Glycosylmanganese pentacarbonyl complexes: An organomanganese-based approach to the synthesis of C-glycosyl derivatives

Article abstract of DOI:10.1016/S0022-328X(99)00431-3

Preparation, structure and reactions of glycosylmanganese pentacarbonyl complexes are discussed. Anomerically pure complexes of pyranosyl and furanosyl complexes were prepared in excellent yield. The conformations of the anomeric glucosyl and mannosyl com

Full text of DOI:10.1016/S0022-328X(99)00431-3

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Journal of Organometallic Chemistry 593–594 (2000) 49–62
Glycosylmanganese pentacarbonyl complexes: an
organomanganese-based approach to the synthesis of C-glycosyl
derivatives
Philip DeShong a,*, Eric D. Soli a, Greg A. Slough a, D. Richard Sidler a,
Varadaraj Elango a, Philip J. Rybczynski a, Laura J.S. Vosejpka a, Thomas A. Lessen a,
Thuy X. Le a, Gary B. Anderson a, Wolfgang von Philipsborn b, Markus Vo¨hler b,
Daniel Rentsch b, Oliver Zerbe b
a Department of Chemistry and Biochemistry, Uni6ersity of Maryland, College Park, MD 20742, USA
b Organisch-chemisches Institut, Uni6ersita¨t Zu¨rich, Winterthurerstrasse 190, CH-8057 Zurich, Switzerland
Received 2 April 1999; accepted 22 July 1999
This paper is dedicated to Professor Fausto Calderazzo.
Abstract
Preparation, structure and reactions of glycosylmanganese pentacarbonyl complexes are discussed. Anomerically pure com-
plexes of pyranosyl and furanosyl complexes were prepared in excellent yield. The conformations of the anomeric glucosyl and
1
mannosyl complexes were derived from detailed analysis of their 1D and 2D H- and 13C-NMR spectra including NOE data. The
complexes are further characterized by 55Mn-NMR chemical shifts and 55Mn, 13C one-bond coupling constants. These compounds
undergo various migratory insertion reactions resulting in formation of C-glycosyl derivatives. Applications of this technology to
the synthesis of C-glycosyl and C-aryl glycosidic systems are discussed. © 2000 Elsevier Science S.A. All rights reserved.
Keywords: C-glycoside; Conformation; Demetalation; Glycosylmanganese; Manganese pentacarbonyl; 55Mn-NMR
1. Introduction
C-Glycosyl compounds are an interesting class of
compounds due to their ability to function as nu-
cleoside surrogates. As such, both naturally occurring
and synthetic C-glycosyl derivatives have served as
biochemical probes [1,2] and were shown to function as
antibiotics [3–6], antitumor and antiviral agents [7].
For example, the naturally occurring C-glycosyls
vineomycinone B2 (1) [8–12], gilvocarcin M (2) [13],
and pyrazofurin (3) [14–17] possess potent biological
activity. Similarly, tiazofurin (4) and its synthetic ana-
logue selenazofurin (5) are in clinical trials as antitumor
agents [18,19].
The goal of this project was to develop a general
approach to the synthesis of C-glycosyl derivatives
based upon an extension of our previous studies into
the chemistry of alkylmanganese pentacarbonyl com-
* Corresponding author. Tel.: +1-301-405-1892; fax: +1-301-314-
9121.
E-mail address: pd10@umail.umd.edu (P. DeShong)
0022-328X/00/$ - see front matter © 2000 Elsevier Science S.A. All rights reserved.
PII: S0022-328X(99)00431-3

50
P. DeShong et al. / Journal of Organometallic Chemistry 593–594 (2000) 49–62
enone 11 with regeneration of the alkene moiety. The
overall transformation occurs with formation of two
carbon–carbon bonds, incorporation of one molecule
of CO, and regioselective functionalization of the
alkene substrate.
Finally, sequential insertion of an alkyne with
methylmanganese pentacarbonyl gives the unsaturated
manganacycle 12. Two modes of demetalation of 12
have also been developed for this complex. In the first,
protonation of the manganacycle provides enone 13.
This reaction was studied mechanistically in our labora-
tory [29].
Alternatively, hydride reduction of manganacycle 12
results in the incorporation of a second molecule of
carbon monoxide and formation of butenolide 14. This
unique transformation involves formation of three car-
bon–carbon bonds, two molecules of CO being incor-
porated, and difunctionalization of an alkyne in a
completely regioselective manner.
Scheme 1.
Having established the versatility of alkylmanganese
pentacarbonyls for the preparation of carbonyl deriva-
tives, it was our intention to extend these transforma-
tions to glycosylmanganese complexes as a means for
preparing C-glycosyl derivatives (Scheme 2). Successful
extension of the manganese methodology would require
the investigation of several new aspects of this chem-
istry. First, it had to be demonstrated that glycosyl
derivatives (16) could be prepared. With the exception
of glycosyl iron [30], cobalt [31], and chromium carben
[32,33], derivatives, stable transition metal analogues of
carbohydrates have not been reported prior to our
studies.
There were also stereochemical features to be consid-
ered. Glycosyl complex 16 could exist as either the a- or
b-anomer, and it was our intention to synthesize 16
from the protected sugar derivative 15 in a highly
stereoselective manner. This is a particularly important
point because migratory and sequential insertion pro-
cesses to give 17–19, respectively, occur with retention
of configuration [34]. Accordingly, the configuration of
glycosyl complex 16 will be transferred to the C-glyco-
syl derivatives which result from migratory insertion.
plexes [20–28]. As summarized in Scheme 1, it was
demonstrated that simple alkyl complexes such as
methylmanganese pentacarbonyl (6) can be trans-
formed into a variety of carbonyl derivatives with
formation of either one, two or three carbon–carbon
bonds [22,23,25].
In the most common reaction of alkylmanganese
complexes, ester, amide, and thioester derivatives (8)
are prepared in excellent overall yield by the Reppe
reaction. Migratory insertion of carbon monoxide af-
fords the acyl complex 7 with formation of a new
carbon–carbon bond. Cleavage of the acyl–metal bond
by alcohols, amines, or thiols in the presence of
Na2CO3 furnishes the respective carboxylic acid deriva-
tives. This transformation, although well studied in the
organometallic literature, will furnish new insights into
the migratory insertion process when applied to com-
plex glycosyl systems (vide infra).
Sequential insertion of carbon monoxide and an elec-
tron-deficient alkene provides manganacycle 9.
Demetallation of complex 9 can be achieved either in a
‘reductive’ manner to furnish ketone 10 or to yield
Scheme 2.

P. DeShong et al. / Journal of Organometallic Chemistry 593–594 (2000) 49–62
51
2. Preparation of pyranosyl- and furanosylmanganese
pentacarbonyl complexes
Pyranosyl and furanosyl bromides and chlorides [35]
react with alkali metal salts of the manganate anion to
yield the corresponding glycosylmanganese pentacar-
bonyl complexes. In most instances, the condensation
proceeds in excellent yield and is highly stereoselective.
For example, a-glucopyranosyl bromide 20 and potas-
sium manganate (21) react at −20°C to give b-complex
22 exclusi6ely in virtually quantitative yield (Scheme 3)
[36]. On the other hand, a mixture of a-complex 24 and
b-complex 22 results from reaction of bromide 20 and
sodium manganate (23) in the presence of tetrabutylam-
monium bromide at −78°C [21,36].
Condensation of sodium manganate 23 with bromide
20 is extremely sensitive to the purity of reagents and
the ratios of anomeric products obtained (22 vs. 24)
vary accordingly. Generally, a-anomer 24 predominates
[21]. We attribute the change in stereoselectivity of the
condensation in the presence of tetrabutylammonium
bromide to in situ anomerization of the bromide. As
the condensation proceeds, bromide ion is liberated and
Scheme 4.
glucopyranosyl complex(es) using the anomeric
fluoride, acetate, or silyloxy derivatives, respectively,
have not been successful [36].
Chromatographic separation of the a-and b-glucopy-
ranosyl complexes 24 and 22, respectively, cannot be
accomplished. However, a chemical discrimination was
developed. The a-complex 24 undergoes migratory in-
sertion of carbon monoxide approximately seven times
faster than b-complex 22 [39]. At 40 psi of carbon
monoxide, it is possible to convert a-complex 24 to its
acyl derivative 25 without inducing formation of the
b-acyl complex (Scheme 4). Chromatographic separa-
tion of a-acyl 25 and b-glycosyl complex 22 is readily
achieved. Gently warming the a-acyl complex induces
deinsertion of CO and regenerates a-glucopyranosyl-
manganese pentacarbonyl (24).
Employing condensation conditions similar to those
developed for the glucopyranosyl system, manganese
pentacarbonyl complexes of the b- and a-mannopyra-
nosyl (26 and 27), b-galactopyranosyl (28), a- and
b-arabinofuranosyl (29) and b-ribofuranosyl (30) sys-
tems were synthesized [20,21,36,40].
reacts with 20 which results in formation of b-bromide.
When the rate of condensation is rapid, as with potas-
sium salt 21, condensation proceeds more rapidly than
anomerization and only b-complex is obtained. How-
ever, when the condensation rate is slower, as with 23,
anomerization occurs at a competitive rate to conden-
sation, and mixtures of anomers are obtained. The
a-anomer predominates under these conditions pre-
sumably because b-bromide is more reactive than a-
bromide 20 [37,38]. Attempts to prepare the
Anomeric complexes of mannose derivatives 26 and
27 and arabinofuranosylmanganese pentacarbonyl (29)
are separated in an analogous fashion to the glucopyra-
nosyl analogs. In these instances, the relative rates of
migratory insertion of a/b are\102 and \103, respec-
tively [36]. This remarkable difference in the rates of
migratory insertion in these systems is attributed to the
orientation of the carbon–metal bond with regard to
the lone pairs on oxygen (an anomeric effect?!) and may
provide insight into the factors that control migratory
insertion processes.
Scheme 3.

52
P. DeShong et al. / Journal of Organometallic Chemistry 593–594 (2000) 49–62
Table 1
1H- and 13C-NMR data (C6D6) of (glucosyl) Mn(CO)5 complexes 22 and 24 and (b-pyranyl) Mn(CO)5 (31)
Complex
l (ppm)
1J(C,H) (Hz)
H
l (ppm)
3J(H,H) (Hz)
i-isomer (22)
1
2
3
4
5
81.7
86.4
90.1
79.6
84.3
141
144
141
142
140
1
2
3
4
5
4.06
3.69
3.56
3.75
3.19
1,2
2,3
3,4
4,5
10.1
7.9
9.0
9.8
5,6a
"
4.1;2.0
11.0
5,6b
6
69.8
142
6a,b
3.6–3.7
2J(6a,6b)
h-isomer (24)
1
2
3
75.9
87.0
81.7
146
141
143
1
2
3
4
5.54
3.46
4.03
4.09
1,2
2,3
3,4
4.5
2.5
2.9
B3.5
7.5
4
"
144;144
76.9;76.4
5
5,6a
"
5
4.09
3.2;2.3
10.2
5,6b
6
70.5
141
6a,b
3.65–3.75
2J(6a,6b)
(i-pyranyl) Mn(CO)5 (31)
1
2
3
4
5
96.3
43.3
21.9
20.0
85.5
141
126;124
126;124
127;125
143;138
1
2e;2a
3e;3a
4e;4a
5e;5a
4.32
1.66;2.09
1.53;1.21
1.5;1.13
3.79;3.11
1a,2a
1a,2e
2a,3a
2a,3e
4a,5a
4e,5a
11.9
1.9
12.0
3.5
12.2
2.1
4e,5e
1.9
12.9
11.1
2J(2a,2e)
2J(5a,5e)
3. Structural characterization of glycosyl-Mn(CO)5
complexes
1J(C,H) value of 146 Hz. On the other hand, the H,H
coupling data contain only small values (2.5–3.5 Hz)
typical for a,e and e,e interactions, with the exception
of J(4,5)=7.5 Hz. These results are incompatible with
4C1 conformation with an axial Mn(CO)5 group and
can be explained by a twist-boat conformation with a
c-equatorial Mn(CO)5 group displaying a large tor-
sional angle (ca. 170°) for the HꢁC(4)ꢁC(5)ꢁH frag-
ment. Only in this conformation HꢁC(1) is eclipsing the
axial lone-pair on the ring oxygen that would explain
the unusual deshielding of this proton by an electric
1
3.1. H- and 13C-NMR spectra
1H- and 13C-NMR spectra provide unambiguous evi-
dence for the configuration, anomeric purity and pre-
ferred conformation of the glycopyranosyl-Mn(CO)5
complexes. The spectra were obtained with the perben-
zylated glucosyl- and mannosyl-Mn(CO)5 complexes
and analyzed and assigned using homo- and heteronu-
clear 2D shift correlation experiments. For comparison,
corresponding spectra were also obtained for pyranyl-
Mn(CO)5 (31) as a model complex. The results are
collected in Table 1.
1
field effect as well as the increased J(C,H) coupling
constant. [41] The twist-boat conformation 24a is fur-
ther confirmed by NOE experiments (vide infra) which,
1
in addition, yield evidence for the C4 chair conforma-
The b-glucosyl-isomer 22 shows the typical vicinal
H,H-coupling pattern for a 4C1 chair conformation
with an equatorial Mn(CO)5 group, i.e. large values of
tion 24b with an equatorial Mn(CO)5 group, in equil-
librium with the twist-boat 24a.
3
3
3
3
8–10 Hz for J(1,2), J(2,3), J(3,4), and J(4,5). These
diaxial coupling constants are 2–4 Hz smaller than in
b-pyranyl complex 31, presumably owing to the addi-
tional oxygen functions in the glucose fragments. No
significant features are observable in the one-bond C,H
coupling constants (1J(C,H)=14292) Hz) of the
ꢀCHꢁO-groups, including the anomeric carbon.
The corresponding 1H- and 13C-NMR data of the
perbenzylated b- and a-mannosyl pentacarbonylman-
ganese complexes 26 and 27 are summarized in Table 2.
1
The H-NMR data of a-isomer 24 display an unusu-
ally deshielded resonance for the anomeric hydrogen
HꢁC(1) (5.54 ppm) together with a slightly larger
4
As expected for the C1 chair conformation 26 of the

P. DeShong et al. / Journal of Organometallic Chemistry 593–594 (2000) 49–62
53
Table 2
1H- and 13C-NMR data (C6D6) of (mannosyl) Mn(CO)5 complexes 26 and 27
Complex
l (ppm)
1J(C,H) (Hz)
H
l (ppm)
3J(H,H) (Hz)
i-isomer (26)
1
2
3
4
5
81.4
84.0
88.3
75.4
85.3
140
141
139
146
140
1
2
3
4
5
4.31
3.62
3.61
4.19
3.28
1,2
2,3
3,4
4,5
B1
ca. 2.5
9.6
9.6
5,6a
"
4.7;1.4
11.3
5,6b
6
70.3
142
6a,b
3.83
3.68
2J(6a,6b)
h-isomer (27)
1
2
3
4
5
73.4
82.1
73.7
74.7
76.0
146
143
145
141
145
1
2
3
4
5
5.24
4.18
4.05
3.96
4.30
1,2
2,3
3,4
4,5
10.2
3.2
3.5
1.4
5,6a
"
7.5;6.5
9.3
5,6b
6
68.8
142
6a,b
3.98
3.93
2J(6a,6b)
b-isomer the axial anomeric proton HꢁC(1) shows a
normal resonance position at 4.31 ppm (31: 4.32 ppm)
and only a very small vicinal coupling to the equatoral
HꢁC(2) proton which is unresolved. Large values of 9.6
Hz are observed for 3J(3,4) and 3J(4,5). The rather
ported by NOE measurements. The a-mannosyl com-
plex (27b) exhibits cross peaks in the 2D
1H,1H-NOESY spectrum for the following dipolar in-
teractions:
HꢁC(1)/HaꢁC(6),
HbꢁC(6)
(strong);
HꢁC(2)/HꢁC(3) (strong); HꢁC(3)/HꢁC(4). There is,
however, no detectable interaction within the diaxial
pairs HꢁC(1)/HꢁC(4) or HꢁC(2)/HꢁC(5) as expected
for a twist-boat conformation (27b). Thus the perbenzy-
lated a-mannosyl pentacarbonylmanganese complex
1
large J(C(4),H) coupling constant (146 Hz) may result
from the influence of the 1,3-diaxial interaction with the
lone-pair on the ring oxygen and the lone-pairs of the
3-hydroxy group (c.f. 24).
1
prefers the C4 chair conformation (27a).
The situation is more complex for the a-glucosyl
complex 24. There is a strong dipolar interaction be-
tween HꢁC(1) and HꢁC(4) and a weaker one between
HꢁC(1) and the C(6) methylene protons. The first NOE
is clearly supporting the twist-boat conformation 24a
whereas the second one proves the presence of the
inverted 1C4 chair conformation 24b in equillibrium
with 24a. A semiquantitative evaluation of conformer
populations, however, is difficult since the cross peak
intensities not only depend on H,H distances but also
on magnetisation transfer effects, i.e. on the ratio of
chair-to-boat interconversion rate and proton spin-lat-
tice relaxation rate T−1 1 [43]. Nevertheless, as a conse-
quence of the NOE results the observed vicinal H,H
coupling constants have to be considered as average
values for the respective dihedral arrangements in 24a
and 24b. As an example, the largest observed value of
7.5 Hz for J(4,5) results from calculated dihedral angles
of 177° in 24a and 72° in 24b (see Table 1) [42,44]1.
The proton spectrum of the a-isomer 27 shows a
3
diaxial J(1,2) coupling of 10.2 Hz that is incompatible
4
with a C1 chair conformation (axial Mn(CO)5 group).
1
The inverted C4 chair (27a) or twist-boat (27b) with
pseudo-equatorial Mn(CO)5 and axial 3-hydroxy
groups display torsional angles for the HꢁC(1)ꢁC(2)ꢁH
fragment of ca. 180° and can be considered for the
preferred conformation of the a-mannosyl complex. As
shown by 2D-NOESY spectra, only (27a) is consistent
with the NOE data (vide infra).
3.2. NOE studies
1 Extensive molecular mechanics and dynamics optimizations of the
carbohydrate complexes have been performed. All conformations 10
kcal mol−1 of the global minimum were optimized and evaluated for
relative contributions to the equilibrium mixture.
The results from proton and 13C-NMR analysis as
well as molecular mechanics calculation [42] are sup-

54
P. DeShong et al. / Journal of Organometallic Chemistry 593–594 (2000) 49–62
3.3. 55Mn-NMR spectra
MnꢁCO bond lengths for equatorial and axial CO
groups [48] This observation was confirmed in the
single-crystal X-ray analysis of b-glucosyl complex (22)
in which the bond lengths of the axial and equatorial
carbonyl groups were found to be virtually identical
[49].
We have made an attempt to prove potential differ-
ences in the C(1)ꢁMn bond in the four glycoside pen-
tacarbonylmanganese complexes by 55Mn-NMR. This
quadrupolar nucleus gives rather broad lines for
organomanganese complexes [27,45–47]. As it proved
impossible to obtain 55Mn-NMR signals for the perben-
zylated derivatives, probably due to excessive line
widths of \25 kHz because of long correlation times
~c, the tetramethylethers (32–35) were prepared and
measured in benzene-d6 solution. The chemical shifts
l(Mn) and line widths Dw(1/2) are presented in Table 3
4. Migratory insertions of glycosylmanganese
pentacarbonyl complexes
Having prepared glycosylmanganese pentacarbonyl
complexes, we turned our attention to demonstrating
that these complexes would undergo the processes indi-
cated in Scheme 1. For the most part, the b-glucopyra-
nosyl complex 22 was employed for these studies. When
appropriate, an analogous reaction of the anomeric
a-complex 24 was performed to demonstrate that mi-
gratory insertion reaction occurs with retention of
configuration at the anomeric center [20,21,36,40].
The Reppe reaction of b-glucopyranosyl complex 22
in the presence of alcohols, amines, or thiols occurs in
excellent yield and complete stereoselectivity to afford
the corresponding carboxylic acid derivatives (Scheme
5). In the case of b-ribofuranosyl complex 30, forma-
tion of ester 41 constitutes a formal total synthesis of
tiazofurin (4) and selenazofurin (5) [18,19]. Careful
monitoring of conditions is mandated due to aroma-
tization of ester 41 under carbonylation conditions.
C-Glycosyl ester 37 (also 38 and 39) can be employed
for the synthesis of a variety of heteroaromatic analogs
as indicated in Scheme 6. Esters were transformed into
isoxazole, imidazole, thiazole, and tetrazine derivatives
employing established protocols [50]. Since both
anomers of the glucopyranosyl system are available
from the manganese methodology, it should be possible
to prepare an array of C-glycosyl analogs for biological
evaluation.
1
together with the J(55Mn,13C) coupling constants ob-
tained by simulation of the 13C line shapes as described
earlier [45–47].
The 55Mn chemical shifts lie in the narrow range of
(−2058910) ppm, typical for alkylmanganese(I) pen-
tacarbonyl complexes. The b-pyranyl reference complex
(31) yields a chemical shift value of −2077 ppm.
Taking into account the experimental error of 910
ppm in the determination of l(Mn) for the rather
broad resonances (Dw(1/2)=10–14 kHz) a significant
difference in shielding cannot be detected for the four
complexes
(32–35).
Similarly,
the
one-bond
C(1)ꢁMn(CO)5 coupling constants lie in the narrow
range of 4692 Hz characteristic for RꢁMn(CO)5 com-
plexes [45]. The accuracy of these data is expected to be
92 Hz, and thus no significant differences are detected
for the four glycosyl complexes. The 1J(55Mn,13CO)
values are also typical for manganese carbonyls and it
is noteworthy that equatorial and axial carbonyls do
not show the characteristic difference observed earlier
for RꢁMn(CO)5 model complexes [45–47]. In this series
of manganese complexes the one-bond coupling con-
stants indicate that there is no significant difference in
In the carbonylation of glycosylmanganese pentacar-
bonyls, a single carbon–carbon bond is formed. Se-
quential insertion, on the other hand, produces at least
two new carbon–carbon bonds in the manganacycle
products and it was gratifying to determine that in most
instances the glycosyl complexes underwent sequential
insertion efficiently. Scheme 7 summarizes a representa-
Table 3
55Mn-NMR data of (glycosyl) Mn(CO)5 complexes (C6D6, 300 K) and (b-pyranyl) Mn(CO)5 (CDC13,300 K)
Complex
l(55Mn) (ppm)
Dw(1/2) (kHz)
1J(Mn,C(1)) (Hz)
1J(Mn,CO)eq
1J(Mn,CO)ax
b-Glucosyl (32)
a-Glucosyl (33)
b-Mannosyl (34)
a-Mannosyl (35)
b-Pyranyl (31)
−2059
−2053
−2056
−2064
−2077
12.0690.02
10.3690.03
13.7790.02
12.6390.03
13.2090.05
47
48
45
46
–
142
147
148
135
–
141
–
153
139
–

P. DeShong et al. / Journal of Organometallic Chemistry 593–594 (2000) 49–62
55
Similarly, sequential insertion of complex 22 with
phenyl vinyl sulfone at 5 kbar provided a 1:1 mixture of
diastereomeric manganacycles 44 (Scheme 7).
Insertion of methyl crotonate with complex 22 pro-
vided a 10:1 mixture of diastereomers 45. Since the
insertion of an alkene is known to occur in a syn-fash-
ion, both diastereomers of manganacycles 45 should
have the anti-relationship between methyl and car-
bomethoxy substituents. They differ only in the relative
configurations relative to the anomeric center. The rela-
tive stereochemistry of the major diastereomer has not
been determined. We propose that the excellent
diastereoselectivity observed in insertion of crotonates
is the result of the proximity of the stereogenic center to
the anomeric center. In the transition state for migra-
tory insertion, the stereogenic center at the anomeric
carbon is close enough to the new stereogenic center to
have an influence on the stereochemical course of the
process. With acrylate esters, the new stereogenic center
is too far from the existing anomeric center to be
influenced. The excellent diastereoselectivity observed
with crotonates suggests it may be possible to induce
remote stereogenic centers in other sequential insertion
processes.
Scheme 5.
The sulfone adducts were not fully characterized due
to their propensity to undergo elimination of phenyl-
sufinic acid. However, the products of the elimination
were stable and their characterization will be discussed
below. [36]
Phenyl acetylene underwent regioselective insertion
with complex 22 at atmospheric pressure to afford
unsaturated manganacycle 46. This result was
analogous to the situation in simple alkylmanganese
complexes where alkynes are more reactive toward
sequential insertion and do not require high pressures
to obtain good yields of manganacycles (Scheme 1)
[22,25].
tive array of examples with b-glucopyranosyl complex
22. As indicated, glucosylmanganese complex 22 under-
goes sequential insertion with electron-deficient alkenes
and terminal alkynes in analogy with the simple alkyl-
manganese complexes. Sequential insertion of methyl
acrylate with 22 at 5 kba [51] yielded a 1:1 mixture of
diastereomeric complexes 43. We had hoped that the
stereogenic center at the anomeric center would induce
high diastereoselectivity in the sequential insertion pro-
cess, but this was not observed with acrylate esters.
As anticipated, demetalation of manganacycle 43
could be accomplished photochemically in the presence
of oxygen and water to produce enone 47 [29]. Alterna-
tively, if the demetalation was performed in the absence
of oxygen, then ketone 48 was the sole product of
demetalation (Scheme 8). A discussion of the mecha-
nism of this demetalation reaction has been published
previously [25,52].
Treatment of ketone 48 with hydrazine (or its deriva-
tives) gave dihydro-pyridazine 49 in good yield. Oxida-
tion to pyridazine 50 has proven to be problematic in
this instance. Enone 47, on the other hand, reacts with
hydrazine to afford dihydropyrazole 51 as a 1:1 mixture
of diastereomers (Scheme 9) [36].
Manganacycle 44, the product of insertion of phenyl
vinyl sulfone with b-complex 22 (Scheme 10), was un-
stable and could not be fully characterized (vide supra).
Photolysis of the crude manganacycle according to
standard protocols provides keto-sulfone 52. Sulfone 52
Scheme 6.

56
P. DeShong et al. / Journal of Organometallic Chemistry 593–594 (2000) 49–62
Scheme 7.
is prone to loss of phenylsulfinic acid to give enone 53
[36].
6. Experimental
When manganacycle 44 is allowed to remain in ether
solution in the dark at atmospheric pressure, a single
diastereomer of butenolide 55 (configuration unknown)
is produced in excellent yield [36]. Presumably, the
butenolide results from formation of manganacycle 54
by loss of phenyl sulfinic acid, protonation of 54,
migratory insertion of an additional molecule of CO
producing ketene 57, enolization, and ring formation.
We have previously demonstrated that this mechanism
is operative in reactions of acetylene derivatives [24].
6.1. General
1
The H-NMR spectra were measured at 200, 400 and
600 MHz, the 13C spectra at 50.0, 100.6 and 150.9 MHz
on a Bruker AF-200, AM-400 and AMX-600 spectrom-
eters, respectively. 2D-COSY, TOCSY and NOESY
experiments were performed using standard Bruker
software. All chemical shifts are given relative to inter-
nal tetramethylsilane. 55Mn-NMR spectra were
recorded at 99.2 and 148.8 MHz on the same instru-
ments and chemical shifts are referred to aqueous
KMnO4 as an external standard and 55Mn, 13C cou-
pling constants were obtained by quantitative lineshape
analysis of the 13C resonances as described earlier [45–
47]. Chemical shifts are reported in parts per million (l)
and coupling constants (J values) are given in Hertz
(Hz). Infrared absorbances are reported in reciprocal
centimeters (cm−1).
5. Conclusion
In this manuscript, the focus was on synthesis, char-
acterization, and transformations of glycosylmanganese
pentacarbonyl complexes. Highly stereoselective synthe-
sis of pyranosyl and furanosyl complexes was accom-
plished by condensations of glycosyl bromides and
chlorides. The conformations of the anomeric glucosyl
and mannosyl complexes were derived from detailed
analysis of their 1D and 2D proton and 13C-NMR
spectra including NOE data. The complexes are further
characterized by 55Mn-NMR chemical shifts and 55Mn,
13C one-bond coupling constants. The glycosyl com-
plexes undergo a variety of migratory insertion pro-
cesses resulting in formation of novel C-glycosyl
derivatives.
Tetrahydrofuran (THF) and diethyl ether (Et2O)
were distilled from sodium/benzophenone ketyl. Ace-
tonitrile (MeCN), benzene and methylene chloride
(CH2Cl2) were distilled from calcium hydride.
Methanol (MeOH) and ethanol (EtOH) were dried and
stored over molecular sieves. Glassware used in the
reactions was dried overnight in an oven at 120°C. All
reactions were performed under an atmosphere of ar-
gon unless noted otherwise. Dimanganese decacarbonyl
(Mn2(CO)10) was obtained from Strem Chemical (Cata-

P. DeShong et al. / Journal of Organometallic Chemistry 593–594 (2000) 49–62
57
Scheme 8.
log no. 25-13330) and was sublimed (70°C/0.1 mmHg)
prior to use.
Preparation of compounds 24 [21], 26 [20], 27 [20], 28
[20], 29 [20], 30 [20], 32 [20], 41 [20], 43 [23] and 48 [23]
were reported by the DeShong group.
J=9.8, 4.1, 2.0, 1H). 13C-NMR (100 MHz, C6D6) l
211.5, 209.6, 139.2, 139.0, 138.7, 128.5–127.5, 90.1,
86.4, 79.6, 78.4, 77.8, 75.5, 74.8, 73.6, 69.8. MS: m/z
Calc. for C34H36O5 [(M++H)−Mn(CO)5] 524.2547.
Found 524.2563.
6.2. 2,3,4,6-Tetra-O-benzyl-i-
D
-glucopyranosylman-
6.3. 2-Manganese pentacarbonyl tetrahydropyran (31)
ganese pentacarbonyl (22)
A solution of tetrahydropyranyl chloride (2.0 ml, 17
mmol) in 15 ml of diethyl ether was added via syringe
to a freshly prepared solution of KMn(CO)5 (ca. 20
mmol) in 15 ml of diethyl ether at −78°C under an
atmosphere of argon. The solution was stirred at −
78°C for 0.5 h in the absence of light, then warmed to
23°C for 1 h. The reaction was diluted with ethyl ether
and quenched with 0.1 ml of water. The mixture was
filtered through Celite and then concentrated in vacuo.
The residue was purified by flash silica chromatography
using a elution gradient from hexanes to 7% ethyl
acetate/hexanes to give 4.6 g (97%) of 2-manganese
pentacarbonyl tetrahydropyran (31) as a clear oil. A
sample of 31 was crystallized from cold hexanes,
filtered at −78°C to give a white solid, then recrystal-
lized from pentanes at −20°C to give white crystals.
M.p. 34–35°C; Rf=0.30 (5% ethyl acetate/hexanes). IR
(CCl4): 2932, 2111, 2056, 2012, 1987. 1H-NMR: (see
Table 1). 13C-NMR (50 MHz, C6D6): l 211.97, 96.3,
85.5, 43.3, 21.9, 20.0. MS m/z (HR): Calc. for
C10H10MnO6 (M++H) 280.9857. Found 280.9858).
Glucopyranosylmanganese complex 22 was prepared
from the corresponding a-bromide 20 [21]. Glucopyra-
nosylmanganese complex 22 may also be prepared from
the chloro-derivative of 20. A solution of 3.24 g (5.8
mmol) of a-chloride [53,54], in 5 ml of anhydrous Et2O
was added via syringe to a freshly prepared solution of
KMn(CO)5 [54] in 10 ml of Et2O at 0°C. The solution
was stirred in the dark at 42°C for 12 h. The reaction
was diluted with 10 ml of Et2O and quenched with 0.1
ml of water until no hydrogen evolved. The mixture
was dried over Na2SO4, filtered through Celite, and
concentrated in vacuo. The red residue was purified by
flash chromatography eluting with hexanes then 5%
EtOAc/hexanes to give 3.9 g (93%) of b-anomer 22 as a
yellow oil. The oil was crystallized from absolute
methanol (avoiding excess heating and exposure to
light) to give white needles. M.p. 69–70°C; Rf=0.66
(33% EtOAc/hexanes). IR (CCl4) 2013, 2050, 2013,
1
1988. H-NMR (400 MHz, C6D6): l 7.09–7.48 (m, 20
H) 5.28 (A of AB q, J=11.9, 1H), 4.73 (B of AB q,
J=11.9, 1H), 5.00 (A of AB q, J=11.1, 1H), 4.75 (B
of AB q, J=11.1, 1H), 4.80 (A of AB q, J=11.1, 1H),
4.68 (B of AB q, J=11.1, 1H), 4.64 (A of AB q,
J=12.3, 1H), 4.55 (B of AB q, J=12.3, 1H), 4.06 (d,
J=10.1, 1H), 3.75 (dd, J=9.8, 9.0, 1H), 3.70 (dd,
J=11.0, 4.1, 1H), 3.65 (dd, J=11.0, 2.0, 1H), 3.69 (dd,
J=10.1, 7.9, 1H), 3.56 (dd, J=9.0, 7.9, 1H), 3.19 (ddd,
Scheme 9.

58
P. DeShong et al. / Journal of Organometallic Chemistry 593–594 (2000) 49–62
Scheme 10.
6.4. 2,3,4,6-Tetra-O-methyl- i-
ganese pentacarbonyl (34) and 2,3,4,6-tetra-O-methyl-h-
-mannopyranosylmanganese pentacarbonyl (35)
D
-mannopyranosylman-
J=7.06, 1H), 3.76 (m, 2H), 3.50 (m, 2H), 3.48 (m, 1H),
3.19 (s, 3H), 3.14 (s, 3H), 3.10 (s, 3H), 3.08 (s, 3H).
13C-NMR (100 MHz, C6D6): l 212.0, 83.2, 76.7, 75.3,
75.1, 72.9, 70.6, 58.6, 58.2, 56.8, 54.4.
D
A solution of 2,3,4,6-tetra-O-methyl-a-
D
-mannopyra-
2,3,4,6-Tetra-O-methyl-b-mannopyranosylmanganese
pentacarbonyl (34) was isolated as a yellow oil. Rf=
0.30 (25% EtOAc/hexanes). IR (CCl4): 2160, 2056, 2012,
nosyl bromide (1.18 g, 1.95 mmol) in 15 ml of anhy-
drous Et2O was added via syringe to a freshly prepared
solution of KMn(CO)5 (1.9 mmol) in 15 ml of anhy-
drous Et2O at −78°C under argon. The solution was
stirred in the dark at −78°C for 0.5 h, then warmed to
23°C for an additional 3 h. The reaction mixture was
diluted with Et2O and quenched with 0.1 ml of water.
The mixture was dried over Na2SO4, filtered through a
pad of Celite, and concentrated in vacuo. The residue
was dissolved in 15 ml of anhydrous CH2Cl2 and
transferred to Fisher–Porter apparatus. The system was
evacuated (18 mmHg) and backfilled five times with
carbon monoxide to 50 psi. The mixture was stirred in
the dark for 4 days. The carbon monoxide was vented,
and the solvent was evaporated in vacuo to give a
yellow oil. The crude product was purified by flash
chromatography eluting with a 5–25% gradient of
EtOAc/hexanes to give 224 mg (28%) of 2,3,4,6-tetra-O-
1
1987. H-NMR (200 MHz, C6D6) l 4.18 (d, J=1.0,
1H), 3.64 (s, 3H), 3.58–3.62 (m, 3H), 3.48 (s, 3H), 3.27
(s, 1H), 3.18 (s, 3H), 3.15–3.17 (m, 3H). 13C-NMR (50
MHz, C6D6) l 211.9, 90.3, 85.0, 84.7, 81.7, 77.1, 72.6,
60.5, 60.5, 60.0, 58.0. MS (CI, m/z): (relative intensity)
415 (M++1, 1), 414 (M+, 2), 359 ((M++1)−2 CO,
12), 343 (2), 327 (6), 313 (4), 274 (6), 219 (10), 187 (15),
157 (71), 143 (10, 125 (12), 101 (100).
2,3,4,6-Tetra-O-methyl-a-mannopyranosyl-1-acylman-
ganese pentacarbony was recrystallized from pentane to
provide white crystals. M.p. 76–77°C; Rf=0.14 (25%
EtOAc/hexanes). IR (CCl4): 2119, 2050, 2031, 2021,
1
1638. H-NMR (400 MHz, C6D6) l 4.12 (d, J=3.6,
1H), 4.88 (t, J=3.4, 1H), 3.67–3.77 (m, 2H), 3.49–3.53
(m, 2H), 3.34 (s, 3H), 3.27 (s, 3H), 3.19 (s, 3H), 3.17 (s,
3H), 3.1 (d, J=5.3, 1H). 13C-NMR (100 MHz, C6D6) l
262.2, 209.4, 92.2, 81.6, 77.1, 77.0, 75.0, 72.4, 59.4, 59.0,
58.5, 57.6.
methyl-b-mannopyranosylmanganese
pentacarbonyl
(34) and 150 mg (17%) of 2,3,4,6-tetra-O-methyl-a-
mannopyranosyl-1-acyl-manganese pentacarbonyl.
Decarbonylation of 2,3,4,6-tetra-O-methyl-a-man-
nopyranosyl-1-acylmanganese pentacarbonyl by heating
to 62°C in benzene for 19 h gave 125 mg (89%) of
2,3,4,6-tetra-O-methyl-a-mannopyranosyl-manganese
pentacarbonyl (35) as an oil. Rf=0.27 (25% EtOAc/
6.5. 2,3,4,6-Tetra-O-benzyl-i-D-glucopyranosyl-1-acyl-
manganese pentacarbonyl (36)
A solution of glucopyranosylmanganese pentacar-
bonyl 22 (0.200 g, 0.278 mmol) in 15 ml of methylene
chloride was sealed in a Fischer–Porter bottle with a gas
inlet and pressure regulator. The solution in the bottle
1
hexanes). IR (CCl4): 2112, 2048, 2014, 1984. H-NMR
(400 MHz, C6D6): l 5.04 (d, J=10.4, 1H), 4.16 (t,

P. DeShong et al. / Journal of Organometallic Chemistry 593–594 (2000) 49–62
59
6.7. 2,6-Anhydro-3,4,5,7-tetrakis-O-(phenyl-
methyl)- -glycero-gulo-heptonic acid amide (38)
was degassed three times via aspiration, backfilling with
carbon monoxide. With an internal carbon monoxide
pressure of 45 psi, the mixture was vigorously stirred at
20°C for 8 h shielded from light. The reaction mixture
was opened to the atmosphere, concentrated under
reduced pressure and the resulting oil purified by
column chromatography eluting 5% ethyl acetate/hex-
anes to give 165 mg (80%) of 2,3,4,6-tetra-O-benzyl-b-
D
A solution of glucopyranosylmanganese pentacar-
bonyl 22 (1.95 g, 2.71 mmol) and potassium carbonate
(1.00 g, 7.21 mmol) in 10 ml of dry methanol was
placed in a Fischer–Porter bottle. To this solution was
added 20 ml of methanol previously saturated with
anhydrous ammonia. The reaction vessel was stirred for
12 h under 40 psi of carbon monoxide in the absence of
light. The yellow solution with a white precipitate was
concentrated under reduced pressure to a paste, diluted
with ethyl acetate, filtered through a pad of Celite and
the filtrate was evaporated to a semi-solid. The crude
amide was purified by column chromatography eluting
with 33% ethyl acetate/hexanes to give a white solid.
Compound 38 was recrystallized from hexanes/ethyl
acetate to give 1.48 g (96%) as a white solid. M.p.
124–126°C; Rf=0.15 (50% hexanes/ethyl acetate).
D
-glucopyranosyl-1-acylmanganese pentacarbonyl (36)
as a clear oil. In addition, 30 mg (15%) of starting
material 22 was recovered as a clear oil. Attempts to
crystallize compound 36 were unsuccessful. Rf=0.27
(10% ethyl acetate/hexanes). IR (CCl4) 2118, 2053,
1
2024, 2000, 1650. H-NMR (200 MHz, C6D6) l 7.48–
7.09 (m, 20H, Ar), 4.90 (AB q, JAB= 10.5 Hz, DwAB
28 Hz, 2H), 4.86 (s, 2H), 4.66 (AB q, JAB=11.4 Hz,
DwAB=61 Hz, 2H), 4.37 (AB q, JAB=11.8 Hz, DwAB
=
=
16 Hz, 2H), 3.80–3.65 (m, 5H), 3.52 (d, JH1=8.6 Hz,
1H), 3.50–3.44 (m, 1H). 13C-NMR (50 MHz, CDCl3) l
256.5, 209.6, 139.3, 139.1, 138.7, 128.5–127.5, 92.2,
87.0, 78.9, 78.4, 77.8, 75.4, 74.8, 73.6, 69.5. MS m/z
(HR): Calc. for C34H36O5 [(M++H)−Mn(CO)5]
524.2547. Found 524.2563.
[h]2D3= +34.6° (c 0.55, CHCl3). IR (CCl4) 1703. H-
1
NMR (200 MHz, C6D6): l 7.47 (d, J=7.2 Hz, 2H),
7.34–7.07 (m, 18H), 5.77 (br s, 1H), 5.29 (br s, 1H),
4.92–4.50 (m, 6H), 4.38–4.20 (m, 3H), 3.83–3.53 (m,
5H), 3.47–3.26 (m, 1H). 13C-NMR (50 MHz, CDCl3) l
171.8, 138.5, 138.2, 128.3–127.2, 85.3, 80.1, 78.3, 78.0,
75.0, 74.5, 73.5, 69.6. MS m/z (HR): Calc. for
C35H38NO7 (M++H) 568.2700. Found 568.2699.
6.6. Methyl 2,6-anhydro-4,5,6,8-tetrakis-O-(phenyl-
methyl)- -glycero-gulo-heptonate (37)
D
A suspension of glucopyranosylmanganese pentacar-
bonyl 22 (0.305 g, 0.507 mmol) and potassium carbon-
ate (0.300 g, 2.17 mmol) in 10 ml of methyl alcohol was
sealed in a Fischer–Porter bottle containing a gas inlet
and pressure regulator. The reaction mixture in the
bottle was degassed three times via aspiration, backfi-
lling with carbon monoxide. With an internal carbon
monoxide pressure to 45 psi, the mixture was stirred at
23°C for 20 h shielded from light. The clear solution,
containing a white precipitate, was concentrated in
vacuo and the resulting oil was diluted with ethyl
acetate. This suspension was filtered through a pad of
Celite, concentrated to a clear oil. The crude ester was
purified by flash column chromatography eluting with
10% ethyl acetate/hexanes to give 270 mg (91%) of 37
as a white solid. Ester 37 was recrystallized from hex-
anes to give white needles. M.p. 71–72°C; Rf=0.30
(25% ethyl acetate/hexanes). [h]2D3= +12.0° (c 0.12,
6.8. N-(phenylmethyl)-2,6-anhydro-3,4,5,7-tetrakis-O-
(phenylmethyl)- -glycero-gulo-heptonic acid amide (39)
D
A solution of glucopyranosylmanganese pentacar-
bonyl 22 (0.460 g, 0.640 mmol), benzyl amine (1.00 ml,
9.15 mmol) and potassium carbonate (1.00 g, 7.10
mmol) in 20 ml of dry methanol was placed in a
Fischer–Porter bottle. The reaction vessel was stirred
for 12 h under 45 psi of carbon monoxide in the
absence of light. A yellow solution with a white precip-
itate was concentrated to a paste, diluted with ethyl
acetate and filtered through a pad of Celite. The filtrate
was washed with 2 N HCl and brine then dried over
sodium sulfate. The organic layer was filtered and
concentrated in vacuo to give a clear oil. The crude
amide was purified by column chromatography eluting
with 25% ethyl acetate/hexanes to give 1.48 g (96%) of
amide 39 as a white solid. Amide 39 was recrystallized
from hexanes/ethyl acetate to give white crystals. M.p.
165–166°C; Rf=0.15 (33% ethyl acetate/hexanes). IR
(CCl4) 1692: 1H-NMR (200 MHz, C6D6) l 7.50 (d,
J=16.6 Hz, 2H), 7.40 (d, J=6.6 Hz, 2 H), 7.20–7.08
(m, 21H), 6.68 (t, J=5.8 Hz, 1H), 4.91 (AB q, J=11.3
Hz, DwAB=27 Hz, 2H), 4.80 (AB q, J=10.8 Hz,
DwAB=33 Hz, 2H), 4.68 (AB q, J=11.2 Hz, DwAB=40
Hz, 2H), 4.49–4.30 (m, 4H), 4.05–3.95 (m, 2H), 3.82–
3.77 (m, 2H), 3.60 (br s, 2H), 3.55–3.45 (m, 1H).
13C-NMR (50 MHz, CDCl3): l 169.0, 138.3, 138.1,
1
CHCl3). IR (CCl4) 1756. H-NMR (200 MHz, C6D6): l
7.34–7.10 (m, 20H), 4.83 (s, 2H), 4.73 (AB q, JAB
=
11.3 Hz, DwAB=35 Hz, 2H), 4.69 (AB q, JAB= 11.3
Hz, DwAB=46 Hz, 2H), 4.38 (AB q, JAB= 12.1 Hz,
DwAB=21 Hz, 2H), 4.05–3.95 (m, 2H), 3.85–3.60 (m,
4H), 3.40–3.25 (m, 1H), 3.27 (s, 3H). 13C-NMR (50
MHz, C6D6) l 169.4, 139.4, 139.2, 139.0, 128.5–127.5,
86.8, 80.6, 80.4, 79.1, 78.4, 75.4, 75.0, 73.8, 69.4, 51.6.
MS m/z (HR): Calc. for C36H39O7 (M++H) 583.2697.
Found 583.2696.

60
P. DeShong et al. / Journal of Organometallic Chemistry 593–594 (2000) 49–62
138.0, 137.9, 128.6–127.4, 85.1, 80.0, 78.4, 77.6, 77.4,
74.9, 74.5, 74.4, 73.4, 68.9, 43.1. MS m/z (H/R): Calc.
for C42 H43 NO6 657.3092. Found 657.2965.
dazine 49 as a white solid. Attempts to recrystallize
compound 49 were unsuccessful. Rf=0.15 (33% ethyl
acetate/hexanes). IR (CCl4) 3431, 1700, 1650, 1495.
1H-NMR (200 MHz, CDCl3): l 8.62 (br s, 1H), 7.37–
7.14 (m, 20H), 4.93 (s, 2H), 4.87–4.78 (m, 2H), 4.62–
4.54 (m, 4H), 3.92 (d, J=9.7 Hz, 1H), 3.78–3.50 (m,
6H), 2.62–2.45 (m, 1H), 2.40–2.25 (m, 2H), 2.05–1.85
(m, 1H). 13C-NMR (50 MHz, C6D6) l 167.0, 155.8,
139.4, 139.1, 138.8, 138.8, 128.5–127.3, 87.4, 81.2, 79.3,
78.9, 78.3, 75.6, 75.0, 74.5, 73.5, 69.2, 26.1, 21.0. MS
m/z (relative intensity): 621 [(M++1) 18], 529 (40), 515
(46), 424 (71), 315 (14), 253 (28), 181 (100), 149 (42).
6.9. Methyl 5,9-anhydro-2,3-dideoxy-6,7,8,10-tetrakis-
O-(phenylmethyl)-D-glycero-D-gulo-dec-2-en-4-
ulosonate (47)
A solution of glucopyranosylmanganese pentacar-
bonyl 22 (0.275, 0.383 mmol) and freshly distilled
methyl acrylate (0.20 ml, 2.2 mmol) in 3 ml THF was
placed in a plastic syringe and sealed with a luer lock
cap. The syringe was placed in a high pressure appara-
tus and pressurized to 4500 bar. After 40 h, the pressure
was released and the solution was concentrated in
vacuo to give the crude manganacycle 43 as a thick red
oil. The unstable manganacycle was used in the next
step without further purification. The manganacycle 43
was diluted with 20 ml acetonitrile and 0.5 ml of water.
This solution was stirred open to the atmosphere while
subjected to photo irradiation (320 nm) for 4 h. Inter-
nal temperature of the reaction mixture reached 60–
65°C due to the light source. The solution became dark
with a brown precipitate which was filtered with Celite
from the reaction mixture. The filtrate was concen-
trated in vacuo and the resulting residue was purified
by column chromatography eluting with 5% ethyl ac-
etate/hexanes to give 163 mg (67%) of methyl ester 47
as a white solid. Attempts to recrystallize compound 47
were unsuccessful. Rf=0.38 (25% ethyl acetate/hex-
6.11. Dihydropyrazole (51)
Sugar ester 47 (71.0 mg, 0.11 mmol) was dissolved in
4 ml of absolute ethanol followed by hydrazine mono-
hydrate (20 ml, 0.41 mmol) and 2 drops of glacial acetic
acid. The reaction was stirred at room temperature
(23°C) for 25 h. The reaction mixture was concentrated
in vacuo and dissolved in 5 ml EtOAc then washed with
2 N HCl followed by brine. The organic layer was
concentrated in vacuo and chromatographed with 25%
EtOAc/hexanes to give 59 mg (81%) of dihydropyrazole
51 as a white solid in a 2:1 diastereomeric mixture.
Attempts to recrystallize compound 51 were unsuccess-
ful. Rf=0.10 (33% EtOAc/hexanes). IR (CCl4): 3350,
1
1743. H-NMR (200 MHz, C6D6): l 7.41–6.92 (m, 20
H), 5.10–4.78 (m, 4 H), 4.71–4.59 (m, 2H), 4.48–4.23
(m, 2 H), 3.85–3.47 (m, 8 H), 3.38–3.17 (m, 4 H), 3.09
(s, 1H), 3.01 (s, 3 H). 13C-NMR (50 MHz, C6D6) l
139.5, 139.2, 139.0, 128.5, 128.0, 127.5, 87.3, 87.1, 86.2,
80.2, 79.6, 79.4, 78.3, 78.1, 77.5, 75.5, 75.1, 74.9, 74.8,
73.9, 73.6, 70.2, 60.3, 51.8. MS m/z (H/R): Calc. for
C39H42N2O7 663.3072. Found 663.2945.
1
anes). IR (CCl4): 1733. H-NMR (200 MHz, C6D6): l
7.52 (d, J=15.9 Hz, 1H), 7.38–7.06 (m, 20H), 6.92 (d,
J=15.9 Hz, 1H), 4.87 (s, 2H), 4.73 (AB q, JAB=8.9
Hz, DwAB=16 Hz, 2H), 4.65 (AB q, JAB=11.1 Hz,
DwAB=16 Hz, 2H), 4.42 (AB q, JAB=12.2 Hz, DwAB
=
19 Hz, 2H), 3.85 (d, J=9.2 Hz, 1H), 3.80–3.54 (m,
5H), 3.37–3.27 (m, 1H), 3.31 (s, 3H). 13C-NMR (50
MHz, C6D6) l 194.2, 165.5, 139.2, 139.0, 138.8, 138.3,
136.49, 131.7, 128.5–127.5, 86.7, 82.4, 82.4, 79.7, 78.9,
77.9, 75.4, 75.0, 74.8, 73.5, 68.9, 51.6.
6.12. Phenylsulfone (52) and furanone (55)
A solution of glucopyranosylmanganese pentacar-
bonyl 22 (0.460 g, 0.640 mmol) and phenyl vinyl sul-
fone (0.20 g, 1.2 mmol) in 3 ml THF was placed in a
plastic syringe and sealed with a luer lock cap. The
syringe was placed in a high pressure apparatus and
pressurized to 4500 bar. After 40 h, the pressure was
released and the solution was concentrated to give the
crude manganacycle 44 as a thick red oil. The unstable
manganacycle was used in the next step without further
purification. A solution of crude manganacycle 44 (0.50
g, 0.56 mmol) in 15.0 ml of acetonitrile and 0.15 ml
water was degassed by a series of freeze/vacuum/thaw
cycles. The solution was stirred under partial vacuum
while being subjected to photo irradiation (320 nm) for
12 h. The internal temperature of the reaction mixture
reached 60–65°C due to the light source. As the clear
yellow solution was opened to the air, the reaction
mixture became dark and eventually formed a red–
6.10. Methyl 5,9-anhydro-2,3-dideoxy-6,7,8,10-
tetrakis-O-(phenylmethyl)-D-glycero-D-gulo-deculo-
sonate pyrimidone (49)
A solution of ketone 48 (55 mg, 86 mmol) in 4 ml of
100% ethyl alcohol and 0.1 ml of glacial acetic acid was
treated with hydrazine (50 ml, 1.0 mmol) under an
atmosphere of nitrogen. The solution was stirred and
heated at reflux for 1 h, then cooled to 23°C for 1 h.
The solution was poured into 2 N HCl and extracted
thoroughly with ethyl acetate. The organic layers were
combined and dried over sodium sulfate, then concen-
trated in vacuo. The resulting residue was purified by
column chromatography eluting with 10% ethyl ac-
etate/hexanes to give 46 mg (86%) of dihydro-pyri-

P. DeShong et al. / Journal of Organometallic Chemistry 593–594 (2000) 49–62
61
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brown precipitate (an oxidized manganese by-product).
After 1 h the suspension was filtered, concentrated in
vacuo, and the resulting residue was purified by column
chromatography eluting with 5% ethyl acetate/hexanes
to give 0.262 g (65%) of butenolide 55 as a white solid
and 139 mg (35%) of keto-sulfone 52 as a white solid.
Sulfone 52 was recrystallized from hexanes to give
white crystals. Rf=0.10 (25% ethyl acetate/hexanes).
IR (CCl4): 1738, 1325, 1156. 1H-NMR (200 MHz,
CDCl3): l 7.90–7.85 (m, 2H), 7.62–7.45 (m, 3H), 7.30–
7.10 (m, 20H), 4.78 (s, 2H), 4.75–4.50 (m, 6H), 4.33–
4.15 (m, 7H), 3.30–3.12 (m, 2H), 3.10–2.95 (m, 2H).
13C-NMR (50 MHz, CDCl3): l 200.3, 139.3–139.3,
133.6, 129.3, 128.4–127.7, 86.2, 82.6, 79.3, 78.7, 78.0,
75.3, 74.8, 74.5, 73.7, 69.4, 50.4, 32.6. MS m/z (HR):
Calc. for C43H44O8S 720.2757. Found 720.2948.
Furanone 55 was recrystallized from hexanes to give
white crystals. Rf=0.15 (25% ethyl acetate/hexanes).
1
IR (CCl4): 1766, 1495. H-NMR (200 MHz, CDCl3): l
7.27–7.10 (m, 20H), 6.77 (dd, J=1.4, 5.7 Hz, 1H), 5.92
(dd J=1.4, 5.8 Hz, 1H), 5.11 (d, J=1.4 Hz, 1H),
4.95–4.72 (m, 6H), 4.53 (dd, J=4.2, 10.2 Hz, 2H), 4.43
(s, 2H), 3.70–3.52 (m, 4H), 3.41–3.30 (m, 1H). 13C-
NMR (50 MHz, C6D6): l 171.8, 151.3, 139.2, 139.2,
138.4, 128.4–127.6, 122.2, 87.5, 82.2, 79.8, 78.8, 78.3,
77.8, 75.4, 74.9, 74.2, 73.7, 69.1. MS m/z (HR): Calc.
for C38H37O7 605.2540. Found 605.2414. Calc. for
C31H31O7 (M–Bn) 515.2070. Found 515.2011.
[24] P. DeShong, D.R. Sidler, J. Org. Chem. 53 (1988) 4892–4894.
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Rheingold, J. Am. Chem. Soc. 110 (1988) 2575–2585.
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Philipsborn, J. Org. Chem. 54 (1989) 5432–5437.
[27] P. DeShong, G.A. Slough, D.R. Sidler, P.J. Rybczynski, W. von
Philipsborn, R.W. Kunz, B.E. Bursten, T.W. Clayton Jr.,
Organometallics 8 (1989) 1381–1388.
Acknowledgements
P.D. thanks the National Institutes of Health for
generous financial support of this project. We also
acknowledge financial support from Tektronix, and
Lederle Laboratories. W.v.P. thanks the Swiss National
Science Foundation and the Dr Helmut Legerlotz
Stiftung for generous funding and Dr V. Torochesh-
nikov for preliminary experiments and valuable advice.
[28] P. DeShong, P.J. Rybczynski, J. Org. Chem. 56 (1991) 3207–
3210.
[29] L.J. Smith, P. DeShong, unpublished results.
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