex G. As a consequence, the only prod-
uct formed is the bicycle of type I. On the other hand, all
other substrates with non-xylo-configuration prefer oppo-
site Si-attack for the same reason as above, i.e., due to
As we already mentioned earlier, the stereochemical out-
come of the transformation is highly dependent on the rel-
ative configuration of substrates. It is obvious that in
polyols with the all-syn (xylo) stereochemistry there is a
preferential nucleophilic attack from the Re-face of an

M. Babjak et al. / Journal of Organometallic Chemistry 691 (2006) 928–940
931
Table 1
Pd(II)-Catalysed bicyclisations of polyols 1 and 6
Entry
Substrate
Product (s)
Yield (%)
79
OH
BnO
HO
1
D-erythro-6a/D-threo-6a
O
O
D-lyxo-13
OBn
BnO
OH OH
HO
HO
O
D-glycero-D-gulo-14
D-gluco-6b
60
33
O
HO
OH OBn
OH
2
+
+
OBn
OH
OBn
OH OH
O
O
O
O
O
D-manno-6b
17
OH OBn
OH
16
OH
HO
HO
OBn
OH
OBn
O
OH OH
O
O
30
43
HO
HO
or
D-gulo-6c
D-ido-6c
19
OH
O
OH
18
OH OBn
3
+
+
BnO
OH OH
O
D-glycero-L-gulo-20
OH OBn
HO
HO
OH
OBn
OBn OH
O
O
O
D-glycero-D-galacto-6d
23
HO
HO
14
16
OH OH OBn
OBn OH
OH
BnO
+
4
5
+
OBn
HO
O
22
D-glycero-D-talo-6d
OH OH OBn
OH
BnO
O
OBn
OH
OBn
OH
OH OH
O
HO
O
O
57
D-manno-6b
and
OH OBn
16
17
HO
OH
BnO
OH OH
O
O
6
7
73
71
L-ido-1
L-glycero-D-gulo-2
D-glycero-D-gulo-2
Ph
Ph
O
OH OBn
OH
Ph
BnO
OH OH
D-gluco-1
O
OH OBn
Ph
OH
the formation of sterically more favoured 2,3-trans-r-Pd-
complex H, which in turn, leads to acetals of the type II
and/or III (Scheme 7).
This conclusion has been tentatively corroborated by
modelling of pertinent transition states (TS) at the semiem-
pirical level of theory (PM5).
Free energies of activation shown in Table 4 as well
as the associated geometries of transition states (Fig. 2)
indicate, in spite of being calculated for vacuum, that a
Re-attack, leading to r-complex with a trans-arrangement
of the methylenepalladium substituent and the neighbour-
ing benzyloxy group, followed by reductive elimination
giving rise to a bicycle of type I proceeded in xylo-sub-
strates through energetically more favoured transition
state. Although Scheme 7 boils the difference between
Si and Re attack down to steric congestion created by
two neighbouring bulky substituents, we felt that calcula-
tions were bound to be more reliable in assessing relative

932
M. Babjak et al. / Journal of Organometallic Chemistry 691 (2006) 928–940
Fig. 1. An ORTEP [19] view of crystal and molecular structure of
D-glycero-L-gulo-21 (hydrogen atoms omitted).
Table 2
Crystal data for D-glycero-L-gulo-21
Empirical formula
C40H30O7
Scheme 5.
Formula weight
622.64
Crystal system, space group
Unit cell dimensions
Monoclinic, P 2(1)
energies of transition states and hence relative reaction
rates of the respective reaction courses. In addition, reac-
tion hypersurfaces, once successfully generated from two
variables plotted against energy, allowed one to glean
possible alternative reaction pathways, even some contra
˚
a (A)
5.800(4)
15.338(3)
18.263(4)
94.28(3)
2, 1620.2(12)
1.276
˚
b (A)
˚
c (A)
b (ꢁ)
3
˚
Z, volume (A )
Dcalc (g cmꢀ3
l (mmꢀ1
F(000)
)
)
1.042
652
Diffractometer
Radiation type
Temperature (K)
Siemens P4
Mo Ka k = 0.71073 A
293(2)
˚
Diffractions collected/unique, Rint
Refinement method
Data/restraints/parameters
Goodness-of-fit on F2
Final R indices (I > 2r(I))
˚
Largest diff. peak and hole (e A
ꢀ3
7510/5697/0.0519
Full matrix, least-squares on F2
5697/1/425
1.000
R = 0.0660, Rw = 0.1705
0.171 and ꢀ0.206
)
Table 3
Selected bond lengths (A) and angles (ꢁ) of D-glycero-L-gulo-21
˚
C1–O2
C1–C6
C1–C7
O2–C3
C3–C4
C4–O5
C4–C7
O5–C6
C6–C16
C7–O8
1.441(5)
1.525(6)
1.538(7)
1.446(6)
1.513(6)
1.449(5)
1.514(6)
1.449(5)
1.514(6)
1.406(5)
O2–C1–C6
O2–C1–C7
C6–C1–C7
C1–O2–C3
O2–C3–C4
O5–C4–C3
O5–C4–C7
C3–C4–C7
C4–O5–C6
O5–C6–C16
O5–C6–C1
C16–C6–C1
O8–C7–C4
O8–C7–C1
C4–C7–C1
108.2(3)
101.6(3)
100.3(3)
105.4(3)
103.9(3)
105.9(3)
103.1(3)
99.8(3)
106.4(3)
110.4(3)
102.5(3)
113.6(4)
111.0(3)
116.8(3)
91.8(3)
Scheme 6.

M. Babjak et al. / Journal of Organometallic Chemistry 691 (2006) 928–940
933
Si face
R
R
OH
O
O
Si-attack
Re-attack
R
acetals II and/or III
bicycles I
2
2
HO
HO
3
3
PdII
PdII
HO BnO
xylo
OBn
OBn
Re face
Si face
2,3-cis-σ-Pd-complex G
2,3-trans-σ-Pd-complex F
R
O
R
O
OH
Si-attack
Re-attack
R
acetals II and/or III
bicycles I
2
2
HO
HO
3
3
PdII
PdII
HO BnO
OBn
OBn
Re face
2,3-trans-σ-Pd-complex H
2,3-cis-σ-Pd-complex I
non-xylo
Scheme 7.
Table 4
Calculated free energie of TS# for Re- and Si-attack on D-ido-6c (xylo) and D-gulo-6c (non-xylo) alkenitols (CAChe-DGauss energies at 298.13 K)
Type of attack
Enthalpya (Kcal/mol)
S#(T) (cal/mol/K)
Enthalpy correction (Kcal/mol)
G#(T) (Kcal/mol)
Re attack at D-ido-6c
Si attack at D-ido-6c
Re attack at D-gulo-6c
Si attack at D-gulo-6c
ꢀ261.6
ꢀ248.8
ꢀ256.0
ꢀ258.6
204.7
202.4
204.1
203.9
19.5
19.2
19.4
19.2
ꢀ322.7
ꢀ309.1
ꢀ316.8
ꢀ319.3
a
Heat of formation.
cis-tetrahydrofurans. We believe that this efficient method-
ology is predisposed to become a powerful synthetic tool
for the preparation of complex oxygenated natural
products.
4. Experimental
4.1. General
Fig. 2. Models of TS# for Re and Si attack on D-ido-6c.
Commercial reagents were used without further purifica-
tion. All solvents were distilled before use. Hexanes and
petrolether (PE) refer to the fraction boiling at 60–65 ꢁC.
Flash column liquid chromatography (FLC) was per-
formed on silica gel Kieselgel 60 (40–63 lm, 230–400 mesh)
and analytical thin-layer chromatography (TLC) was per-
formed on aluminum plates pre-coated with either
0.2 mm (DC-Alufolien, Merck) or 0.25 mm silica gel 60
F254 (ALUGRAMꢂ SIL G/UV254, Macherey-Nagel). The
compounds were visualised by UV fluorescence and by dip-
ping the plates in an aqueous H2SO4 solution of cerium sul-
phate/ammonium molybdate followed by charring with a
heat gun. HPLC analyses were performed on Varian Dyna-
max system with variable wavelength UV detector: column
intuitive ones. In the absence of other accessible probes to
monitor the exceedingly complex reaction mixtures, even
such simplified theoretical models proved to be useful
beyond expectation and we intend to develop it towards
real predictive power [21].
3. Conclusion
In conclusion, we have found a novel type of PdCl2/
CuCl2-catalysed bicyclisation of sugar-derived unsaturated
polyols that leads to 1,4:2,5-dianhydroalditols in good
yields [22]. This useful synthetic method is highly sub-
strate-selective and displays a strong stereochemical prefer-
ence for alkenitols with C3,C4,C5-all-syn (xylo) relative
configuration. Moreover, the transformation is diastereo-
specific due to the formation of new C-2 stereogenic centre
with threo-relationship exclusively (Scheme 8).
Finally, the tandem bicyclisation-ring opening repre-
sents a new synthetic access to 2,3-trans-tetrahydrofuran
skeleton and thus is complementary to known oxycarbony-
lation methodology [5,8] producing diastereomeric 2,3-
2
O 2
OBn
OH
OBn
O
HO
4
4
R
R
xylo
2,4-threo
Scheme 8.

934
M. Babjak et al. / Journal of Organometallic Chemistry 691 (2006) 928–940
SEPARON SGX 10 lm, 25 · 4 mm, mobile phase: 4.7%
MeOH in CHCl3, flow rate: 1 ml/min, UV detection:
254 nm, 25 ꢁC. Melting points were obtained using a Boe-
cius apparatus and/or Kofler hot plate and are uncor-
rected. Optical rotations were measured with a POLAR
L-lP polarimeter (IBZ Messtechnik) with a water-jacketed
PhCH2), 70.4, 71.0, 71.4 (all d, C-4, C-5, C-6), 82.5 (d,
C-3), 118.2 (t, C-1), 127.1, 127.3, 128.0, (all d, Ph), 136.0
(d, C-2), 138.8 (s, Ph); D-manno-6b 63.7 (t, C-7), 69.9 (t,
PhCH2), 69.6, 71.0, 71.1 (all d, C-4, C-5, C-6), 80.2, (d,
C-3), 117.5, (t, C-1), 127.1, 127.3, 128.0, (all d, Ph), 137.7
(d, C-2), 138.7 (s, Ph).
10,000 cm cell at the wavelength of sodium line
D
(k = 589 nm). Specific rotations are given in units of
10ꢀ1 deg cm2 gꢀ1 and concentrations are given in
g/100 mL. Elemental analyses were run on FISONS
EA1108 instrument. Infrared spectra were recorded either
on a Philips Analytical PU9800 FTIR spectrometer or a
Perkin–Elmer 1750 FTIR spectrophotometer as KBr discs
(KBr) or as thin films on KBr plates (film). NMR spectra
were recorded on a Varian VXR-300 spectrometer. Chem-
ical shifts (d) are quoted in ppm and are referenced to the
tetramethylsilane (TMS) as internal standard. The COSY,
NOESY and DIFNOE techniques were used in assignment
4.2.2. 4,5:6,7-Di-O-isopropylidene-D-gulo-1-heptenitol (D-
gulo-4c) and 4,5:6,7-di-O-isopropylidene-D-ido-1-heptenitol
(D-ido-4c)
Vinylmagnesium bromide (1 M in THF, 4 ml, 4 mmol,
1.85 equiv.) was added at once to a CH2Cl2 solution
(10 ml) of aldehyde D-xylo-3c [11] (500 mg, 2.17 mmol) at
15 ꢁC under Ar and the resulting mixture was stirred over-
night at r.t. The reaction was quenched with sat. aq. NH4Cl
solution (10 ml) and extracted with Et2O (3 · 10 ml). Com-
bined org. extracts were dried (Na2SO4) and concentrated
in vacuo. Purification of the crude product by FLC (15 g,
gradient elution: AcOEt/hexanes 25% ! 33%) yielded D-
gulo-4c/D-ido-4c as colourless oil (300 mg, 54%, syn/
anti = 1:1); Rf 0.7 and 0.64 (AcOEt/toluene 1:1); 1H
NMR (300 MHz, CDCl3) D-gulo-4c/D-ido-4c (1:1): 1.38,
1.43, 1.44 (12H, all s, all CH3), 2.34 (1H, bs, OH), 3.86-
4.22 (6H, m, H-3, H-4, H-5, H-6, H-7), 4.30 (1H, bs,
OH), 5.28 (1H, dd, J1E,1Z = 1.7, J1Z,2 = 10.7 Hz, H-1Z),
5.41 (1H, ddd, J1E,3 = 1.3, J1E,1Z = 1.7, J1E,2 = 17.5 Hz,
H-1E), 5.93 (1H, m, H-2); 13C NMR (75 MHz, CDCl3):
25.5, 26.1, 27.0, 27.4, 27.2, 27.3 (all q, all CH3), 65.7,
65.9 (2 · t, C-7), 71.9, 72.3, 74.9, 75.4, 76.7, 76.9, 79.2,
79.6 (all d, C-3, C-4, C-5, C-6), 109.6 (s, (CH3)2C), 109.7,
109.9 (2 · s, (CH3)2C), 116.9, 117.1 (2 · t, C-1), 135.9,
137.0 (2 · d, C-2).
1
of H–1H relationships and the determination of relative
configuration. The multiplicities of carbons were assigned
from a broadband decoupled analysis used in conjunction
with either APT or DEPT programs. The HETCOR and
HMQC techniques were used throughout for the assign-
1
ment of the H–13C relationships. Compounds are num-
bered according to carbohydrate naming scheme.
4.2. Synthesis of polyols 1 and 6
4.2.1. 3-O-Benzyl-D-gluco-1-heptenitol (D-gluco-6b) and 3-
O-benzyl-D-manno-1-heptenitol (D-manno-6b)
The suspension of hexanes washed NaH (60% in paraf-
fin, 140 mg, 3.44 mmol, 1.6 equiv.) in dry DMF (10 ml) was
cooled to ꢀ30 ꢁC and the solution of protected alkenitols
D-gluco-4b/D-manno-4b [10] (556 mg, 2.15 mmol) in DMF
(10 ml) was added in several portions. The resulting mix-
ture was stirred for 1 h and benzyl bromide (0.28 ml,
404 mg, 2.37 mmol, 1.1 equiv.) was added at once. The
reaction was left to stir overnight, quenched with water
(25 ml) and aq. layer was extracted with Et2O (3 · 25 ml).
Combined org. extracts were dried (Na2SO4) and concen-
trated in vacuo. The obtained crude oil (750 mg) was dis-
solved in 70% EtOH (20 ml) and conc. HCl (2 ml) was
added. The solution was stirred at r.t. under continuous
TLC monitoring (ca. 4 h). When no isopropylidene inter-
mediate was detected (Rf = 0.66, 17% AcOEt in toluene),
solvents were removed in vacuo and the residue was dis-
solved in AcOEt (20 ml) and dried over anhydrous
K2CO3. The crude product was concentrated and crystal-
lised from AcOEt (ca. 10 ml) to afford D-gluco-6b/D-
manno-6b (310 mg, 54%, 63:37) as colourless crystals; Tr:
10.8 min for D-gluco-6b and 12.0 min for D-manno-6b; Rf
0.2 (AcOEt); m.p. 132–136 ꢁC; 1H NMR (300 MHz,
DMSO-d6): 3.27–3.73 (5H, m, H-4, H-5, H-6, H-7), 3.87
(1H, m, H-3), 4.14–4.57 (12H, m, 4xOH, PhCH2), 5.27
(2H, m, J1Z,2 = 11.0, J1E,2 = 15.7 Hz, H-1E, H-1Z), 5.71-
5.93 (1H, m, H-2), 7.23–7.46 (5H, m, Ph); 13C NMR
(75 MHz, DMSO-d6) D-gluco-6b: 63.4 (t, C-7), 69.7 (t,
4.2.3. 3-O-Benzyl-D-gulo-1-heptenitol (D-gulo-6c) and 3-O-
benzyl-D-ido-1-heptenitol (D-ido-6c)
The suspension of hexanes washed NaH (60% in paraf-
fin, 179 mg, 4.47 mmol, 1.5 equiv.) in dry DMF (10 ml) was
cooled to 0 ꢁC and the solution of acetonides D-gulo-4c/D-
ido-4c (768 mg, 2.98 mmol) in DMF (5 ml) was added
dropwise during 10 min. The resulting mixture was stirred
for 1 h and benzyl bromide (0.4 ml, 560 mg, 3.3 mmol,
1.1 equiv.) was added at once. The reaction was left to stir
at r.t. overnight, quenched with water (3 ml), volatiles were
removed in vacuo and the residue was dissolved in Et2O
(30 ml). Insoluble solids (NaBr) were filtered off (Celite
pad) and the filtrate was concentrated. Crude oil contain-
ing benzylated intermediate (Rf 0.72 (17% AcOEt in tolu-
ene)) was dissolved in 75% EtOH (20 ml), conc. HCl
(1 ml) was added and the solution was stirred for 8 h at
r.t. After concentration in vacuo, the crude material was
purified by FLC (25 g, AcOEt) yielding an equimolar mix-
ture of D-gulo-6c/D-ido-6c (530 mg, 66%, 1:1) as pale brown
1
oil; Rf 0.26 (10% MeOH in CHCl3); H NMR (300 MHz,
DMSO-d6): 3.40–3.57, 3.67 (5H, m, H-4, H-5, H-6, H-7),
3.87 (1H, m, H-3), 4.32–4.56 (6H, m, 2 · OH, 2 · PhCH2),
5.27 (2H, m, J1Z,2 = 9.2, J1E,2 = 16.3 Hz, H-1E, H-1Z),
5.77-5.91 (1H, m, H-2), 7.29–7.41 (5H, m, Ph); 13C NMR

M. Babjak et al. / Journal of Organometallic Chemistry 691 (2006) 928–940
935
(75 MHz, DMSO-d6): 62.4 (t, C-7), 69.7, 69.8 (2 · t,
PhCH2), 69.1, 70.0, 72.7, 72.9, 73.1, 73.5 (all d, C-4, C-5,
C-6), 80.3, 81.7 (2 · d, C-3), 117.8, 118.1 (2 · t, C-1),
127.1, 127.1, 127.4, 128.0, 128.1 (all d, all Ph), 136.0,
136.9 (2 · d, C-2), 138.6, 138.7 (2 · s, Ph).
NMR (250 MHz, DMSO-d6): 1.29, 1.35 (2 · 3H, 2 · s,
2 · CH3), 3.34 (1H, dd, J1A,1B = 10.0, J1A,2 = 4.9 Hz,
H-1A), 3.46 (1H, dd, J1A,1B = 10.0, J1B,2 = 2.1 Hz, H-1B),
3.54 (1H, dddd, J2,3 = 8.4, J2,0H = 5.3, J 1A,2 = 4.9, J1B,2
= 2.1 Hz, H-2), 3.59 (1H, dd, J2,3 = 8.4, J3,4 = 1.3 Hz, H-
3), 3.75 (1H, ddd, J4,OH = 8.6, J4,5 = 1.4, J3,4 = 1.3 Hz,
H-4), 3.83 (1H, dd, J5,6 = 7.4 Hz, J4,5 = 1.4 Hz, H-5),
3.95 (1H, dd, J7A,7B = 8.5, J6,7A = 5.5 Hz, H-7A), 4.02
(1H, dd, J7A,7B = 8.5, J6,7B = 6.3 Hz, H-7B), 4.26 (1H,
ddd, J5,6 = 7.4, J6,7B = 6.3, J6,7A = 5.5 Hz, H-6), 4.72
(1H, d, J4,OH = 8.6 Hz, 4-OH), 5.36 (1H, d, J2,0H
= 5.3 Hz, 2-OH), 5.61 (1H, s, PhCH), 7.35–7.49 (5H, m,
Ph); 13C NMR (63 MHz, DMSO-d6): 15.5 (t, C-1), 25.3,
26.6 (2 · q, 2 · CH3), 60.8 (d, C-4), 65.7 (t, C-7), 66.3 (d,
C-2), 73.4 (d, C-6), 80.0 (d, C-5), 82.1 (d, C-3), 99.7 (d,
PhCH), 108.0 (s, (CH3)2C), 126.0, 127.8, 128.5, 138.1
(Ph); Found: C, 45.33; H, 5.15; I, 27.93. C17H23O6I
(450.27) requires C, 45.35; H, 5.15; I, 28.18%.
4.2.4. 3,5(R)-O-Benzylidene-6,7-O-isopropylidene-1-
methanesulphonyl-D-glycero-D-gulitol (8)
To a mixture of triol 7 (5.0 g, 14.7 mmol) and Et3N
(1.78 g, 17.64 mmol, 1.2 equiv.) in dry CH2Cl2 (100 ml) a
solution of MsCl (1.25 ml 16.16 mmol, 1.1 equiv.) in
dichloromethane (50 ml) was added dropwise over 6 h
under Ar at r.t. The reaction mixture was stirred for further
12 h, then water (50 ml) was added and the aq. layer was
extracted with CH2Cl2 (3 · 30 ml). Combined org. extracts
were dried (Na2SO4) and evaporated in vacuo. Purification
of the crude product by FLC (60 g, 19 · 3 cm, PE:AcOEt
1:1) yielded 8 as a colourless solid (4.42 g, 72%); m.p.
18
163–164 ꢁC; ½aꢁD ꢀ 6:3 (c 0.22, CHCl3); IR (KBr): 3500–
3200 (s, br, OH), 1453 (m), 1410 (m), 1345 (s), 1220 (m),
1181 (s), 1097 (s), 1071 (s), 1033 (s), 1020 (s), 956 (s), 811
4.2.6. 3,5(S)-O-Benzylidene-1,2-dideoxy-6,7-O-
isopropylidene-D-gluco-1-heptenitol (10)
1
(m), 755 (m), 700 (m); H NMR (250 MHz, DMSO-d6):
The suspension of iodide 9 (7.13 g, 15.83 mmol) and Zn–
Cu (19 g) in a mixture of acetone/water (300 ml, 4:1) was
refluxed for 1.5 h. After cooling, filtration of solids and
evaporation in vacuo, the residual aqueous layer was
extracted with dichloromethane (3 · 60 ml). Combined
org. phases were dried (Na2SO4) and evaporated in vacuo.
Purification of the crude product by FLC (45 g, 15 · 3 cm,
PE:AcOEt 3:1) yielded 10 as a colourless oil (4.17 g, 86%);
1.29, 1.35 (2 · 3H, 2 · s, 2 · CH3), 3.14 (3H, s, CH3SO2),
3.76 (1H, ddd, J4,OH = 8.5, J3,4 = 1.4, J4,5 = 1.4 Hz, H-4),
3.80 (1H, dd, J2,3 = 9.0, J3,4 = 1.4 Hz, H-3), 3.85 (1H, dd,
J5,6 = 7.4, J4,5 = 1.4 Hz, H-5), 3.96 (1H, dd, J7A,7B = 8.5,
J6,7A = 5.4 Hz, H-7A), 3.97–4.04 (1H, m, H-2), 4.03 (1H,
dd, J7A,7B = 8.5, J6,7B = 6.2 Hz, H-7B), 4.23 (1H, dd, J
1A,1B = 10.6, J1A,2 = 5.2 Hz, H-1A), 4.23–4.28 (1H, m, H-
6), 4.33 (1H, dd, J1A,1B = 10.6, J1B,2 = 2.4 Hz, H-1B),
4.75 (1H, d, J4,OH = 8.5 Hz, 4-OH), 5.43 (1H, d,
J2,OH = 6.1 Hz, 2-OH), 5.65 (1H, s, PhCH), 7.35–7.50
(5H, m, Ph); 13C NMR (63 MHz, DMSO-d6): 25.3, 26.6
(2 · q, 2 · CH3), 36.5 (q, CH3SO2), 60.7 (d, C-4), 65.7 (t,
C-7), 66.0 (d, C-2), 71.9 (t, C-1), 73.4 (d, C-6), 78.6 (d,
C-3), 80.0 (d, C-5), 99.6 (d, PhCH), 108.0 (s, (CH3)2C),
126.1, 127.8, 128.5, 138.1 (Ph); Found: C 51.84, H 6.22, S
7.46, C18H26O9S (418.47) requires C, 51.66; H, 6.26; S,
7.66%.
22
½aꢁD þ 10:6 (c 0.368, CHCl3); IR (film): 3600–3300 (m, br,
OH), 2986 (s), 2934 (m), 2872 (m), 1453 (m), 1381 (s),
1339 (m), 1257 (s), 1219 (s), 1148 (s), 1094 (s), 1064 (s),
1029 (s), 928 (m), 889 (m), 844 (s), 812 (w), 759 (s), 700
(s); 1H NMR (250 MHz, CDCl3): 1.38, 1.45 (2 · 3H,
2 · s, 2 · CH3), 2.29 (1H, d, J4,OH = 10.2 Hz, OH), 3.75
(1H, ‘‘dt’’, ddd, J4,OH = 10.2, J3,4 = 1.3, J4,5 = 1.3 Hz, H-
4), 3.80 (1H, dd, J5,6 = 8.0, J4,5 = 1.3 Hz, H-5), 4.05 (1H,
dd, J7A,7B = 8.7, J6,7A = 6.0 Hz, H-7A), 4.12 (1H, dd,
J7A,7B = 8.7, J6,7B = 4.8 Hz, H-7B), 4.38 (1H, ddd,
J5,6 = 8.0, J6,7A = 6.0, J6,7B = 4.8 Hz, H-6), 4.45 (1H,
dddd, J2,3 = 4.9, J1E,3 = 1.6, J1Z,3 = 1.6, J3,4 = 1.3 Hz, H-
3), 5.34 (1H, ‘‘dt’’, ddd, J1E,2 = 10.7, J1E,1Z = 1.6,
J1E,3 = 1.6 Hz, H-1E), 5.48 (1H, ‘‘dt’’, ddd, J1Z,2 = 17.4,
J1E,1Z = 1.6, J1Z,3 = 1.6 Hz, H-1Z), 5.67 (1H, s, PhCH),
5.99 (1H, ddd, J1Z,2 = 17.4, J1E,2 = 10.7, J2,3 = 4.9 Hz, H-
2), 7.34–7.52 (5H, m, Ph); 13C NMR (63 MHz, DMSO-
d6): 25.2, 27.0 (2 · q, 2 · CH3), 65.2 (d, C-4), 66.7 (t,
C-7), 73.4 (d, C-6), 80.6 (d, C-3), 100.8 (d, PhCH), 109.3
(s, (CH3)2C), 117.8 (t, C-1), 126.0, 128.3, 129.1, 134.1
(Ph), 137.5 (d, C-2); Found: C, 66.56; H, 7.32; C17H22O5
(306.36) requires C, 66.65; H, 7.24%.
4.2.5. 3,5(R)-O-Benzylidene-1-deoxy-6,7-O-isopropylidene-
1-iodo-D-glycero-D-gulitol (9)
The mixture of mesylate 8 (3.0 g, 7.2 mmol) and NaI
(8.6 g, 57.4 mmol, 8 equiv.) in butanone (250 ml) was
refluxed for 1.5 h. After cooling and evaporation in vacuo,
a mixture of dichloromethane (100 ml), H2O (80 ml),
K2CO3 (1.04 g) and Na2S2O5 Æ 5H2O (2.35 g) was added
to the residue and the resulting mixture was stirred for
20 min at r.t.. Phases were separated and aq. layer was
extracted with dichloromethane (3 · 40 ml). Combined
org. extracts were dried (Na2SO4) and evaporated in vacuo.
Purification of the crude product by FLC (55 g, 17 · 3 cm,
AcOEt) yielded 9 as a colourless solid (2.82 g, 87%); m.p.
4.2.7. 3,5(S)-O-Benzylidene-1,2-dideoxy-D-gluco-1-
heptenitol (11)
The solution of acetonide 10 (1.519 g, 4.96 mmol) in
85% AcOH (90 ml) was stirred at r.t. for 13.5 h. After evap-
oration in vacuo, the crude solid was purified by FLC
20
173–175 ꢁC; ½aꢁD ꢀ 8:4 (c 0.213, CHCl3); IR (KBr): 3500–
3200 (m, br, OH), 2991 (m), 2935 (m), 2875 (m), 1387
(m), 1372 (m), 1210 (m), 1183 (m), 1168 (m), 1091 (s),
1
1063 (s), 1032 (s), 1016 (s), 838 (m), 752 (m), 702 (s); H

936
M. Babjak et al. / Journal of Organometallic Chemistry 691 (2006) 928–940
(80 g, 26 · 3.5 cm, CH2Cl2:MeOH 3:1) to furnish 11 as
colourless solid (1.212 g, 92%); m.p. 170–171 ꢁC;
(1H, ‘‘dt’’, ddd, J1Z,2 = 17.3, J1Z,3 = J1Z,1E = 1.5 Hz, H-
1Z), 5.70 (1H, s, PhCH), 5.86 (1H, ddd, J1Z,2 = 17.3,
J1E,2 = 10.8, J2,3 = 5.0 Hz, H-2), 7.27–7.60 (10H, m,
2 · Ph); 13C NMR (100 MHz, CDCl3): 65.0 (d, C-4), 73.3
(d, C-6), 80.6 (d, C-3), 84.8 (d, C-5), 101.2 (d, PhCH),
117.9 (t, C-1), 126.2, 127.3, 128.3, 128.3, 128.5, 129.3, (all
d, all Ph) 133.6 (d, C-2), 137.3, 138.3, (2 · s, 2 · Ph); Found:
C, 73.02; H, 6.45; C19H20O4 (312.36) requires C, 73.06; H,
21
½aꢁD þ 4:5 (c 0.11, MeOH); IR (KBr): 3400–3200 (s, br,
OH), 2947 (m), 2923 (m), 2868 (w), 1453 (m), 1420 (m),
1383 (m), 1352 (m), 1324 (m), 1166 (m), 1105 (s), 1071
(s), 1024 (s), 991(w), 918 (m), 887 (m), 848 (m), 731 (m),
696 (s), 669 (m); 1H NMR (500 MHz, CD3OD): 3.67
(1H, dd, J7A,7B = 11.6, J6,7A = 5.0 Hz, H-7A), 3.77 (1H,
‘‘t’’, dd, J3,4 = J4,5 = 1.5 Hz, H-4), 3.78 (1H, dd,
J7A,7B = 11.6, J6,7B = 2.7 Hz, H-7B), 3.87 (1H, dd,
J5,6 = 8.8, J4,5 = 1.5 Hz, H-5), 3.91 (1H, ddd, J5,6 = 8.8,
J6,7A = 5.0, J6,7B = 2.7 Hz, H-6), 4.45 (1H,‘‘dq’’, dddd,
J2,3 = 5.5, J3,4 = J1Z,3 = 1.5 Hz, J1E,3 = 1.5 Hz, H-3), 5.25
(1H, ddd, J1E,2 = 10.7, J1Z,1E = 1.6, J1E,3 = 1.5 Hz, H-
1E), 5.41 (1H, ‘‘dt’’, ddd, J1Z,2 = 17.4, J1Z,1E = 1.6,
J1Z,3 = 1.5 Hz, H-1Z), 5.67 (1H, s, PhCH), 3.03 (1H, ddd,
J1Z,2 = 17.4, J1E,2 = 10.7, J2,3 = 5.5 Hz, H-2), 7.30–7.57
(5H, m, Ph); 13C NMR (125 MHz, CD3OD): 64.2 (t, C-
7), 66.2 (d, C-4), 70.8 (d, C-6), 80.6 (d, C-5), 82.7 (d, C-
3), 102.2 (d, PhCH), 117.2 (t, C-1), 127.5, 129.0, 129.7,
136.7 (Ph), 139.9 (d, C-2) ; Found: C, 63.27; H, 6.88;
C14H18O5 (266.30) requires C, 63.14; H, 6.81%.
22
6.45%. Data for D-gluco-12: m.p. 144–147 ꢁC; ½aꢁD þ 30:8
(c 0.08, CHCl3); IR (KBr): 3500–3250 (s, br, OH), 3057
(m), 3034 (m), 2910 (m), 2926 (m), 2861 (m), 2845 (m),
1497 (w), 1458 (m), 1450 (m), 1418 (m), 1340 (m), 1333
(m), 1213 (m), 1163 (s), 1097 (s), 1086 (s), 1074 (s), 1061
1
(s), 1038 (s), 1013 (s), 935 (s), 839 (s), 756 (s), 700 (s); H
NMR (400 MHz, CDCl3): 2.94 (1H, s, OH), 3.29 (1H, s,
OH), 3.83 (1H, s, H-4), 3.89 (1H, dd, J5,6 = 6.6,
J3,5 = 1.2 Hz, H-5), 4.36 (1H, dddd, J2,3 = 5.0,
J1E,3 = J1Z,3 = 1.6, J3,5 = 1.2 Hz, H-3), 5.05 (1H, d,
J5,6 = 6.6 Hz, H-6), 5.33 (1H, ‘‘dt’’, ddd, J1E,2 = 10.7,
J1E,3 = 1.6, J1Z,1E = 1.5 Hz, H-1E), 5.34 (1H, ‘‘dt’’, ddd,
J1Z,2 = 17.3, J1Z,3 = 1.6, J 1Z,1E = 1.5 Hz, H-1Z), 5.61
(1H, s, PhCH), 5.96 (1H, ddd, J1Z,2 = 17.3, J 1E,2 = 10.7,
J2,3 = 5.0 Hz, H-2), 7.25-7.48 (10H, m, 2 · Ph); 13C NMR
(100 MHz, CDCl3): 65.5 (d, C-4), 73.3 (d, C-6), 80.5 (d,
C-3), 82.3 (d, C-5), 100.6 (d, PhCH), 117.7 (t, C-1), 125.0,
126.5, 127.8, 128.1, 128.3, 128.9, (all d, all Ph), 133.9 (d,
C-2), 137.5, 140.7 (2 · s, 2 · Ph); Found: C 73.06, H 6.40,
C19H20O4 (312.36) requires C, 73.06; H, 6.45%.
4.2.8. 3,5(S)-O-Benzylidene-1,2-dideoxy-6-phenyl-L-ido-1-
hexenitol (L-ido-12) and 3,5(S)-O-benzylidene-1,2-dideoxy-
6-phenyl-D-gluco-1-hexenitol (D-gluco-12)
The suspension of triol 11 (5.104 g, 19.17 mmol) and
NaIO4 (4.51 g, 21.08 mmol, 1.1 equiv.) in a mixture of
MeOH/H2O (900 ml, 2:1) was stirred at r.t. for 1.5 h. After
filtration and evaporation in vacuo, the residual aq. layer
was extracted with dichloromethane (4 · 100 ml). Com-
bined org. phases were dried (Na2SO4) and evaporated in
vacuo obtaining a crude aldehyde as colourless oil (4.2 g),
which was immediately used in a Grignard addition without
any purification. Thus, a solution of crude aldehyde (4.20 g,
17.93 mmol) in dry THF (40 ml) was slowly added dropwise
to the stirred solution of PhMgBr (freshly prepared from
PhBr (15.42 g, 98.19 mmol, 5.5 equiv.) and magnesium
turnings (2.40 g, 98.19 mmol, 5.5 equiv.)) in dry THF
(100 ml) under Ar. The reaction mixture was stirred at r.t.
for 24 h and then hydrolysed with sat. aq. NH4Cl solution
(20 ml). The mixture was extracted with Et2O (3 · 40 ml).
Combined org. phases were dried (Na2SO4) and evaporated
in vacuo. Purification of the crude residue by FLC (60 g,
20 · 5 cm, PE:AcOEt 8:2) yielded L-ido-12 (2.246 g, 41%)
and D-gluco-12 (0.613 g, 21%) as colourless solids. Data
4.2.9. 3-O-Benzyl-1,2-dideoxy-6-phenyl-L-ido-1-hexenitol
(L-ido-1)
To a solution of acetal L-ido-12 (372 mg, 1.19 mmol) and
NaBH3CN (236 mg, 3.57 mmol, 3 equiv.) in dry MeCN (40
ml) was added through septum TiCl4 (678 mg, 3.57 mmol,
3 equiv.) dropwise at 0 ꢁC over 1 min under Ar. The reac-
tion mixture was stirred for 24 h, while the temperature
reached r.t. After hydrolysis with sat. aq. NH4Cl solution
(20 ml), the mixture was evaporated in vacuo. The residue
was extracted with CH2Cl2 (3 · 20 ml), combined org.
extracts were dried (Na2SO4) and evaporated in vacuo.
Purification of the crude product by FLC (14 g, 9 · 2.5
cm, PE:AcOEt 7:3) yielded L-ido-1 as colourless oil
24
(242 mg, 65%); ½aꢁD þ 54:0 (c 0.12, CHCl3); IR (film):
3600–3150 (s, br, OH), 3063 (m), 3031 (m), 2902 (m, br),
1604 (w), 1495 (m), 1454 (m), 1393 (m), 1200 (m), 1070
(s, br), 933 (w), 761 (m), 754 (m), 700 (s); 1H NMR
(500 MHz, CDCl3): 2.88 (1H, d, J5,OH = 7.6 Hz, OH-5),
3.01 (1H, dd, J4,OH = 2.9, J5,4OH = 1.1 Hz, OH-4), 3.24
(1H, d, J6,OH = 1.8 Hz, OH-6), 3.43 (1H, ddd, J3,4 = 7.7,
J4,OH = 2.9, J4,5 = 1.3 Hz, H-4), 3.62 (1H, dddd,
J5,OH = 7.6, J5,6 = 6.5, J4,5 = 1.3, J5,4OH = 1.1 Hz, H-5),
3.96 (1H, ‘‘t’’, dd, J2,3 = 7.9, J3,4 = 7.7 Hz, H-3), 4.32,
4.61 (2 · 1H, 2 · d, JOCH2Ph = 11.4 Hz, OCH2Ph), 4.81
(1H, dd, J5,6 = 6.5, J6,OH = 1.8 Hz, H-6), 5.38 (1H, dd,
J1E,2 = 10.0, J1Z,1E = 1.6 Hz, H-1E), 5.39 (1H, dd,
J1Z,2 = 17.6, J1Z,1E = 1.6 Hz, H-1Z), 5.59 (1H, ddd,
J1Z,2 = 17.6, J1E,2 = 10.0, J2,3 = 7.9 Hz, H-2), 7.28–7.40
24
for L-ido-12: m.p. 89–90 ꢁC; ½aꢁD þ 27:0 (c 0.13, CHCl3);
IR (KBr): 3550–3300 (s, br, OH), 3034 (m), 2938 (m),
2901 (m), 2866 (m), 1557 (s), 1495 (m), 1422 (s), 1323 (m),
1198 (m), 1155 (s), 1117 (m), 1067 (s, br). 927 (s), 891 (m),
1
845 (m), 760 (s), 700 (s); H NMR (400 MHz, CDCl3):
2.46 (1H, d, J4,OH = 10.7 Hz, OH-4), 2.95 (1H, s, OH-6),
3.20 (1H, ‘‘dt’’, ddd, J4,OH = 10.7, J3,4 = 1.5,
J4,5 = 1.2 Hz, H-4), 3.83 (1H, dd, J5,6 = 8.5, J4,5 = 1.5 Hz,
H-5), 4.27 (1H, dddd, J2,3 = 5.0, J3,4 = J1Z,3 = J1E,3 = 1.5
Hz, H-3), 5.03 (1H, d, J5,6 = 8.5 Hz, H-6), 5.28 (1H, ‘‘dt’’,
ddd, J1E,2 = 10.8, J1E,3 = J1Z,1E = 1.5 Hz, H-1E), 5.39

M. Babjak et al. / Journal of Organometallic Chemistry 691 (2006) 928–940
937
(10H, m, 2 · Ph); 13C NMR (125 MHz, CDCl3): 70.6 (t,
OCH2Ph), 73.1 (d, C-4), 74.4 (d, C-5), 75.6 (d, C-6), 82.0
(d, C-3), 121.5 (t, C-1), 126.9, 128.0, 128.0, 128.4, 128.6
(all d, all Ph), 134.0 (d, C-2), 137.5, 140.1 (2 · d, 2 · Ph);
Found: C, 72.18; H, 7.07. C19H22O4 (314.38) requires C,
72.59; H, 7.05%.
phase was extracted with AcOEt (2 · 20 ml) and combined
org. layers were washed with 10% aq. NaHCO3 solution
(30 ml), dried (Na2SO4) and concentrated in vacuo. Purifi-
cation of the crude product by FLC (12 g, 33% AcOEt in
hexanes) yielded two fractions: first one with Rf 0.5 con-
tained a mixture of acetals 16/17 (50 mg, 33%) as colourless
1
oil; H NMR (300 MHz, CDCl3): 1.46 (3H, s, CH3), 1.48
(3H, s, CH3), 3.50 (bd, J = 4.8 Hz), 3.63 (1H, bs), 3.81
(2H, dd, J = 7.6, J = 5.8 Hz), 3.93 (1H, bs), 4.04 (2H, dd,
J = 2.2, J = 12.4 Hz), 4.05 (1H, s), 4.25 (1H, d,
J = 7.7 Hz), 4.46 (2H, m), 4.51 (2H, d, JA,B = 11.7 Hz,
PhCH2), 4.67 (1H, s), 4.71 (2H, d, JA,B = 11.7 Hz, PhCH2),
7.27–7.38 (5H, m, Ph); 13C NMR (75 MHz, CDCl3) major
isomer: 20.8 (q, C-1), 65.6 (t, PhCH2), 68.9 (d, C-6), 71.2 (t,
C-7), 71.8 (d, C-5), 75.5 (d, C-4), 77.4 (d, C-3), 107.2 (s,
C-2), 127.7, 128.1, 128.5 (all d, all Ph), 136.9 (s, Ph),minor
isomer: 20.3 (q, C-1), 63.6 (d, C-6), 66.9 (t, PhCH2), 72.0 (t,
C-7), 78.2 (d, C-5), 79.3 (d, C-4), 81.0 (d, C-3), 107.0 (s,
C-2), 127.7, 128.1, 128.5 (all d, all Ph), 136.9 (s, Ph). The
second fraction with Rf 0.36 contained pure bicycle D-glycero-
D-gulo-14 (90 mg, 60%) as colourless oil; 1H NMR
(300 MHz, CDCl3): 3.78 (1H, d, J1A,1B = 8.7 Hz, H-1A),
3.85 (1H, d, J 1A,1B = 8.7 Hz, H-1B), 3.91 (1H, m, H-6),
4.01 (1H, bs, OH), 4.11 (3H, m, H-3, H-7), 4.17 (1H, m,
H-5), 4.24 (1H, m, H-3), 4.39 (1H, m, H-4), 4.60 (2H, s,
PhCH2), 7.27–7.38 (5H, m, Ph); 13C NMR (75 MHz,
CDCl3): 64.5 (t, PhCH2), 70.0 (d, C-6), 72.2 (t, C-7), 73.6
(t, C-1), 75.8 (d, C-4), 76.8 (d, C-2), 80.8 (d, C-5), 81.4
(d, C-3), 127.8, 128.0, 128.5 (all d, all Ph), 137.1 (s, Ph).
An analogous bicyclisation of diastereomerically pure D-
manno-6b [17,10b] in the same reaction conditions gave
identical mixture of acetals 16/17 (57%).
4.2.10. 3-O-Benzyl-1,2-dideoxy-6-phenyl-D-gluco-1-
hexenitol (D-gluco-1)
To a solution of acetal D-gluco-12 (400 mg, 1.28 mmol)
and NaBH3CN (254 mg, 3.84 mmol, 3 equiv.) in dry
MeCN (40 ml) was added through septum TiCl4 (729 mg,
3.84 mmol, 3 equiv.) dropwise at 0 ꢁC over 1 min under
Ar. The reaction mixture was stirred for 24 h, while the
temperature reached r.t. After hydrolysis with sat. aq.
NH4Cl solution (20 ml), the mixture was evaporated. The
residue was extracted with CH2Cl2 (3 · 20 ml), combined
org. extracts were dried (Na2SO4) and evaporated in vacuo.
Purification of the crude product by FLC (13 g, 9 · 2.5 cm,
PE:AcOEt 3:1) yielded D-gluco-1 as colourless solid
21
(254 mg, 63%); m.p. 86–88 ꢁC; ½aꢁD þ 13:6 (c 0.12, CHCl3);
IR (KBr): 3533 (s, OH), 3463 (s, br, OH), 3398 (s, br, OH),
3029 (w), 2946 (w), 2910 (w), 2887 (m), 2871 (m), 1496 (w),
1454 (m), 1391 (m), 1329 (m), 1285 (m), 1206 (m), 1129 (s),
1059 (s), 1038 (s), 1020 (s), 988 (m), 939 (m), 769 (s), 730
(s), 700 (s); 1H NMR (500 MHz, CDCl3): 3.04 (1H, d,
J5,OH = 8.0 Hz, OH-5), 3.10 (1H, dd, J4,OH = 2.8,
J5,OHꢀ4 = 1.0 Hz, OH-4), 3.40 (1H, d, J6,OH = 7.3 Hz,
OH-6), 3.64 (1H, ddd, J3,4 = 7.3, J4,OH = 2.8, J4,5
1.2 Hz, H-4), 3.76 (1H, dddd, J5,OH = 8.0, J5,6 = 5.3,
J4,5 = 1.2, J5,4OH = 1.0 Hz, H-5), 3.97 (1H, dd, J2,3 = 8.2,
J3,4 = 7.3 Hz, H-3), 4.30, 4.60 (2·1H, 2·d, JOCH2Ph
11.4 Hz, OCH2Ph), 4.93 (1H, dd, J5,6 = 5.3, J6,OH
= 7.3 Hz, H-6), 5.38 (1H, dd, J1Z,2 = 17.9, J1Z,1E
1.8 Hz, H-1Z), 5.39 (1H, dd, J1E,2 = 9.8, J1Z,1E = 1.6 Hz,
H-1E), 5.64 (1H, ddd, J1Z,2 = 17.9, J1E,2 = 9.8, J2,3 = 8.2
Hz, H-2), 7.28–7.40 (10H, m, 2 · Ph); 13C NMR
(125 MHz, CDCl3): 70.6 (t, OCH2Ph), 72.2 (d, C-4), 73.1
(d, C-5), 76.3 (d, C-6), 82.2 (d, C-3), 121.2 (t, C-1), 125.8,
127.6, 128.0, 128.0, 128.5, 128.6, (all d, all Ph), 134.1 (d,
C-2), 137.5, 140.9 (2 · d, 2 · Ph); Found: C 72.21, H
7.12, C19H22O4 (314.38) requires C, 72.59; H, 7.05%.
=
=
4.3.2. 1,4:2,5-Dianhydro-3-O-benzyl-7-O-(1,10-biphenyl-4-
yl)carbonyl-D-glycero-D-gulo-heptitol (D-glycero-D-gulo-15)
To a solution of crude D-glycero-D-gulo-14 (50 mg,
0.19 mmol) and Et3N (96 mg, 0.95 mmol, 5 equiv.) in
CH2Cl2 (7 ml) was added 1,10-biphenyl-4-carbonyl chloride
(103 mg, 0.47 mmol, 2.5 equiv.) in CH2Cl2 (3 ml) and the
reaction mixture was stirred at r.t. for 36 h. Solvents were
removed in vacuo and the residue was purified by FLC
(30 g, 5% AcOEt in toluene). Combined fractions with Rf
0.45 (17% AcOEt in toluene) were concentrated in vacuo
and the obtained solid was crystallised from AcOEt/Et2O
providing D-glycero-D-gulo-15 (46 mg, 54%) as colourless
=
4.3. Palladium(II)-catalysed bicyclisation of polyols 1 and 6
25
1
needles; m.p. 166–167 ꢁC; ½aꢁD ꢀ 30:4 (c 0.17, CHCl3); H
NMR (300 MHz, CDCl3): 3.89 (1H, d, J1A,1B = 8.3 Hz,
H-1A), 3.95 (1H, bd, J1A,1B = 8.3 Hz, H-1B), 4.25 (2H,
bs, H-5, H-6), 4.26 (1H, bs, H-4), 4.33 (1H, bs, H-3),
4.42 (1H, d, J1B,2 = 2.7 Hz, H-2), 4.50 (1H, dd,
J6,7A = 4.3, J7A,7B = 11.3 Hz, H-7A), 4.62, 4.69 (2H,
4.3.1. General procedure: 1,4:2,5-Dianhydro-3-O-benzyl-D-
glycero-D-gulo-heptitol (D-glycero-D-gulo-14)
The mixture of benzylated alkenitols D-gluco-6b/D-
manno-6b (150 mg, 0.56 mmol, 63:37), PdCl2 (10 mg,
0.06 mmol, 0.1 equiv.), anhydrousCuCl2 (225 mg, 1.68 mmol,
3 equiv.) and anhydrous AcONa (138 mg, 1.68 mmol,
3 equiv.) in glacial AcOH (15 ml) were stirred at 25–30 ꢁC
under Ar for 23 h. Reaction mixture was filtered through
Celiteꢂ pad (1 · 2 cm) and washed with AcOH (2 · 5 ml).
Solvent was evaporated in vacuo and the residue distrib-
uted between water (30 ml) and AcOEt (20 ml). Water
2 · d,
JA,B = 12.2 Hz,
PhCH2),
4.78
(1H,
d,
J7A,7B = 11.3 Hz, H-7B), 7.29–7.51, 7.60–7.70 (14H 2 · m,
Ph); 13C NMR (75 MHz, CDCl3): 67.6 (t, PhCH2), 72.3
(d, C-6), 69.1 (t, C-7), 73.7 (t, C-1), 75.9 (C-2), 77.0 (d,
C-4), 81.0 (t, C-5, C-3), 127.0, 127.2, 127.8, 128.1, 128.2,
128.5, 128.9, 130.2 (all d, all Ph), 137.2, 139.9, 143.9 (all

938
M. Babjak et al. / Journal of Organometallic Chemistry 691 (2006) 928–940
s, all Ph), 167.0 (s, CO); Found: C, 72.84; H, 5.82.
C27H26O6 (446.49) requires C, 72.63; H, 5.87%.
1.71 mmol, 3 equiv.) in glacial AcOH (5 ml), r.t., 8 h, col-
our of the reaction mixture remained blue-green, FLC
(10 g, 33% AcOEt in hexanes): D-glycero-b-D-talo-ulofura-
nose 22 (35 mg, 16%) as a pale yellow oil; Rf 0.45; 1H
NMR (300 MHz, CDCl3): 1.51 (3H, s, H-1), 3.36 (1H,
ddd, J7,8B = 2.5, J7,8A = 3.0, J5,7 = 9.2 Hz, H-7), 3.58
(1H, dd, J7,8A = 3.5, J8A,8B = 11.5 Hz, H-8A), 3.61 (1H,
dd, J5,6 = 4.3, J6,7 = 9.2 Hz, H-6), 3.69 (1H, dd,
J7,8B = 2.6, J8A,8B = 11.5 Hz, H-8B), 4.01 (1H, d,
J3,4 = 6.2 Hz, H-4), 4.38 (1H, d, J5,6 = 4.3 Hz, H-5), 4.50
(1H, d, J3,4 = 6.2 Hz, H-3), 4.53 (1H, d, JA,B = 11.3 Hz,
PhCH2), 4.66 (1H, d, JA,B = 11.5 Hz, PhCH2), 4.68 (1H,
d, JA,B = 11.3 Hz, PhCH2), 4.73 (1H, d, JA,B = 11.5 Hz,
PhCH2), 7.28–7.44 (10H, m, Ph); 13C NMR (75 MHz,
CDCl3): 19.5 (q, C-1), 62.3 (t, PhCH2), 69.2, 69.8 (2 · d,
C-4, C-7), 72.1 (t, C-8), 73.9 (d, C-6), 74.7 (t, PhCH2),
81.6, 82.2 (2 · d, C-3, C-5), 106.8 (s, C-2), 128.0, 128.1,
128.3, 128.5, 128.6 (all d, all Ph), 136.6, 137.4 (all s, Ph)
and D-glycero-b-D-galacto-ulofuranose 23 (30 mg, 14%) as
a colourless oil; Rf 0.61; 1H NMR (300 MHz, CDCl3):
1.46 (3H, s, H-1), 3.60-3.85 (5H, m, J = 2.4, J = 2.7,
J = 11.4, J = 12.0 Hz, H-4, H-5, H-7, H-8), 4.07 (1H, d,
J = 3.9 Hz, H-3), 4.37 (1H, d, J = 1.8 Hz, H-6), 4.60 (2H,
‘‘dd’’, overlapped 2 · d, JA,B = 11.5 Hz, PhCH2), 4.71
(2H,s, PhCH2); 13C NMR (75 MHz, CDCl3): 22.5 (q, C-
1), 61.8 (t, PhCH2), 69.8 (d, C-7), 72.4, 72.9 (2 · t, C-8,
PhCH2), 74.0, 75.5 (2 · d, C-4, C-6), 81.8 (d, C-5), 91.0
(d, C-3), 104.3 (s, C-2), 127.9, 128.0, 128.1, 128.2, 128.5,
128.6 (all d, all Ph), 137.4, 137.9 (2 · s, 2 · Ph).
4.3.3. 1,4:2,5-Dianhydro-3-O-benzyl-D-glycero-L-gulo-
heptitol (D-glycero-L-gulo-20)
According to general procedure 4.3.1.: mixture of D-
gulo-6c/D-ido-6c (150 mg, 0.56 mmol, 52:48), PdCl2
(10 mg, 0.06 mmol, 0.1 equiv.), CuCl2 (225 mg, 1.68 mmol,
3 equiv.), AcONa (138 mg, 1.68 mmol, 3 equiv.) in glacial
AcOH (10 ml), r.t., 44 h: D-glycero-L-gulo-20 (64 mg,
43%) as colourless oil; Rf 0.21 (AcOEt); 13C NMR
(75 MHz, CDCl3): 64.3 (t, PhCH2), 70.9 (d, C-6), 72.3 (t,
C-7), 73.6 (t, C-1), 76.1 (d, C-4), 77.2 (d, C-2), 78.4 (d,
C-5) 81.4 (d, C-3), 127.8, 127.9, 128.2, 128.5, 128.7 (all d,
all Ph), 137.3 (s, Ph) and 18 or 19 (44 mg, 30%) as colour-
less oil; Rf 0.56 (AcOEt); 13C NMR (75 MHz, CDCl3): 20.9
(q, C-1), 64.3 (t, PhCH2), 71.3 (d, C-6), 72.0 (t, C-7), 75.3
(d, C-5), 76.0 (t, C-7), 77.4(d, C-4), 81.4(d, C-3), 107.3 (s,
C-2), 127.8-128.7 (2 · d, Ph), 137.1 (s, Ph).
4.3.4. 1,4:2,5-Dianhydro-3-O-benzyl-6,7-bis-O-(1,10-
biphenyl-4-yl)carbonyl-D-glycero-L-gulo-heptitol (D-glycero-
L-gulo-21)
To a solution of crude D-glycero-L-gulo-20 (50 mg,
0.19 mmol) and Et3N (96 mg, 0.95 mmol, 5 equiv.) in
CH2Cl2 (10 ml) was added 1,10-biphenyl-4-carbonyl chlo-
ride (103 mg, 0.47 mmol, 2.5 equiv.) and the reaction mix-
ture was stirred at r.t. for 36 h. Solvents were removed in
vacuo and the residue was purified by FLC (30 g, 5%
AcOEt in toluene). Combined fractions with Rf 0.45
(17% AcOEt in toluene) were concentrated in vacuo and
the obtained solid was crystallised from AcOEt/Et2O pro-
viding D-glycero-L-gulo-21 (60 mg, 50%) as colourless nee-
4.3.6. 1,4:2,5-Dianhydro-3-O-benzyl-6-phenyl-L-glycero-D-
gulitol (L-glycero-D-gulo-2)
According to general procedure 4.3.1.: mixture of hexen-
itol L-ido-1 (200 mg, 0.636 mmol), PdCl2 (11 mg,
0.064 mmol, 0.1 equiv.), CuCl2 (257 mg, 1.91 mmol,
3 equiv.) and AcONa (157 mg, 1.91 mmol, 3 equiv.) in gla-
cial AcOH (8 ml), r.t., 26 h, colour of the reaction mixture
changed from grass-green to ochre, FLC (3 g, 8 · 1 cm,
PE:AcOEt 1:2): L-glycero-D-gulo-2 (145 mg, 73%) as col-
25
dles; m.p. 188–189 ꢁC; ½aꢁD þ 30:6 (c 0.06, CHCl3); 1H
NMR (300 MHz, CDCl3): 3.94 (1H, bd, J1A,1B = 8.8 Hz,
H-1A), 4.12 (1H, d, J1A,1B = 8.8 Hz, H-1B), 4.66 (1H, d,
J5,6 = 8.3 Hz, H-5), 4.63 (1H, bs, H-4), 4.61 (1H, s, H-3),
4.35 (1H, s, H-2), 4.28 (1H, ddd, J6,7A = J6,7B = 3.0,
J7A,7B = 9.4 Hz,
H-7),
4.58,
4.72
(4H,
2 · d,
20
JA,B = 11.7 Hz, PhCH2), 5.90 (1H, ddd, J6,7A = 3.8,
J6,7B = 4.7, J5,6 = 8.3 Hz, H-6), 7.29–7.51, 7.59–7.70
(23H, 2 · m, Ph); 13C NMR (75 MHz, CDCl3): 63.7 (t,
PhCH2), 72.3 (d, C-6), 72.4 (t, C-7), 73.5 (t, C-1), 75.6 (d,
C-2), 76.1 (d, C-4), 80.7 (d, C-5), 81.5 (d, C-3), 127.0,
127.1, 127.3, 127.9, 128.1, 128.2, 128.3, 128.6, 128.7,
128.9, 130.2, 130.4 (all d, all Ph), 137.2, 139.9, 140.0,
145.7, 145.9 (all s, all Ph), 166.0 (s, CO). Found: C,
72.84; H, 5.82. C40H43O7 (626.67) requires C, 76.63; H,
5.52%.
ourless solid; m.p. 129–130 ꢁC; ½aꢁD ꢀ 5:1 (c 0.415, CHCl3).
IR (KBr): 3454 (s, br, OH), 3030 (m), 3006 (m), 2958 (m),
2935 (m), 2894 (m), 1493 (m), 1450 (m), 1403 (m), 1359 (m),
1114 (s), 1152 (s), 1143 (s), 1006 (s), 958 (m), 895 (s), 872
1
(s), 832 (m), 764 (s), 753 (s), 703 (s); H NMR (500 MHz,
CDCl3): 2.83 (1H, d, J6,OH = 1.7 Hz, OH), 3.73 (1H, dd,
J2,3 = 2.6, J1A,2 = 1.2 Hz, H-2), 3.95 (1H, ‘‘dt’’, ddd,
J1A,1B = 8.6, J1A,2 = 1.2, J1A,4 = 1.0 Hz, H-1A), 4.04 (1H,
d, J1A,1B = 8.6 Hz, H-1B), 4.15 (1H, d, J2,3 = 2.6 Hz, H-
3), 4.20 (1H, d, J5.6 = 8.9 Hz, H-5), 4.37 (1H, bs, H-4),
4.50, 4.61 (2H, 2 · d, JA,B = 11.9 Hz, PhCH2), 4.99 (1H,
dd, J5.6 = 8.9, J6,OH = 1.7 Hz, H-6), 7.24–7.42 (10H, m,
2 · Ph); 13C NMR (125 MHz, CDCl3): 72.3 (t, PhCH2),
73.7 (t, C-1), 74.3 (d, C-6), 75.8 (d, C-2), 77.3 (d, C-4),
81.6 (d, C-5), 86.8 (d, C-3), 126.7, 127.8, 128.0, 128.1,
128.4, 128.5 (all d, all Ph), 137.2, 139.7 (2 · s, Ph). Found:
C 73.15, H 6.46, C19H20O4 (312.36) requires C, 73.06; H,
6.45%.
4.3.5. 2,7-Anhydro-3,6-di-O-benzyl-D-glycero-b-D-talo-oct-
2-ulofuranose (22) and 2,7-anhydro-3,6-di-O-benzyl-D-
glycero-b-D-galacto-oct-2-ulofuranose (23)
According to general procedure 4.3.1.: mixture of
D-glycero-D-talo-6d/D-glycero-D-galacto-6d [14] (220 mg,
0.57 mmol), PdCl2 (10 mg, 0.06 mmol, 0.1 equiv.), CuCl2
(264 mg, 1.71 mmol, 3 equiv.) and AcONa (140 mg,

M. Babjak et al. / Journal of Organometallic Chemistry 691 (2006) 928–940
939
[2] L.S. Hegedus, Tetrahedron 40 (1984) 2415.
4.3.7. 1,4:2,5-Dianhydro-3-O-benzyl-6-phenyl-D-glycero-D-
gulitol (D-glycero-D-gulo-2)
[3] (a) J.P. Collman, L.S. Hegedus, J.R. Norton, R.G. Finke, in:
Principles and Applications of Organotransition Metal Chemistry,
2nd ed., University Science Books, 1987;
According to general procedure 4.3.1.: mixture of hexen-
itol D-gluco-1 (164 mg, 0.522 mmol) PdCl2 (9 mg,
0.052 mmol, 0.1 equiv.), CuCl2 (210 mg, 1.56 mmol,
3 equiv.) and AcONa (128 mg, 1.56 mmol, 3 equiv.) in gla-
cial AcOH (6 ml), 50 ꢁC, 26 h, colour of the reaction mix-
ture changed from grass-green to ochre, FLC (8 g,
7 · 2 cm, PE:AcOEt 2:1): D-glycero-D-gulo-2 (115 mg,
(b) L.S. Hegedus, in: Transition Metals in the Synthesis of Complex
Organic Molecules, University Science Books, 1994;
(c) L.S. Hegedus, Coord. Chem. Rev. 147 (1996) 443;
(d) J. Tsuji, in: Organic Synthesis with Palladium Compounds,
Springer Verlag, Berlin, 1980;
(e) J.-L. Malleron, J.-C. Fiaud, J.-Y. Legros, in: Handbook of
Palladium Catalysed Organic Reactions, Academic Press, UK, 1997;
(f) Y. Tamaru, M. Hojo, Z.-I. Yoshida, J. Org. Chem. 56 (1991)
1099;
20
71%); m.p. 86–88 ꢁC; ½aꢁD ꢀ 54:4 (c 0.125, CHCl3). IR
(KBr): 3385 (s, br, OH), 3062 (w), 3024 (w), 2956 (w),
2910 (m), 2890 (m), 1492 (m), 1450 (m), 1364 (m), 1197
(m), 1143 (s), 1049 (s), 1009 (s), 901 (s), 870 (s), 845 (m),
751 (s), 741 (s), 701 (s); 1H NMR (500 MHz, CDCl3):
2.53 (1H, d, J6,OH = 4.8 Hz, OH), 3.97 (1H, ‘‘dt’’, ddd,
J1A,1B = 8.5, J1A,2 = 1.2, J1A,4 = 1.0 Hz, H-1A), 4.02 (1H,
d, J1A,1B = 8.5 Hz, H-1B), 4.23 (1H, d, J2,3 = 2.6 Hz, H-
3), 4.31 (1H, d, J1A,4 = 1.0 Hz, H-4), 4.36 (1H, d,
(g) M.F. Semmelhack, C. Bodurow, J. Am. Chem. Soc. 106 (1994)
1496.
[4] (a) M. Orena, 4th ed., in: G. Helmchen, R. Hoffmann, J. Mulzer
(Eds.), Cycloetherification, Houben Weyl, vol. E21c, Georg Thieme
Verlag Stuttgart, New York, 1995, p. 4698;
(b) D. Elbracht, 4th ed., in: G. Helmchen, R. Hoffmann, J. Mulzer
(Eds.), Addition to Olefinic Double Bonds Catalysed by Transition
Metals, Houben Weyl, vol. E21c, Georg Thieme Verlag Stuttgart,
New York, 1995, p. 2488;
(c) H.G. Schmalz, in: Ei-ichi Negishi (Ed.), Handbook of Organ-
opalladium Chemistry for Organic Syntheses, vol. 2, John Wiley &
Sons, Inc., New York, 2002, p. 2377;
(d) V. Farina, M. Eriksson, in: Ei-ichi Negishi (Ed.), Handbook of
Organopalladium Chemistry for Organic Syntheses, vol. 2, John
Wiley & Sons, Inc., New York, 2002, p. 2351;
J5,6 = 8.2 Hz, H-5), 4.40 (1H, dd, J2,3 = 2.6, J1A,2
=
1.2 Hz, H-2), 4.56, 4.65 (2H, 2 · d, J A,B = 11.9 Hz,
PhCH2), 4.92 (1H, dd, J5,6 = 8.2, J6,OH = 4.8 Hz, H-6),
7.27–7.50 (10H, m, 2 · Ph); 13C NMR (125 MHz, CDCl3):
72.2 (t, PhCH2), 72.8 (d, C-6), 74.0 (t, C-1), 76.2 (d, C-2),
76.8 (d, C-4), 81.1 (d, C-3), 84.7 (d, C-5), 126.8, 127.8,
128.0, 128.1, 128.5(all d, all Ph), 137.3, 141.9 (2 · s, Ph).
Found: C, 72.85; H, 6.52. C19H20O4 (312.36) requires C,
73.06; H, 6.45%.
(e) J. Muzart, Tetrahedron 61 (2005) 5955.
[5] (a) Lꢀ. Remenˇ, PhD Thesis, Slovak University of Technology,
Bratislava, 1998;
(b) T. Gracza, V. Ja¨ger, Synlett (1992) 191;
(c) T. Gracza, V. Ja¨ger, Synthesis (1994) 1359.
[6] X.-P. Fang, J.E. Anderson, C.-J. Chang, J.L. McLaughlin, J. Nat.
Prod. 54 (1991) 1034.
4.4. Crystal structure determination of D-glycero-L-gulo21
[7] W. Frey, Lꢀ. Remenˇ, V. Ja¨ger, T. Gracza, Z. Kristallogr. NCS 214
(1999) 257.
[8] (a) V. Ja¨ger, T. Gracza, E. Dubois, T. Haseno¨hrl, W. Hummer, U.
¨
Crystals of D-glycero-L-gulo-21 suitable for X-ray struc-
ture analysis were obtained by crystallisation from AcOEt/
Et2O. Diffraction data have been collected on a Siemens P4
diffractometer using graphite monochromated Mo Ka radi-
Kautz, B. Kirschbaum, A. Lieberknecht, L.Lꢀ. Remenˇ, D. Shaw, U.
Stahl, O. Stephan, in: G. Helmchen (Ed.), Organic Synthesis via
Organometallics (OSM5), Vieweg & Sohn Verlagsgesellschaft, Braun-
schweig/Wiesbaden, 1997, p. 321;
˚
ation (k = 0.71073 A) and Siemens XSCANS software [23].
(b) T. Gracza, T. Haseno¨hrl, U. Stahl, V. Ja¨ger, Synthesis (1991)
1108.
[9] (a) G.J.F. Chittenden, Carbohydr. Res. 84 (1980) 350;
(b) Ch.R. Schmid, J.D. Bryant, Organic Syntheses 72 (1995) 6.
[10] (a) Ch. Schneider, U. Kazmaier, Synthesis (1998) 1321;
(b) D. Walton, Can. J. Chem. 46 (1968) 3679.
The structure was solved by direct methods with SHELXS-97
[24] and refined by LSQ procedure against F2(hkl) with
SHELXL-97 [25]. Geometrical calculations were performed
using SHELXL-97 [25].
´
ˇ
[11] R. Fischer, A. Druckova, L. Fisera, C. Hametner, ARKIVOC (2002)
5. Supplementary material
80, Part 8.
[12] (a) M.P. van Boggelen, B.F.G.A. van Dommelen, Sh. Jiang, G.
Singh, Tetrahedron Lett. 36 (1995) 1899;
Crystallographic data for the structural analysis have
been deposited at the Cambridge Crystallographic Data
Centre, CCDC No. 285097.
(b) M.P. van Boggelen, B.F.G.A. van Dommelen, Sh. Jiang, G.
Singh, Tetrahedron 53 (1997) 16897.
´
´
[13] M. Babjak, P. Zalupsky, T. Gracza, ARKIVOC 45 (2005).
[14] J.M. Contelles, E. de Opazo, J. Carbohydr. Chem. 21 (2002) 201.
[15] (a) T.K.M. Shing, H.-Ch. Tsui, Z.-H. Zhou, W.C.T. Mak, J. Chem.
Soc., Perkin Trans 1 (1992) 887;
Acknowledgements
This work was supported by Slovak Grant Agencies
(VEGA, Slovak Academy of Sciences and Ministry of
Education, Bratislava, Project No. 1/7314/20, and APVT,
Bratislava, Project No. APVT-27-010702).
(b) S. Henkel, W. Frey, L. Remenˇ, T. Gracza, V. Ja¨ger, Z. Kristallogr.
213 (1998) 71 (X-ray analysis of 3,6-di-O-benzylidene-D-
gluconolactone).
[16] M. Babjak, PhD Thesis, Slovak University of Technology, Bratislava,
2004.
[17] H. Regeling, G.J.F. Chittenden, Carbohydr. Res. 190 (1989) 313.
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