Synthesis of ABO histo-blood group type v and VI antigens

Article abstract of DOI:10.1071/CH09058

The ABO histo-blood group antigens have long been of interest to chemists, biochemists, and evolutionary biologists. However, to date, a complete synthesis of all ABO histo-blood group antigens has not been conducted, despite the potential for such a pane

Full text of DOI:10.1071/CH09058

RESEARCH FRONT
Full Paper
CSIRO PUBLISHING
Aust. J. Chem. 2009, 62, 558–574
www.publish.csiro.au/journals/ajc
Synthesis of ABO Histo-Blood GroupTypeV andVI Antigens∗
Peter J. MeloncelliA and Todd L. LowaryA,B
ADepartment of Chemistry and Alberta Ingenuity Centre for Carbohydrate Science, Gunning-Lemieux
Chemistry Centre, University of Alberta, Edmonton, AB T6G 2G2, Canada.
BCorresponding author. Email: tlowary@ualberta.ca
The ABO histo-blood group antigens have long been of interest to chemists, biochemists, and evolutionary biologists.
However, to date, a complete synthesis of allABO histo-blood group antigens has not been conducted, despite the potential
for such a panel to provide a more detailed understanding of the biological roles of these glycan motifs. Here we report the
chemical synthesis of the A, B, and H type V and VI antigens in multi-milligramme quantities as part of an overall goal
to prepare all 18 A, B, and H antigens. The A and B type V and VI antigens were prepared with a 7-octen-1-yl linker, to
enable future conjugation to a protein or solid support. The H type V and VI antigens were prepared as the octyl glycoside,
to facilitate detailed enzyme kinetics studies.
Manuscript received: 28 January 2009.
Final version: 11 March 2009.
Introduction
do influence biochemical function. For example, Palcic and
coworkers showed that this minor structural variation can have
a significant effect on the kinetics of GTA and GTB.[13] In that
study, the kinetics of GTA and GTB were measured for both the
H type I and type II antigens and it was shown for both enzymes
that the rate of transfer was significantly higher for the H type I
antigen.[13] Another study, by Oriol and coworkers, explored the
cross reactivity of Anti-Lea and Anti-Leb antibodies with sev-
eral Lewis and histo-blood group antigens, showing a significant
variation in binding between subtypes.[14]
To date, numerous synthetic investigations have been under-
taken towards the synthesis of the histo-blood group antigens.
Most of these studies have focussed on the preparation of the di-
saccharide H antigens and trisaccharide A and B antigens.[15–17]
When the trisaccharide H antigen and tetrasaccharide A and
B antigens have been synthesized, the more prevalent type I
and type II structures have been the target of most synthetic
efforts.[18–22] In other investigations, the B type III and type
IV tetrasaccharide determinants were prepared by Bovin and
coworkers via a [3 + 1] block chemical synthesis,[23] while an
earlier synthesis by the same group reported the synthesis of the
A, B, and H type III determinants.[24] In addition, the synthe-
ses of both H type V and type VI antigens have been previously
reported by several groups[25–27] and the enzymatic synthesis
of the A type V and type VI structures was reported by Thiem
and coworkers.[27] In the present paper, we report the chemical
synthesis of the A, B, and H type V and type VI antigens (4–9,
Fig. 2), as part of a larger program to complete the synthesis of all
18 histo-blood group antigens in quantities suitable for detailed
biochemical studies (∼100 mg). Access to such quantities of
this material would enable, for example, the direct comparison
of GTA and GTB kinetics for the H antigens and antibody affin-
ity studies to be conducted on the A, B, and H determinants as a
function of type I–VI subtype.
Despite the discovery of the ABO histo-blood group system
by Landsteiner over 100 years ago,[1] questions still remain
unanswered. This includes the prevalence, distribution, and anti-
body affinity of the ABO subtypes, as well as the kinetics of the
enzymes responsible for their synthesis.[2] The structures of the
carbohydratesresponsiblefortheABOhisto-bloodgroupsystem
were elucidated by Morgan and Watkins in 1957.[3] Their work
demonstrated that the H antigen is a disaccharide consisting of
l-fucose and d-galactose (1, Fig. 1), whereas A and B antigens
(2 and 3) are trisaccharides containing this disaccharide linked
to an additional N-acetyl galactosamine or galactose residue,
respectively. All individuals, with the exception of those of the
Bombay phenotype, are capable of producing the core H antigen
structure;[4,5] people with the O blood type are only able to pro-
duce the H antigen. Individuals who are blood group A possess
the glycosyltransferase GTA, which attaches an N-acetyl galac-
tosamine residue to the 3-OH group of the galactose moiety of
the H antigen. Alternatively, blood group B individuals possess
a different glycosyltransferase, GTB, which attaches galactose
to this same hydroxyl group.[4,6,7] It was not until the 1990s
that the genetic basis for the ABO blood group antigens was
determined.[8–10] A direct comparison of the genes responsible
for coding GTA and GTB showed a 99% sequence homology,
differing by only seven base pairs, with three of those resulting
in silent mutations. Thus, the proteins differ only by four amino
acids.[2]
The ABO histo-blood group system can be further subtyped
according to the carbohydrate residue present at the reduc-
ing end, into what is now referred to as type I through to
type VI (Table 1).[4,11,12] To date, limited studies have been
done to determine the biological importance of these struc-
tural subtypes. However, those studies that have been carried
out suggest, not surprisingly, that these structural differences
∗Dedicated to Professor Robert V. Stick on the occasion of his retirement.
© CSIRO 2009
10.1071/CH09058
0004-9425/09/060558

RESEARCH FRONT
ABO Histo-Blood Group Type V and VI Antigens
559
HO
HO
HO
OH
OH
HO
OH
O
HO
OH
O
HO
O
O
OH
O
HO
O
OR
HO
HO
AcHN
O
OR
O
OR
O
O
O
OH
O
O
OH
OH
OH
HO
OH
OH
HO
HO
H antigen
A antigen
B antigen
1
2
3
Fig. 1. Carbohydrate structures for A, B, and H antigens. R = glycoprotein or glycolipid.
Table 1. Carbohydrate moieties responsible for the six subtypes of
human blood, where R are the ABO blood group antigens[4]
to give, in 72% yield, the diol 13. With the diol in hand, it was
necessary to differentiate the two secondary hydroxyl groups.
Introduction of the benzyl group on the C-2 hydroxyl group
was achieved by first selectively protecting the C-3 hydroxyl
group as a p-methoxybenzyl ether. This approach was inspired
by similar work reported by Nakashima and coworkers, the only
difference being the presence of an n-pentenyl glycoside instead
of the n-octenyl glycoside in 13.[30] This transformation was
achieved by the preparation of a stannylene acetal by heating
13 with di-n-butyltin oxide at reflux in toluene, followed by
reaction with p-methoxybenzyl chloride, which led to the for-
mation of a mixture of 14 and 15 in a 1:2 ratio in a combined
yield of 95%. Fortunately, conversion of the undesired isomer 14
into 13 was possible by treatment with 2,3-dichloro-5,6-dicyano-
1,4-benzoquinone (DDQ), analogously to the conversion of 16
into 18 (see below). Confirmation of the regioselectivity of the
reaction was achieved by acetylation of 15 and observation of
the downfield shift of the resonance from H2 from a multiplet
between 3.91 and 4.06 ppm to a doublet of doublets at 5.34 ppm.
With the correct regiochemistry confirmed, benzylation of 15
(benzyl bromide, sodium hydride) afforded 16 in 89% yield.
Removal of the p-methoxybenzyl ether to give 18 was achieved
in good yield (95%) using DDQ in a mixture of dichloromethane
and water.
Selection of the appropriate donor for the introduction of
the galactose core was key to the efficient synthesis of the
target. Treatment of the previously prepared acceptor 18 with
trichloroacetimidate donor 19[31] and the appropriate promoter
(BF3·OEt2) afforded the disaccharide 20 with complete stereo-
selectivity (Scheme 2). Deacetylation to afford 21 was necessary
to facilitate separation from the trichloroacetimidate by-product,
the glycosyl N-trichloroacetamide. Selective protection of the
3ꢀ position of 21 was achieved using trimethylacetyl chloride
in pyridine, similarly to previous work reported by Zhang and
coworkers.[32] This strategy, although counter-intuitive at first,
effectively circumvents the difficulties that could be observed
by complex protecting group manipulations at a later stage in
the synthesis. Introduction of the α-l-fucopyranosyl linkage
was achieved using β-l-fucopyranosyl trichloroacetimidate 23,
which has been successfully used by Schmidt and coworkers
to prepare several α-l-fucopyranosides in a stereoselective
manner.[33] Removal of the pivaloate ester from 24 proved to
be more problematic than anticipated. Its cleavage required the
forcing conditions of refluxing lithium methoxide in methanol
Type
Carbohydrate
Type I
R-β-(1→3)-β-d-GlcpNAc
R-β-(1→4)-β-d-GlcpNAc
R-β-(1→3)-α-d-GalpNAc
R-β-(1→3)-β-d-GalpNAc
R-β-(1→3)-β-d-Galp
Type II
Type III
Type IV
Type V
Type VI
R-β-(1→4)-β-d-Glcp
Results and Discussion
To prepare 4–9, it was decided that a linear chemical synthesis
would offer the most expedited synthesis while still allow-
ing appreciable quantities to be produced. Although a block
synthesis of the tetrasaccharides, where, for example, a donor
consisting of the non-reducing-end trisaccharide was added to
a monosaccharide would be more convergent, such an approach
would not allow access to the H structures, which were also
targets. A versatile group at the reducing end was required to
ensure that the targets could be used in a wide range of studies,
and for this reason a 7-octen-1-yl linker was chosen. This group
would enable ready access to the octyl glycoside for enzyme
kinetic studies,[28] while still enabling the attachment of a linker
to enable conjugation to a protein or solid support. As part of
a larger project within our group, developing tolerogens for
ABO-incompatible transplants, we have been able to success-
fully attach the A type I antigen to stainless steel stents and
nanoparticles (M. Jeyakanthan, V. W. Wright, P. J. Meloncelli,
et al., unpubl. data). It is anticipated that the A and B type V and
VI antigens could also be attached in a similar manner.
Synthesis of Type V Antigens
Key to the synthesis of the type V antigens was the prepa-
ration of the β-d-galactopyranoside derivative 18 (Scheme 1).
The benzyl ethers and benzylidene acetal in this intermediate
were selected to enable their one-step removal at the end of the
sequence. The octenyl glycoside 11 was prepared directly from
the known trichloroacetimate 10[29] with subsequent deacety-
lation to afford the tetrol 12 in 73% yield over the two steps.
Introduction of the benzylidene acetal was achieved using ben-
zaldehyde dimethyl acetal and catalytic p-toluenesulfonic acid

RESEARCH FRONT
560
P. J. Meloncelli and T. L. Lowary
HO
HO
OH
OH
O
O
HO
O
HO
HO
O
HO
OH
OH
OH
OH
HO
HO
O
O
O
O
HO
AcHN
O
O
O
O
O
HO
O
HO
O
O
OH
OH
OH
OH
HO
HO
4
5
A type V antigen
B type V antigen
HO
HO
HO
OH
OH
OH
O
O
O
OH
O
O(CH2)7CH3
HO
HO
O
O
O(CH2)7CH3
O
O
HO
HO
HO
O
O
OH
OH
OH
OH
HO
HO
6
7
H type V antigen
H type VI antigen
HO
HO
HO
OH
OH
O
O
HO
O
HO
O
OH
O
OH
O
HO
OH
OH
AcHN
HO
O
O
O
O
HO
O
O
O
O
HO
HO
HO
O
O
OH
OH
OH
OH
HO
HO
8
9
A type VI antigen
B type VI antigen
Fig. 2. Histo-blood group antigen targets, A, B, and H type V and VI.
to provide 25 in moderate (58%) yield; however, some starting
material (24) was recovered and could be recycled.
the known trichloroacetimidate 26[34] to afford the tetrasaccha-
ride with complete stereoselectivity. Purification of the product
at this stage proved difficult owing to contamination with by-
products arising from trichloroacetimidate 26. Thus, the azide
was reduced and the product amine was acetylated, generating
the expected N-acetyl derivative 27, in 51% overall yield from 25
and 26. Deacetylation, followed by a Birch reduction, afforded
tetrasaccharide 4 in good (90%) yield. The solubility problems
that plagued the deprotection of 25 were not problematic here.
The B type V antigen was prepared in a manner analogous
to the A type structure (Scheme 5). First, treatment of the
trisaccharide acceptor 25 with the trichloroacetimidate 28[35]
in the presence of trimethylsilyltrifluoromethane sulfonate
(TMSOTf) afforded the tetrasaccharide 29 with complete stereo-
selectivity. Unfortunately contamination with by-products of the
trichloroacetimidate 28, as was observed in the synthesis of 6,
again did not permit full characterization until removal of the
benzyl ethers and benzylidene acetals by a Birch reduction to
give 5 in 50% yield. As was seen in the deprotection of 25,
the poor yield resulted from the poor solubility of 29 under the
With trisaccharide 25 in hand, the H type V antigen was pre-
pared with the view of undertaking enzyme kinetic studies with
GTA and GTB. For these investigations, the octyl glycoside 6
was required and this compound was obtained as illustrated in
Scheme 3. First, removal of the benzylidene acetals and ben-
zyl ethers using a Birch reduction, followed by reduction of the
alkene by hydrogenation afforded 6 in 49% yield. The low yield
can be attributed to the low solubility of 25 under the reaction
conditions, and a significant portion (33%) of starting material
was recovered, and could be recycled. Although direct hydro-
genation of 25 provided 6, surprisingly, it was not possible to
isolate 25 in adequate purity when the protecting groups were
removed in this manner and thus we employed this two-step
approach.
In addition to being used for the synthesis of the H type
V antigen, trisaccharide 25 also served as the precursor to the
corresponding A and B structures. Access to the A type V anti-
gen (Scheme 4) was achieved by glycosylation of 25 using

RESEARCH FRONT
ABO Histo-Blood Group Type V and VI Antigens
561
Ph
O
O
RO
AcO
AcO
OR
OAc
(c)
(a)
O
O
O
O
O
RO
HO
RO
HO
13
AcO
10
O
CCl3
R ϭ Ac 11
R ϭ H 12
(b)
NH
O
Ph
Ph
Ph
O
O
O
O
O
(d)
(f)
O
O
O
O
O
O
HO
PMBO
PMBO
PMBO
HO
15
BnO
16
14
(g)
(e)
Ph
Ph
O
O
O
O
O
O
O
O
PMBO
HO
AcO
17
BnO
18
Scheme 1. (a) 7-octen-1-ol, 4-Å MS, TMSOTf, CH2Cl2; (b) NaOCH3, CH3OH, 73% (two steps); (c) PhCH(OCH3)2, p-TsOH, DMF, 72%; (d) n-Bu2SnO,
n-Bu4NI, p-methoxybenzyl chloride, PhCH3, 95%; (e) Ac2O, pyridine, DMAP, 99%; (f) BnBr, NaH, DMF, 89%; (g) DDQ, CH2Cl2, H2O, 95%.
reaction conditions; fortunately, the unreacted starting material
was easily recoverable and could be submitted to the reaction
again.
confirmed by acetylation and a downfield shift of H4 from a
multiplet at 3.52–3.63 ppm to one at 4.92–5.01 ppm.
Once 36 had been synthesized, we commenced the prepa-
ration of the oligosaccharides as illustrated in Scheme 7. First,
glycosylation of 36 with the trichloroacetimidate 19[31] afforded
the disaccharide product. Deacetylation was again necessary to
facilitate purification as the disaccharide was contaminated by
the glycosyl N-trichloroacetamide by-product arising from 19.
Disaccharide diol 37 was obtained in 91% yield over the two
steps. Selective protection of the 3ꢀ position with a pivaloate ester
yielded alcohol 38, which was subsequently glycosylated, in
78% yield, using β-l-fucopyranosyl trichloroacetimidate 23.[33]
Removal of the pivaloate ester in 39 afforded 40, the low yield
was again attributed to the low reactivity of 39 under the reaction
conditions. Fortunately, unreacted 39 was easily recovered.
The H type VI antigen 7 was required for enzyme kinetic
studies, as was its H type V counterpart. Preparation of this
trisaccharide was achieved through Birch reduction of 40 fol-
lowed by hydrogenation of the alkene to afford the H type VI
trisaccharide 7 (Scheme 8).Although direct treatment of 40 with
H2 and Pd–C did provide 7, it was found advantageous in terms
of product purity of 7 to conduct the two-step process.
Synthesis of Type VI Antigens
A pathway analogous to the one used for the preparation of
the type V structures was also employed to prepare the type
VI antigens. The same building blocks were required, except
that the protected galactoside acceptor 18, the precursor to the
‘reducing-end’ residue, was replaced with the requisite β-d-
glucopyranoside (36, Scheme 6). This compound was prepared
commencing from the previously reported trichloroacetimidate
30[35] by glycosidation with 7-octen-1-ol to afford the glycoside
31. Subsequent deacetylation afforded the tetrol 32 in 57% yield
over two steps. Next, introduction of the benzylidene acetal was
achieved, yielding 33 in 95% yield. Benzylation of the diol under
standard conditions yielded 35, and then the opening of the ben-
zylidene acetal provided the 2,3,6-tri-O-benzyl glucopyranoside
derivative 36 in 63% yield over the two steps. To effect the ben-
zylidene ring opening, several sets of conditions were explored,
including the more conventional trifluoromethanesulfonic acid
(TfOH)–NaCNBH3 method originally reported by Kiessling.[36]
However, in terms of reproducibility, the Et3SiH–BF3·OEt2 con-
ditions reported byToone[37] were found to be the most effective.
The regiochemistry of the benzylidene acetal ring opening was
Access to the A type VI antigen was achieved by glycosy-
lation of 40 with the trichloracetimidate 26,[34] followed by
conversion of the azide to an N-acetyl using thioacetic acid
in pyridine (Scheme 9). Again, like the A type V counterpart,
conversion of the azide was necessary to facilitate purification

RESEARCH FRONT
562
P. J. Meloncelli and T. L. Lowary
Ph
O
O
O
Ph
AcO
AcO
Ph
Ph
Ph
CCl3
O
O
O
O
O
O
19
O
O
O
NH
(a)
(c)
O
O
O
O
O
O
RO
O
PivO
O
Ph
BnO
RO
(b)
BnO
HO
R ϭ Ac 20
R ϭ H 21
O
22
O
NH
O
(d)
O
HO
CCl3
O
OBn
Ph
O
Ph
BnO
OBn
O
O
18
BnO
O
O
23
O
O
O
RO
O
O
BnO
R ϭ Piv
O
24
OBn
(e)
R ϭ H 25
OBn
BnO
Scheme 2. (a) BF3·OEt2, CH2Cl2, 4-Å MS; (b) NaOCH3, CH3OH, 59% (two steps); (c) (CH3)3COCl, pyridine, 85%; (d) TMSOTf, Et2O, 4 Å MS, 98%;
(e) LiOCH3, CH3OH, 58%.
Ph
Ph
O
O
O
O
HO
HO
O
OH
OH
(a)
O
O
O
O
O
O(CH2)7CH3
O
HO
HO
O
O
BnO
HO
O
O
OBn
OH
OH
OBn
HO
BnO
25
6
Scheme 3. (a) (i) NH3, Na, CH3OH, THF; (ii) H2, 10% Pd–C, CH3OH, 49%.
and remove by-products derived from the trichloroacetimidate
26.[34] Deacetylation, followed by removal of the benzyl ethers
and benzylidene acetals using Birch conditions afforded 8. The
B type VI antigen was accessed by glycosylation of 40 with
the trichloroacetimidate 28[35] to afford the tetrasaccharide 42
in 60% yield. Unfortunately, like the B typeVI counterpart, con-
tamination with by-products related to the trichloroacetimidate
28 prevented complete characterization. Global deprotection
using Birch conditions afforded 9 in 72% yield. Unlike the B
type V counterpart, the yield was not significantly affected by
poor solubility of 42.
routes to these targets were the preparation of the two reducing-
end building blocks 18 and 36. Also crucial to the efficiency
of this synthesis were the highly stereoselective glycosylations
utilizing glycosyl trichloroacetimidates, most notably the α-l-
fucopyranosyl, the 2-azido-2-deoxy-α-d-galactopyranosyl and
the α-d-galactopyranosyl linkages of the H type intermediates
25 and 40, the A type intermediates 27 and 41 and the B
type intermediates 29 and 42 respectively. Importantly, the final
deprotection, taking advantage of a Birch reduction, enabled the
removal of the benzyl ethers and benzylidene acetals while leav-
ing the 7-octen-1-yl linker intact. The 7-octen-1-yl linker will be
important in future work aimed at conjugation of the antigens
to a protein or solid support. The methodology developed here
should be readily adaptable to the 12 remainingA, B, and H anti-
gens. A range of biological investigations, including their use in
binding studies with anti-A, B, and H antibodies and enzyme
kinetics studies of GTA and GTB are under way.
Conclusions
In summary, through the use of a linear chemical synthesis,
we have demonstrated the syntheses of the A, B, and H type
V and VI histo-blood group antigens (4–9). Key steps in the

RESEARCH FRONT
ABO Histo-Blood Group Type V and VI Antigens
563
Ph
Ph
O
O
Ph
Ph
O
O
O
O
AcO
AcO
O
O
OAc
O
O
O
O
O
HO
O
BnO
O
O
AcHN
O
(a)
O
O
O
OBn
O
BnO
OBn
25
BnO
O
OBn
27
OBn
AcO
AcO
BnO
OAc
O
O
CCl3
N3
(b)
NH
HO
OH
26
O
HO
O
HO
O
OH
OH
HO
O
O
AcHN
O
O
HO
O
OH
OH
HO
4
Scheme 4. (a) (i) TMSOTf, 4-Å MS, Et2O; (ii) AcSH, pyridine, 51%; (b) (i) NaOCH3, CH3OH, 96%; (ii) Na, NH3, CH3OH, THF, 90%.
Ph
Ph
O
O
O
O
Ph
Ph
O
O
O
O
HO
O
O
BnO
BnO
OBn
O
O
BnO
O
O
O
O
O
OBn
BnO
(a)
O
OBn
O
O
25
BnO
O
BnO
O
OBn
BnO
OBn
O
OBn
BnO
29
O
CCl3
BnO
OBn
28
NH
(b)
HO
OH
O
HO
O
HO
O
OH
OH
HO
O
O
HO
O
O
HO
O
OH
OH
HO
5
Scheme 5. (a) TMSOTf, Et2O, 4-Å MS, 60%; (b) NH3, Na, CH3OH, THF, 50%.

RESEARCH FRONT
564
P. J. Meloncelli and T. L. Lowary
OAc
OR
O
Ph
O
(c)
O
AcO
(a)
RO
RO
O
O
O
AcO
AcO
O
HO
RO
O
CCl3
HO
R ϭ Ac 31
R ϭ H 32
30
33
(b)
NH
(d)
OBn
O
OBn
Ph
O
O
(f)
(e)
O
AcO
BnO
HO
BnO
O
O
O
O
BnO
BnO
BnO
BnO
35
36
34
Scheme 6. (a) 7-Octen-1-ol, TMSOTf, CH2Cl2, 4-Å MS; (b) NaOCH3, CH3OH, 57% (two steps); (c) PhCH(OCH3)2, p-TsOH, DMF, 95%; (d) BnBr,
NaH, DMF, 98%; (e) Et3SiH, BF3·OEt2, CH2Cl2, 64%; (f) Ac2O, pyridine, DMAP, 88%.
Ph
O
O
O
Ph
AcO
O
AcO
O
CCl3
O
19
(a)
NH
O
OBn
O
RO
O
O
HO
BnO
OBn
BnO
O
HO
BnO
O
R ϭ H 37
(b)
BnO
36
R ϭ Piv 38
NH
Ph
O
OBn
CCl3
(c)
O
O
OBn
O
BnO
23
O
OBn
O
RO
O
O
O
BnO
BnO
O
OBn
(d)
OBn
R ϭ Piv 39
R ϭ H 40
BnO
Scheme 7. (a) (i) BF3·OEt2, CH2Cl2, 4-Å MS; (ii) NaOCH3, CH3OH, 91%; (b) (CH3)3CCOCl, pyridine, 95%; (c) TMSOTf, Et2O, CH2Cl2, 4 Å MS, 78%;
(d) LiOCH3, CH3OH, 68%.
Experimental
stained by heating (>200◦C) with either p-anisaldehyde in 5%
General Methods
sulfuric acid in EtOH or 10% ammonium molybdate in 10%
sulfuric acid. Unless otherwise indicated, all column chromato-
graphy was performed on silica gel 60 (40–60 µm). Iatrobeads
refers to a beaded silica gel 6RS-8060, which is manufactured
by Iatron Laboratories (Tokyo). C-18 silica gel (35–70 µm)
was manufactured by Toronto Research Chemicals. Optical
All reagents were purchased from commercial sources and
were used without further purification, unless otherwise stated.
Reaction solvents were purchased and were used without purifi-
cation; dry solvents were purified by successive passage through
columns of alumina and copper under nitrogen. All reactions
were carried out at room temperature under a positive pres-
sure of argon, unless otherwise stated. TLC was performed on
Merck silica gel 60 F254 aluminium-backed plates that were
1
rotations were measured at 22 2◦C. H NMR spectra were
recorded at 400 and 500 MHz, chemical shifts were referenced
to the peak for TMS (0.0 ppm, CDCl3) or CD3OD (3.30 ppm).

RESEARCH FRONT
ABO Histo-Blood Group Type V and VI Antigens
565
Ph
O
O
HO
OH
O
OH
O
OBn
(a)
O
O
HO
O
HO
O
O(CH2)7CH3
O
O
HO
O
BnO
HO
BnO
O
O
OH
OBn
OH
OBn
HO
BnO
40
7
Scheme 8. (a) (i) Na, NH3, CH3OH, THF; (ii) H2, Pd–C, CH3OH, 61%.
13C NMR (attached proton test) spectra were recorded at 125
or 100 MHz, and 13C chemical shifts were referenced to the
peak for internal CDCl3 (77.1 ppm) or CD3OD (49.0). All spec-
tra were recorded in CDCl3 unless specified otherwise. Melting
points were measured using a Perkin–Elmer Pyris 1 Differen-
tial Scanning Calorimeter. Electrospray (ESI) mass spectra were
recorded on samples suspended in mixtures ofTHF with CH3OH
and added NaCl.
70.8 (CH=CH2(CH2)5CH2O), 63.4, 62.54, 62.51 (C6, C6ꢀ,
C6ꢀꢀꢀ), 51.30 (C2ꢀꢀꢀ), 34.9 (CH=CH2(CH2)5CH2O), 30.8 (2C,
CH=CH2(CH2)5CH2O), 30.1 (CH=CH2(CH2)5CH2O), 27.0
(CH=CH2(CH2)5CH2O), 22.9 (CH3C=O), 16.8 (C6ꢀꢀ). m/z
(ESI) calc. [C34H59NO20]Na+: 824.3523. Found: 824.3513.
7-Octen-1-yl 3-O-[2-O-(α-L-Fucopyranosyl)-3-O-
(α-D-galactopyranosyl)-β-D-galactopyranosyl]-
β-D-galactopyranoside 5
The nomenclature for NMR assignments is shown in Fig. 3,
using the A type V antigen as an example.
Redistilled liquid ammonia (20 mL) was collected in a flask
cooled to −78◦C and treated with sodium until the blue
colour persisted. A solution of the tetrasaccharide 29 (260 mg,
0.157 mmol) in THF (4 mL) and CH3OH (63 µL, 1.57 mmol)
was added dropwise and the solution was stirred (−78◦C, 1 h).
The reaction was then quenched by the addition of CH3OH
(4 mL) and the ammonia evaporated to dryness. The solution
was taken up in CH3OH (100 mL), neutralized with Amber-
lite IR 120 (H+), filtered, and the residue subjected to chro-
matography (Iatrobeads, CH2Cl2/CH3OH, 1:1) to afford first
unreacted 29 (104 mg, 40%); further elution (CH2Cl2/CH3OH,
2:1) afforded the fully deprotected compound 5 (60 mg, 50%).
[α] +7.2 (c = 0.2, CH3OH). δH (500 MHz, CD3OD) 5.85–5.75
7-Octen-1-yl 3-O-[3-O-(2-N-Acetyl-2-deoxy-α-D-
galactopyranosyl)-2-O-(α-L-fucopyranosyl)-β-D-
galactopyranosyl]-β-D-galactopyranoside 4
A
stirred solution of the tetrasaccharide 27 (186 mg,
0.127 mmol) in CH3OH (25 mL) was treated with a catalytic
amount of NaOCH3 in CH3OH and the solution was stirred
(2 h). The solution was neutralized with Amberlite IR 120 (H+),
filtered, and the residue subjected to flash chromatography
(Iatrobeads, CH2Cl2/CH3OH, 9:1) to afford the triol (162 mg,
96%)asacolourlessoil. Redistilledliquidammonia(20 mL)was
collected in a flask cooled to −78◦C and treated with sodium
until the blue colour persisted. A solution of the tetrasaccha-
ride (160 mg, 0.120 mmol) in THF (4 mL) and CH3OH (29 µL,
0.718 mmol) was added dropwise and the mixture was stirred
(−78◦C, 1 h). The reaction was then quenched by the addition
of CH3OH (4 mL) and the ammonia evaporated to dryness. The
solution was taken up in CH3OH (100 mL), neutralized with
Amberlite IR 120 (H+), filtered, and the residue subjected to
C-18 chromatography (CH3OH/H2O, 1:1) to afford the fully
deprotected tetrasaccharide 4 (85 mg, 90%) as a colourless oil.
[α] +24.4 (c = 0.3, CH3OH). δH (500 MHz, CD3OD) 5.85–5.75
(1H, m, CH2=CH), 5.29 (1H, d, J1 ,2 3.8, H1ꢀꢀ), 5.16 (1H,
ꢀꢀ ꢀꢀ
3.6, H1ꢀꢀꢀ), 5.01–4.94 (1H, m, CH=CH2), 4.93–4.88
ꢀꢀꢀ,2ꢀꢀꢀ
d, J1
(1H, m, CH=CH2), 4.67 (1H, d, J1 ,2 7.5, H1ꢀ), 4.61 (1H,
ꢀ
ꢀ
q, J5 ,6 6.3, H5ꢀꢀ), 4.23 (1H, d, J1,2 7.0, H1), 4.01 (1H, dd,
ꢀꢀ ꢀꢀ
J2 ,3 8.1, J1 ,2 7.5, H2ꢀ), 4.19–4.09, 3.97–3.65, 3.64–3.49 (22H,
3 × m, H2, H2ꢀꢀ, H2ꢀꢀꢀ, H3, H3ꢀ, H3ꢀꢀ, H3ꢀꢀꢀ, H4, H4ꢀ, H4ꢀꢀ,
H4ꢀꢀꢀ, H5, H5ꢀ, H5ꢀꢀꢀ, H6, H6ꢀ, H6ꢀꢀꢀ, CH=CH2(CH2)5CH2O),
2.08–2.00 (2H, m, CH=CH2(CH2)5CH2O), 1.66–1.57 (2H, m,
CH=CH2(CH2)5CH2O), 1.45–1.27 (6H, m, CH=CH2(CH2)5
ꢀ
ꢀ
ꢀ
ꢀ
CH2O), 0.56 (3H, d, J5 ,6 6.3, H6ꢀꢀ). δC (125 MHz, CD3OD)
ꢀꢀ ꢀꢀ
140.1 (CH2=CH), 114.8 (CH2=CH), 105.04, 104.98 (C1, C1ꢀ),
100.3 (C1ꢀꢀ), 96.1 (C1ꢀꢀꢀ), 84.3, 79.4, 76.3, 76.0, 74.4, 73.8,
73.1, 71.64, 71.61, 71.4, 71.2, 70.32, 70.30, 70.0, 68.0, 66.6
(C2, C2ꢀ, C2ꢀꢀ, C2ꢀꢀꢀ, C3, C3ꢀ, C3ꢀꢀ, C3ꢀꢀꢀ, C4, C4ꢀ, C4ꢀꢀ, C4ꢀꢀꢀ,
C5, C5ꢀ, C5ꢀꢀ, C5ꢀꢀꢀ), 70.8 (CH=CH2(CH2)5CH2O), 63.3, 62.56,
62.54 (C6, C6ꢀ, C6ꢀꢀꢀ), 34.9 (CH=CH2(CH2)5CH2O), 30.8
(CH=CH2(CH2)5CH2O), 30.10 (2C, CH=CH2(CH2)5CH2O),
27.0 (CH=CH2(CH2)5CH2O), 16.7 (C6ꢀꢀ). m/z (ESI) calc.
[C32H56O20]Na+: 783.3257. Found: 783.3258.
(1H, m, CH2=CH), 5.30 (1H, d, J1 ,2 3.8, H1ꢀꢀ), 5.16 (1H, d,
ꢀꢀ ꢀꢀ
J1
3.7, H1ꢀꢀꢀ), 5.01–4.93 (1H, m, CH=CH2), 4.93–4.88 (1H,
ꢀꢀꢀ,2ꢀꢀꢀ
m, CH=CH2), 4.67 (1H, d, J1 ,2 7.7, H1ꢀ), 4.65 (1H, q, J5 ,6
ꢀ
ꢀ
ꢀꢀ ꢀꢀ
6.5, H5ꢀꢀ), 4.22 (1H, d, J1,2 6.9, H1), 4.01 (1H, dd, J2 ,3 9.7, J1 ,2
ꢀ
ꢀ
ꢀ
ꢀ
7.7, H2ꢀ), 4.34–4.30, 4.20–4.09, 3.95–3.80, 3.63–3.47 (22H,
4 × m, H2, H2ꢀꢀ, H2ꢀꢀꢀ, H3, H3ꢀ, H3ꢀꢀ, H3ꢀꢀꢀ, H4, H4ꢀ, H4ꢀꢀ, H4ꢀꢀꢀ,
H5, H5ꢀ, H5ꢀꢀꢀ, H6, H6ꢀ, H6ꢀꢀꢀ, CH=CH2(CH2)5CH2O), 2.01
(3H, s, CH3C=O), 2.09–2.00 (2H, m, CH=CH2(CH2)5CH2O),
1.69–1.58 (2H, m, CH=CH2(CH2)5CH2O), 1.45–1.26 (6H,
m, CH=CH2(CH2)5CH2O), 1.22 (3H, d, J5 ,6 6.5, H6ꢀꢀ). δC
ꢀꢀ ꢀꢀ
Octyl 3-O-[2-O-(α-L-Fucopyranosyl)-β-D-galactopyranosyl]-
β-D-galactopyranoside 6
(125 MHz, CD3OD) 174.4 (C=O), 140.1 (CH2=CH), 114.8
(CH2=CH), 105.02, 104.96 (C1, C1ꢀ), 100.2 (C1ꢀꢀ), 93.7
(C1ꢀꢀꢀ), 84.2, 77.8, 76.3, 76.2, 74.0, 73.8, 72.8, 71.7, 71.6,
70.5, 70.33, 70.25, 70.0, 68.1, 64.8 (C2, C2ꢀ, C2ꢀꢀ, C3,
C3ꢀ, C3ꢀꢀ, C3ꢀꢀꢀ, C4, C4ꢀ, C4ꢀꢀ, C4ꢀꢀꢀ, C5, C5ꢀ, C5ꢀꢀ, C5ꢀꢀꢀ),
Redistilled liquid ammonia (10 mL) was collected in a flask
cooled to −78◦C and treated with sodium until the blue
colour persisted. A solution of the trisaccharide 25 (330 mg,

RESEARCH FRONT
566
P. J. Meloncelli and T. L. Lowary
Ph
O
O
O
OBn
O
HO
O
O
O
BnO
BnO
O
OBn
OBn
BnO
40
BnO
BnO
AcO
OAc
OBn
O
O
O
CCl3
O
CCl3
AcO
BnO
N3
NH
NH
28
26
(c)
(a)
Ph
Ph
O
O
BnO
AcO
AcO
OBn
OAc
O
O
O
O
BnO
O
O
OBn
O
OBn
BnO
AcHN
O
O
O
O
O
O
O
O
O
BnO
BnO
BnO
BnO
O
O
OBn
42
OBn
41
OBn
(d)
OBn
BnO
BnO
(b)
HO
HO
HO
HO
OH
OH
O
HO
O
HO
OH
OH
O
OH
O
OH
AcHN
HO
O
O
O
O
HO
O
O
HO
O
O
O
O
HO
HO
O
O
OH
OH
OH
OH
HO
8
HO
9
Scheme 9. (a) (i) TMSOTf, Et2O, 4-Å MS; (ii) AcSH, pyridine, 47%; (b) (i) NaOCH3, CH3OH, 95%; (ii) Na, NH3, CH3OH, THF, 90%; (c) TMSOTf,
Et2O, 4 Å MS, 60%; (d) Na, NH3, CH3OH, THF, 72%.
0.291 mmol) in THF (4 mL) and CH3OH (70 µL, 1.74 mmol)
was added dropwise and the solution was stirred (−78◦C, 2 h).
The reaction was then quenched by the addition of CH3OH
(4 mL) and the ammonia was evaporated to dryness.The solution
wastakenupinCH3OH(100 mL), neutralizedwithAmberliteIR
120 (H+), filtered, and the residue subjected to chromatography
(Iatrobeads, CH2Cl2/CH3OH, 1:1) to afford first unreacted 25
(110 mg, 33%); further elution (CH2Cl2/CH3OH, 2:1) afforded
the alkene as a colourless oil (114 mg). The residue was then
taken up in CH3OH, treated with Pd/C (10%, 20 mg) and sub-
jected to a H2 atmosphere ((rt), 1 day). The mixture was then
filtered and concentrated to afford the octyl glycoside 6 as a
colourless oil (98 mg, 49%). [α] −30.0 (c = 0.15, CH3OH).
δH (500 MHz, CD3OD/CDCl3) 5.18 (1H, d, J1 ,2 2.0, H1ꢀꢀ),
ꢀꢀ ꢀꢀ
4.62 (1H, d, J1 ,2 7.2, H1ꢀ), 4.32 (1H, q, J5 ,6 6.7, H5ꢀꢀ),
ꢀ
ꢀ
ꢀꢀ ꢀꢀ
4.27 (1H, d, J1,2 7.5, H1), 4.12 (1H, d, J3 ,4 2.0, H4ꢀ), 3.93–
3.82, 3.81–3.62, 3.63–3.47 (16H, 3 × m, H2, H2ꢀ, H2ꢀꢀ, H3,
H3ꢀ, H3ꢀꢀ, H4, H4ꢀꢀ, H5, H5ꢀ, H6, H6ꢀ, CH3(CH2)6CH2O),
1.67–1.56 (2H, m, CH3(CH2)6CH2O), 1.41–1.20 (10H, m,
ꢀ
ꢀ
CH3(CH2)6CH2O), 1.24 (3H, d, J5 ,6 6.7, H6ꢀꢀ), 0.89 (3H,
ꢀꢀ ꢀꢀ
t, J 6.8, CH3(CH2)6CH2O). δC (100 MHz) 105.1, 104.5 (C1,
C1ꢀ), 102.4 (C1ꢀꢀ), 84.9, 80.9, 76.5, 76.1, 74.7, 73.6, 71.7, 71.6,
70.9, 70.1, 70.0, 69.2 (C2, C2ꢀ, C2ꢀꢀ, C3, C3ꢀ, C3ꢀꢀ, C4, C4ꢀ,
C4ꢀꢀ, C5, C5ꢀ, C5ꢀꢀ), 70.8 (CH3(CH2)6CH2O), 62.6, 62.5 (C6,

RESEARCH FRONT
ABO Histo-Blood Group Type V and VI Antigens
567
HO
OH
colourless oil. Redistilled liquid ammonia (20 mL) was col-
lected in a flask cooled to −78◦C and treated with sodium
until the blue colour persisted. A solution of the tetrasaccha-
ride (90 mg, 0.063 mmol) in THF (4 mL) and CH3OH (18 µL,
0.44 mmol) was added dropwise and the solution was stirred
(−78◦C, 1 h). The reaction was then quenched by the addition
of CH3OH (4 mL) and the ammonia evaporated to dryness.
The solution was taken up in CH3OH (100 mL), neutralized
with Amberlite IR 120 (H+), filtered, and the residue sub-
jected to C-18 chromatography (CH3OH/H2O, 1:1) to afford the
fully deprotected tetrasaccharide 8 (45.0 mg, 90%) as a colour-
less oil. [α] +17.1 (c = 0.3, CH3OH). δH (500 MHz, CD3OD)
O
HO
O
HO
O
OH
OH
HO
O
O
AcHN
H1
O
O
ٞ
H1Ј
HO H1
H1
OH
Љ
O
OH
HO
4
Fig. 3. Ring numbering system for NMR assignments.
5.87–5.73 (1H, m, CH2=CH), 5.34 (1H, d, J1 ,2 3.9, H1ꢀꢀ),
ꢀꢀ ꢀꢀ
5.16 (1H, d, J1
3.9, H1ꢀꢀꢀ), 5.01–4.95 (1H, m, CH=CH2),
ꢀꢀꢀ,2ꢀꢀꢀ
C6ꢀ), 33.1 (CH3(CH2)6CH2O), 30.9 (2C, CH3(CH2)6CH2O),
30.6 (CH3(CH2)6CH2O), 30.5 (CH3(CH2)6CH2O), 27.2
(CH3(CH2)6CH2O), 16.8 (C6ꢀꢀ) 14.7 (CH3(CH2)6CH2O). m/z
(ESI) calc. [C26H48O15]Na+: 623.2885. Found: 623.2887.
4.94–4.89 (1H, m, CH=CH2), 4.52 (1H, d, J1 ,2 7.8, H1ꢀ),
ꢀ
ꢀ
4.35–4.28 (2H, m, H2ꢀꢀꢀ, H5ꢀꢀ), 4.26 (1H, d, J1,2 7.8, H1),
4.00 (1H, dd, J2 ,3 9.7, J1 ,2 7.8, H2ꢀ), 4.20–4.15, 4.13–4.09,
3.94–3.61, 3.57–3.50, 3.32–3.23 (21H, 5 × m, H2, H2ꢀꢀ, H3ꢀ,
H3ꢀꢀ, H3ꢀꢀꢀ, H4, H4ꢀ, H4ꢀꢀ, H4ꢀꢀꢀ, H5, H5ꢀ, H5ꢀꢀꢀ, H6, H6ꢀ, H6ꢀꢀꢀ,
CH=CH2(CH2)5CH2O), 3.46 (1H, d, J2,3 9.1, J3,4 9.1, H3), 2.01
(3H, s, CH3C=O), 2.09–1.98 (2H, m, CH=CH2(CH2)5CH2O),
1.65–1.58 (2H, m, CH=CH2(CH2)5CH2O), 1.44–1.30 (6H,
ꢀ
ꢀ
ꢀ
ꢀ
Octyl 4-O-[2-O-(α-L-Fucopyranosyl)-β-D-galactopyranosyl]-
β-D-glucopyranoside 7
Redistilled liquid ammonia (10 mL) was collected in a flask
cooled to −78◦C and treated with sodium until the blue
colour persisted. A solution of the trisaccharide 40 (370 mg,
0.301 mmol) in THF (4 mL) and CH3OH (85 µL, 2.11 mmol)
was added dropwise and the solution was stirred (−78◦C, 2 h).
The reaction was then quenched by the addition of CH3OH
(4 mL) and the ammonia evaporated to dryness. The solution
wastakenupinCH3OH(100 mL), neutralizedwithAmberliteIR
120 (H+), filtered, and the residue subjected to chromatography
(Iatrobeads, CH2Cl2/CH3OH, 1:1) to afford first unreacted 40
(120 mg, 33%); further elution afforded the alkene as a colour-
less oil (140 mg). The residue was then taken up in CH3OH,
treated with Pd/C (10%, 20 mg) and subjected to an H2 atmo-
sphere (rt, 1 day).The mixture was then filtered and concentrated
to afford the octyl glycoside 7 as a colourless oil (110 mg, 61%).
[α] −60.5 (c = 0.26, CH3OH). δH (500 MHz, CD3OD) 5.24 (1H,
m, CH=CH2(CH2)5CH2O), 1.22 (3H, d, J5 ,6 6.5, H6ꢀꢀ). δC
ꢀꢀ ꢀꢀ
(125 MHz, CD3OD) 174.5 (C=O), 140.1 (CH2=CH), 114.8
(CH2=CH), 104.3 (C1), 102.2 (C1ꢀ), 100.2 (C1ꢀꢀ), 93.6 (C1ꢀꢀꢀ),
78.2, 78.0, 77.0, 76.8, 76.5, 74.9, 73.6, 73.5, 72.7, 71.9, 70.6,
70.0, 67.7, 64.9 (C2, C2ꢀ, C2ꢀꢀ, C3, C3ꢀ, C3ꢀꢀ, C3ꢀꢀꢀ, C4, C4ꢀ,
C4ꢀꢀ, C4ꢀꢀꢀ, C5, C5ꢀ, C5ꢀꢀꢀ), 71.0 (CH=CH2(CH2)5CH2O), 69.9
(C5ꢀꢀ), 63.4, 62.5, 61.7 (C6, C6ꢀ, C6ꢀꢀꢀ), 51.3 (C2ꢀꢀꢀ), 34.8
(CH=CH2(CH2)5CH2O), 30.8 (CH=CH2(CH2)5CH2O), 30.08
(CH=CH2(CH2)5CH2O), 30.07 (CH=CH2(CH2)5CH2O), 27.0
(CH=CH2(CH2)5CH2O), 22.8 (CH3C=O), 16.6 (C6ꢀꢀ). m/z
(ESI) calc. [C34H59NO20]Na+: 824.3523. Found: 824.3526.
7-Octen-1-yl 4-O-[2-O-(α-L-Fucopyranosyl)-3-O-
(α-D-galactopyranosyl)-β-D-galactopyranosyl]-
β-D-glucopyranoside 9
d, J1 ,2 3.4, H1ꢀꢀ), 4.48 (1H, d, J1 ,2 7.0, H1ꢀ), 4.34 (1H, d, J1,2
ꢀꢀ ꢀꢀ
ꢀ
ꢀ
Redistilled liquid ammonia (10 mL) was collected in a flask
cooled to −78◦C and treated with sodium until the blue
colour persisted. A solution of the tetrasaccharide 42 (160 mg,
0.091 mmol) in THF (4 mL) and CH3OH (41 µL, 1.01 mmol)
was added dropwise and the solution stirred (−78◦C, 1 h).
The reaction was then quenched by the addition of CH3OH
(4 mL) and the ammonia evaporated to dryness. The solu-
tion was taken up in CH3OH (100 mL), neutralized with
Amberlite IR 120 (H+), filtered, and the residue subjected to
chromatography (Iatrobeads, CH2Cl2/CH3OH, 1:1) to afford
the fully deprotected compound 9 (50 mg, 72%). [α] −3.0
(c = 1.0, CH3OH). δH (500 MHz, CD3OD) 5.86–5.76 (1H,
7.8, H1), 4.18 (1H, q, J5 ,6 6.5, H5ꢀꢀ), 3.91–3.64, 3.59–3.45,
ꢀꢀ ꢀꢀ
3.34–3.29 (16H, 3 × m, H2ꢀ, H2ꢀꢀ, H3, H3ꢀ, H3ꢀꢀ, H4, H4ꢀ, H4ꢀꢀ,
H5, H5ꢀ, H6, H6ꢀ, CH3(CH2)6CH2O), 3.25 (1H, dd, J2,3 8.5,
J1,2 7.8, H2), 1.42–1.23 (2H, m, CH3(CH2)6CH2O), 1.65–1.57
(10H, m, CH3(CH2)6CH2O), 1.20 (3H, d, J5 ,6 6.5, H6ꢀꢀ), 0.89
ꢀꢀ ꢀꢀ
(3H, t, J 6.9, CH3(CH2)6CH2O). δC (100 MHz, CD3OD) 104.3
(C1), 102.6 (C1), 101.7 (C1ꢀꢀ), 78.8, 78.0, 77.0, 76.8, 76.4, 75.3,
74.8, 73.6, 71.7, 70.70, 70.66, 68.30 (C2, C2ꢀ, C2ꢀꢀ, C3, C3ꢀ, C3ꢀꢀ,
C4, C4ꢀ, C4ꢀꢀ, C5, C5ꢀ, C5ꢀꢀ), 71.0(CH3(CH2)6CH2O), 62.6, 61.6
(C6, C6ꢀ), 33.0 (CH3(CH2)6CH2O), 30.8 (CH3(CH2)6CH2O),
30.6 (CH3(CH2)6CH2O), 30.4 (CH3(CH2)6CH2O), 27.1
(CH3(CH2)6CH2O), 23.7 (CH3(CH2)6CH2O), 16.8 (C6ꢀꢀ),
14.5 (CH3(CH2)6CH2O). m/z (ESI) calc. [C68H78O15]Na+:
623.2885. Found: 623.2885.
m, CH2=CH), 5.33 (1H, d, J1 ,2 3.8, H1ꢀꢀ), 5.17 (1H, d,
ꢀꢀ ꢀꢀ
J1
3.7, H1ꢀꢀꢀ), 5.00–4.95 (1H, m, CH=CH2), 4.93–4.89
ꢀꢀꢀ,2ꢀꢀꢀ
(1H, m, CH=CH2), 4.53 (1H, d, J1 ,2 7.6, H1ꢀ), 4.29 (1H,
ꢀ
ꢀ
q, J5 ,6 6.6, H5ꢀꢀ), 4.28 (1H, d, J1,2 8.2, H1), 3.47 (1H, dd,
ꢀꢀ ꢀꢀ
7-Octen-1-yl 4-O-[3-O-(2-N-Acetyl-2-deoxy-α-D-
galactopyranosyl)-2-O-(α-L-fucopyranosyl)-β-D-
galactopyranosyl]-β-D-glucopyranoside 8
J2,3 9.1, J3,4 9.1, H3), 4.19–4.10, 4.03–3.50, 3.31–3.24 (22H,
3 × m, H2, H2ꢀ, H2ꢀꢀ, H2ꢀꢀꢀ, H3ꢀ, H3ꢀꢀ, H3ꢀꢀꢀ, H4, H4ꢀ, H4ꢀꢀ,
H4ꢀꢀꢀ, H5, H5ꢀ, H5ꢀꢀꢀ, H6, H6ꢀ, H6ꢀꢀꢀ, CH=CH2(CH2)5CH2O),
2.09–2.00 (2H, m, CH=CH2(CH2)5CH2O), 1.66–1.57 (2H, m,
CH=CH2(CH2)5CH2O), 1.44–1.25 (6H, m, CH=CH2(CH2)5
Astirredsolutionofthetetrasaccharide41(240 mg, 0.154 mmol)
in CH3OH (25 mL) was treated with a catalytic amount of
NaOCH3 in CH3OH and the solution was stirred (2 h). The
solution was neutralized with Amberlite IR 120 (H+), filtered,
and the residue subjected to flash chromatography (Iatrobeads,
CH2Cl2/CH3OH, 9:1) to afford the triol (210 mg, 95%) as a
CH2O), 1.20 (3H, d, J5 ,6 6.6, H6ꢀꢀ). δC (125 MHz, CD3OD)
ꢀꢀ ꢀꢀ
140.1 (CH2=CH), 114.8 (CH2=CH), 104.3 (C1ꢀ), 102.2 (C1),
100.3 (C1ꢀꢀ), 96.1 (C1ꢀꢀꢀ), 79.8, 78.3, 77.0, 76.5, 76.4, 74.8,
73.7, 73.6, 73.1, 71.8, 71.4, 71.3, 71.0, 69.9, 67.7, 65.8

RESEARCH FRONT
568
P. J. Meloncelli and T. L. Lowary
(C2, C2ꢀ, C2ꢀꢀ, C2ꢀꢀꢀ, C3, C3ꢀ, C3ꢀꢀ, C3ꢀꢀꢀ, C4, C4ꢀ, C4ꢀꢀ,
C4ꢀꢀꢀ, C5, C5ꢀ, C5ꢀꢀ, C5ꢀꢀꢀ), 71.0 (CH=CH2(CH2)5CH2O), 63.3,
62.5, 61.7 (C6, C6ꢀ, C6ꢀꢀꢀ), 34.8 (CH=CH2(CH2)5CH2O), 30.8
(2C, CH=CH2(CH2)5CH2O), 30.1 (CH=CH2(CH2)5CH2O),
27.0 (CH=CH2(CH2)5CH2O), 16.6 (C6ꢀꢀ). m/z (ESI) calc.
[C32H56O20]Na+: 783.3257. Found: 783.3258.
the 3-O-p-methoxybenzyl derivative 15 as a white solid (4.7 g,
62%). Mp 139–141◦C. [α] +34.8 (c = 0.6, CH2Cl2). Rf 0.56
(EtOAc/hexanes, 1:1). (Found: C 70.03, H 7.79. C29H38O7
requires C 69.86, H 7.68%). δH (500 MHz) 7.55–7.51 (2H, m,
Ph), 7.38–7.30 (5H, m, Ph), 6.89–6.85 (2H, m, Ph), 5.86–5.76
(1H, m, CH=CH2), 5.47 (1H, s, PhCH), 5.03–4.91 (2H, m,
CH=CH2), 4.71, 4.69 (2H, AB, J 12.0, PhCH2), 4.33–4.27 (2H,
m, H1, H6), 4.11 (1H, d, J3,4 3.5, H4), 4.06–3.91 (3H, m, H2, H6,
CH=CH2(CH2)5CH2O), 3.80 (3H, s, CH3O), 3.54–3.45 (2H,
m, H3, CH=CH2(CH2)5CH2O), 3.36–3.33 (1H, m, H5), 2.45
(1H, d, J 1.65, OH), 2.08–2.01 (2H, m, CH=CH2(CH2)5CH2O),
1.70–1.61 (2H, m, CH=CH2(CH2)5CH2O), 1.44–1.30 (6H,
m, CH=CH2(CH2)5CH2O). δC (125.7 MHz) 159.3 (Ph),
139.0 (CH=CH2), 137.8 (Ph), 130.2 (Ph), 129.5 (Ph), 128.8
(Ph), 128.0 (Ph), 126.4 (Ph), 114.2 (CH=CH2), 113.8 (Ph),
102.9 (C1), 101.1 (PhCH), 78.8 (C3), 73.2 (C4), 71.1
(PhCH2), 70.0 (C2), 69.7, 69.3 (C6, CH=CH2(CH2)5CH2O),
66.7 (C5), 55.2 (CH3O), 33.7 (CH=CH2(CH2)5CH2O), 29.4
(CH=CH2(CH2)5CH2O), 28.9 (CH=CH2(CH2)5CH2O), 28.8
(CH=CH2(CH2)5CH2O), 25.7 (CH=CH2(CH2)5CH2O). m/z
(ESI) calc. [C29H38O7]Na+: 521.2518. Found: 521.2510.
Further elution afforded the 2-O-p-methoxybenzyl deriva-
tive 14 as a white solid (2.52 g, 33%). Mp 90–92◦C. [α] +17.1
(c = 0.8, CH2Cl2). Rf 0.37 (EtOAc/hexanes, 1:1). δH (500 MHz)
7.55–7.50 (2H, m, Ph), 7.40–7.30 (5H, m, Ph), 6.90–6.85 (2H,
m, Ph), 5.86–5.77 (1H, m, CH=CH2), 5.56 (1H, s, PhCH),
5.00–4.91 (3H, m, PhCH2, CH=CH2), 4.66 (1H, A of AB,
J 10.8, PhCH2), 4.38 (1H, d, J1,2 7.7, H1), 4.33 (1H, dd,
J6,6 12.4, J5,6 1.3, H6), 4.20 (1H, d, J3,4 3.7, H4), 4.07 (1H,
dd, J6,6 12.4, J5,6 1.8, H6), 4.01 (1H, ddd, J 9.4, 6.5, 6.5,
CH=CH2(CH2)5CH2O), 3.80 (3H, s, CH3O), 3.74–3.68 (1H,
m, H3), 3.61 (1H, dd, J2,3 9.6, J1,2 7.7, H2), 3.52 (1H, ddd, J 9.4,
6.9, 6.9, CH=CH2(CH2)5CH2O), 3.44–3.41 (1H, m, H5), 2.48
(1H, d, J 7.1, OH), 2.09–2.01 (2H, m, CH=CH2(CH2)5CH2O),
1.74–1.62 (2H, m, CH=CH2(CH2)5CH2O), 1.49–1.32 (6H,
m, CH=CH2(CH2)5CH2O). δC (125.7 MHz) 159.3 (Ph),
139.0 (CH=CH2), 137.7 (Ph), 130.8 (Ph), 129.6 (Ph), 129.1
(Ph), 128.2 (Ph), 126.5 (Ph), 114.3 (CH=CH2), 113.8 (Ph),
103.6 (C1), 101.4 (PhCH), 78.8 (C2), 74.5 (PhCH2), 75.5,
72.4 (C3, C4), 70.0, 69.2 (C6, CH=CH2(CH2)5CH2O),
66.5 (C5), 55.3 (CH3O), 33.7 (CH=CH2(CH2)5CH2O), 29.7
(CH=CH2(CH2)5CH2O), 29.0 (CH=CH2(CH2)5CH2O), 28.9
(CH=CH2(CH2)5CH2O), 26.0 (CH=CH2(CH2)5CH2O). m/z
(ESI) calc. [C29H38O7]Na+: 521.2518. Found: 521.2510.
7-Octen-1-yl 4,6-O-Benzylidene-β-D-galactopyranoside 13
A stirred solution of 2,3,4,6-tetra-O-acetyl-α-d-galactopyranosyl
trichloroacetimidate 10[29] (20.9 g, 42.5 mmol) and 7-octen-1-
ol (6.53 g, 51.0 mmol) was treated with 4-Å molecular sieves
(5 g) and the mixture stirred (rt, 1 h). The mixture was then
cooled (−40◦C), treated with TMSOTf (0.5 mL), and the mix-
ture was allowed to warm (rt, 1 h). The reaction was quenched
by the addition of Et3N (2 mL), filtered, and subjected to flash
chromatography (EtOAc/hexanes, 2:3) to afford a colourless
oil. The oil was taken up in CH3OH (200 mL), treated with a
catalytic amount of NaOCH3 in CH3OH and stirred (rt, 2 h);
the NaOCH3 was neutralized with Amberlite IR120 (H+), fil-
tered, and then concentrated. The residue was subjected to flash
chromatography (EtOAc/hexanes, 5:1) to afford the tetrol 12 as
a white solid (9.0 g, 73%), which was immediately used in the
subsequent step. A solution of the tetrol 12 (9.0 g, 31.0 mmol)
in dry DMF (100 mL) was treated with benzaldehyde dimethyl
acetal (5.9 mL, 38.7 mmol), p-TsOH (300 mg), and the solution
was stirred (40◦C, 18 h). The solution was neutralized with Et3N
(1.5 mL), concentrated and subjected to flash chromatography
(EtOAc/hexanes, 1:1) to afford the diol 13 (8.4 g, 72%) as a white
solid. Mp 156–158◦C. [α] −26.0 (c = 0.7, CH2Cl2). (Found: C
66.54, H 8.05. C21H30O6 requires C 66.65, H 7.99%). Rf 0.37
(EtOAc/hexanes, 7:10). δH (500 MHz) 7.54–7.48 (2H, m, Ph),
7.40–7.34 (3H, m, Ph), 5.86–5.77 (1H, m, CH=CH2), 5.56 (1H,
s, PhCH), 5.03–4.92 (2H, m, CH=CH2), 4.35 (1H, dd, J6,6 12.5,
J5,6 1.4, H6), 4.28 (1H, d, J1,2 7.5, H1), 4.22 (1H, d, J3,4 3.8, H4),
4.10 (1H, dd, J6,6 12.5, J5,6 1.9, H6), 3.97 (1H, ddd, J 9.4, 6.8, 6.8,
CH=CH2(CH2)5CH2O), 3.76 (1H, ddd, J2,3 9.4, J1,2 7.5, J 1.7,
H2), 3.70 (1H, ddd, J2,3 9.4, J 8.9, J3,4 3.8, H3), 3.54–3.48 (2H,
m, H5, CH=CH2(CH2)5CH2O), 2.51 (1H, d, J 8.9, OH), 2.45
(1H, d, J 1.7, OH), 2.10–2.02 (2H, m, CH=CH2(CH2)5CH2O),
1.72–1.63 (2H, m, CH=CH2(CH2)5CH2O), 1.46–1.30 (6H, m,
CH=CH2(CH2)5CH2O). δC (125.7 MHz) 139.3 (CH=CH2),
137.6 (Ph), 129.2 (Ph), 128.2 (Ph), 126.4 (Ph), 114.3
(CH=CH2), 102.8 (C1), 101.4 (PhCH), 75.4 (C4), 72.7, 71.7
(C2, C3), 70.0, 69.2 (C6, CH=CH2(CH2)5CH2O), 66.66 (C5),
33.7 (CH=CH2(CH2)5CH2O), 29.5 (CH=CH2(CH2)5CH2O),
28.9 (CH=CH2(CH2)5CH2O), 28.8 (CH=CH2(CH2)5CH2O),
25.8 (CH=CH2(CH2)5CH2O). m/z (ESI) calc. [C21H30O6]Na+:
401.1935. Found: 401.1937.
7-Octen-1-yl 2-O-Benzyl-4,6-O-benzylidene-3-O-[(4-
methoxyphenyl)methyl]-β-D-galactopyranoside 16
A stirred solution of the alcohol 15 (5.5 g, 11.0 mmol) in dry
DMF (75 mL) was cooled (−20◦C), treated with BnBr (2.10 mL,
17.6 mmol) and NaH (60%, 572 mg, 14.3 mmol) and allowed to
warm (rt, 1 h).The mixture was then treated with CH3OH (1 mL)
and partially concentrated; the residue was taken up in EtOAc
(250 mL) and washed with water and brine. The organic extract
was dried, concentrated, and then subjected to flash chromato-
graphy (EtOAc/hexanes, 2:3) to afford the benzyl ether 16 as
a white solid (5.83 g, 89%). Mp 99–103◦C. [α] +42.7 (c = 0.5,
CH2Cl2). Rf 0.74 (EtOAc/hexanes, 1:1). (Found: C 73.47, H
7.54. C29H38O7 requires C 73.44, H 7.53%). δH (500 MHz)
7.60–7.54 (2H, m, Ph), 7.41–7.26 (10H, m, Ph), 6.88–6.82 (2H,
m, Ph), 5.86–5.76 (1H, m, CH=CH2), 5.50 (1H, s, PhCH), 5.02–
4.92 (3H, m, PhCH2, CH=CH2), 4.78 (1H, A of AB, J 10.8,
PhCH2), 4.73, 4.69 (2H, AB, J 11.9, PhCH2), 4.38 (1H, d, J1,2
7-Octen-1-yl 4,6-O-Benzylidene-2-O-[(4-
methoxyphenyl)methyl]-β-D-galactopyranoside 14 and
7-Octen-1-yl 4,6-O-Benzylidene-3-O-[(4-
methoxyphenyl)methyl]-β-D-galactopyranoside 15
A stirred mixture of the diol 13 (5.83 g, 15.4 mmol) and
n-Bu2SnO (4.21 g, 17.0 mmol) in dry toluene (200 mL) was
heated at reflux with azeotropic removal of water (1 h). The
solution was treated with n-Bu4NI (7.95 g, 21.6 mmol) and
p-methoxybenzyl chloride (2.9 mL, 21.6 mmol) and then heated
at reflux further (4 h). The solution was partially concentrated,
taken up in EtOAc (300 mL), washed with water, brine, and
dried. The organic extract was then concentrated and subjected
to flash chromatography (EtOAc/hexanes, 2:3) to afford first

RESEARCH FRONT
ABO Histo-Blood Group Type V and VI Antigens
569
7.8, H1), 4.31 (1H, dd, J6,6 12.2, J5,6 1.3, H6), 4.08 (1H, d,
J3,4 3.7, H4), 4.05–3.96 (2H, m, H6, CH=CH2(CH2)5CH2O),
3.85–3.80 (4H, m, H2, CH3O), 3.54 (1H, dd, J2,3 9.7, J3,4
3.7, H3), 3.53–3.48 (1H, m, CH=CH2(CH2)5CH2O), 3.31
(1H, s, H5), 2.09–1.98 (2H, m, CH=CH2(CH2)5CH2O), 1.73–
1.60 (2H, m, CH=CH2(CH2)5CH2O), 1.49–1.27 (6H, m,
CH=CH2(CH2)5CH2O). δC (125.7 MHz) 159.2 (Ph), 139.1
(CH=CH2), 139.0 (Ph), 137.9 (Ph), 130.5 (Ph), 129.3 (Ph),
128.9 (Ph), 128.2 (Ph), 128.1 (Ph), 128.0 (Ph), 127.5 (Ph),
126.5 (Ph), 114.2 (CH=CH2), 113.7 (Ph), 103.7 (C1), 101.3
(PhCH), 78.8, 78.5 (C2, C3), 74.1 (C4), 75.2 (PhCH2),
71.7 (PhCH2), 69.9, 69.3 (C6, CH=CH2(CH2)5CH2O), 66.42
(C5), 55.27 (CH3O), 33.7 (CH=CH2(CH2)5CH2O), 29.7
(CH=CH2(CH2)5CH2O), 29.0 (CH=CH2(CH2)5CH2O), 28.8
(CH=CH2(CH2)5CH2O), 26.0 (CH=CH2(CH2)5CH2O). m/z
(ESI) calc. [C36H44O7]Na+: 611.2979. Found: 611.2977.
4.22 (1H, dd, J3,4 3.8, J4,5 0.9, H4), 4.01 (1H, ddd, J 9.4, 6.5, 6.5,
CH=CH2(CH2)5CH2O), 3.74 (1H, ddd, J2,3 9.6, J 7.3, J3,4 3.8,
H3), 3.63 (1H, dd, J2,3 9.6, J1,2 7.7, H2), 3.52 (1H, ddd, J 9.4,
6.9, 6.9, CH=CH2(CH2)5CH2O), 3.43–3.44 (1H, m, H5), 2.53
(1H, d, J 7.3, OH), 2.08–2.01 (2H, m, CH=CH2(CH2)5CH2O),
1.61–1.73 (2H, m, CH=CH2(CH2)5CH2O), 1.49–1.30 (6H, m,
CH=CH2(CH2)5CH2O). δC (125.7 MHz) 139.0 (CH=CH2),
138.6 (Ph), 137.6 (Ph), 129.1 (Ph), 128.3 (Ph), 128.2 (Ph),
127.9 (Ph), 127.6 (Ph), 126.5 (Ph), 114.2 (CH=CH2), 103.6
(C1), 101.4 (PhCH), 79.3 (C2), 75.6 (C4), 74.8 (PhCH2),
72.5 (C3), 70.0, 69.2 (C6, CH=CH2(CH2)5CH2O), 66.5 (C5),
33.7 (CH=CH2(CH2)5CH2O), 29.7 (CH=CH2(CH2)5CH2O),
28.9 (CH=CH2(CH2)5CH2O), 28.8 (CH=CH2(CH2)5CH2O),
26.0 (CH=CH2(CH2)5CH2O). m/z (ESI) calc. [C28H36O6]Na+:
491.2404. Found: 491.2402.
7-Octen-1-yl 2-O-Benzyl-3-O-(4,6-O-benzylidene-
β-D-galactopyranosyl)-4,6-O-benzylidene-
β-D-galactopyranoside 21
7-Octen-1-yl 2-O-Acetyl-4,6-O-benzylidene-3-O-[(4-
methoxyphenyl)methyl]-β-D-galactopyranoside 17
A solution of the acceptor 18 (3.59 g, 7.67 mmol) in dry CH2Cl2
(50 mL) was stirred over 4-Å molecular sieves (3 g) and the
mixture stirred (rt, 1 h). The solution was then cooled (−40◦C),
treated with BF3·OEt2 (0.5 mL) followed by dropwise addition
of the trichloroacetimidate 19[31] (7.57 g, 15.34 mmol) and then
the mixture allowed to warm (0◦C).The mixture was neutralized
with Et3N (2 mL), concentrated, and subjected to flash chro-
matography (EtOAc/hexanes, 1:1) to afford a colourless oil,
which was immediately used in the next step. The colourless
oil was taken up in CH3OH (100 mL), treated with a solu-
tion of NaOCH3 in CH3OH and stirred (rt, 3 h). The solution
was neutralized with Amberlite IR 120 (H+), filtered, and sub-
jected to flash chromatography (EtOAc/hexanes, 7:3) to afford
the diol 21 as a colourless oil (3.24 g, 59%). [α] +14.0 (c = 0.4,
CH2Cl2). Rf 0.44 (EtOAc/hexanes, 7:3). δH (500 MHz) 7.60–
7.23 (15H, m, Ph), 5.87–5.76 (1H, m, CH2=CH), 5.56 (1H,
s, PhCH), 5.51 (1H, s, PhCH), 5.04–4.92 (3H, m, PhCH2,
CH2=CH), 4.70 (1H, A of AB, J 10.4, PhCH2), 4.69 (1H, d,
A stirred solution of the alcohol 15 (75.0 mg, 0.134 mmol) in
pyridine (2 mL) was treated with Ac2O (0.5 mL) and 4-(N,N-
dimethylamino)pyridine (DMAP) (5 mg) and stirred (rt, 2 h).
The solution was treated with CH3OH (1 mL), concentrated
and subjected to flash chromatography (EtOAc/hexanes, 1:1) to
afford 17 as a colourless oil (80 mg, 99%). [α] +32.8 (c = 1.0,
CH2Cl2). Rf 0.62 (EtOAc/hexanes, 1:1). δH (500 MHz) 7.57–
7.53 (2H, m, Ph), 7.39–7.32 (3H, m, Ph), 7.28–7.23 (2H, m,
Ph), 6.89–6.84 (2H, m, Ph), 5.86–5.76 (1H, m, CH=CH2), 5.48
(1H, s, PhCH), 5.34 (1H, dd, J2,3 10.1, J1,2 8.0, H2), 5.03–4.91
(2H, m, CH=CH2), 4.57, 4.63 (2H, AB, J 12.6, PhCH2), 4.40
(1H, d, J1,2 8.0, H1), 4.30 (1H, dd, J6,6 12.3, J5,6 1.3, H6), 4.14
(1H, d, J3,4 3.6, H4), 4.03 (1H, dd, J6,6 12.3, J5,6 1.6, H6), 3.90
(1H, ddd, J 9.5, 6.3, 6.3, CH=CH2(CH2)5CH2O), 3.81 (3H, s,
CH3O), 3.57 (1H, dd, J2,3 10.1, J3,4 3.6, H3), 3.45 (1H, ddd, J
9.5, 6.9, 6.9, CH=CH2(CH2)5CH2O), 3.33 (1H, br s, H5), 2.06
(3H, s, CH3CO), 2.09–2.01 (2H, m, CH=CH2(CH2)5CH2O),
1.64–1.49 (2H, m, CH=CH2(CH2)5CH2O), 1.42–1.26 (6H, m,
CH=CH2(CH2)5CH2O). δC (125.7 MHz) 169.3 (C=O), 159.2
(Ph), 139.00 (CH=CH2), 137.7 (Ph), 130.1 (Ph), 129.1 (Ph),
128.8 (Ph), 128.0 (Ph), 126.4 (Ph), 114.1 (CH=CH2), 113.7
(Ph), 101.2, 101.1 (C1, PhCH), 76.8 (C3), 73.3 (C4), 70.7
(PhCH2), 70.1 (C2), 69.1, 69.0 (C6, CH=CH2(CH2)5CH2O),
66.52 (C5), 55.20 (CH3O), 33.6 (CH=CH2(CH2)5CH2O), 29.3
(CH=CH2(CH2)5CH2O), 28.81 (2C, CH=CH2(CH2)5CH2O),
28.78 (CH=CH2(CH2)5CH2O), 21.0 (CH3C=O). m/z (ESI)
calc. [C31H40O8]Na+: 563.2615. Found: 563.2613.
J1 ,2 8.3, H1ꢀ), 4.41 (1H, d, J1,2 7.1, H1), 4.35 (1H, d, J3,4 2.8,
ꢀ
ꢀ
ꢀ
ꢀ
H4), 4.31 (1H, dd, J6,6 12.3, J5,6 1.2, H6), 4.26 (1H, dd, J6 ,6
12.4, J5 ,6 1.1, H6ꢀ), 4.11 (1H, d, J3 ,4 3.7, H4ꢀ), 4.08–4.00 (m,
3H, H6, H6ꢀ, CH=CH2(CH2)5CH2O), 3.92–3.85 (2H, m, H2,
ꢀ
ꢀ
ꢀ
ꢀ
H3), 3.78 (1H, dd, J2 ,3 8.5, J1 ,2 8.3, H2ꢀ), 3.63–3.57 (1H, m,
H3ꢀ), 3.54 (1H, ddd, J 9.4, 6.9, 6.9, CH=CH2(CH2)5CH2O),
3.39 (1H, s, H5), 3.31 (1H, s, H5ꢀ), 2.87 (1H, s, OH), 2.59
(1H, d, J 8.3, OH), 2.08–2.01 (2H, m, CH=CH2(CH2)5CH2O),
1.77–1.61 (2H, m, CH=CH2(CH2)5CH2O), 1.50–1.30 (6H,
m, CH=CH2(CH2)5CH2O). δC (100 MHz) 139.0 (CH2=CH),
138.3 (Ph), 138.0 (Ph), 137.6 (Ph), 129.2 (Ph), 128.9 (Ph),
128.7 (Ph), 128.4 (Ph), 128.3 (Ph), 128.1 (Ph), 127.9 (Ph),
126.7 (Ph), 126.3 (Ph), 114.3 (CH2=CH), 103.9 (PhCH),
103.7 (PhCH), 101.3, 101.2 (C1, C1ꢀ), 78.4, 77.4 (C2,
C3), 76.4 (C4), 75.1 (PhCH2), 75.3, 72.5, 71.8 (C2ꢀ, C3ꢀ,
C4ꢀ), 70.1 (CH=CH2(CH2)5CH2O), 69.2, 69.1 (C6, C6ꢀ),
66.6, 66.5 (C5, C5ꢀ), 33.7 (CH=CH2(CH2)5CH2O), 28.7
(CH=CH2(CH2)5CH2O), 29.0 (CH=CH2(CH2)5CH2O), 28.9
(CH=CH2(CH2)5CH2O), 26.1 (CH=CH2(CH2)5CH2O). m/z
(ESI) calc. [C41H50O11]Na+: 741.3245. Found: 741.3245.
ꢀ
ꢀ
ꢀ
ꢀ
7-Octen-1-yl 2-O-Benzyl-4,6-O-benzylidene-
β-D-galactopyranoside 18
A stirred solution of 16 (5.60 g, 9.52 mmol) in CH2Cl2/H2O
(19:1, 100 mL) was treated with 2,3-dichloro-5,6-dicyano-p-
benzoquinone (2.59 g, 11.4 mmol) and the solution was stirred
(2 h). The mixture was then diluted with CH2Cl2 (300 mL) and
washed twice with saturated NaHCO3 (300 mL). The solution
was dried, concentrated, and subjected to flash chromatography
(EtOAc/hexanes, 1:1) to afford the alcohol 18 as a white non-
crystalline solid (4.22 g, 95%). [α] +9.0 (c = 0.6, CH2Cl2). Rf
0.48 (EtOAc/hexanes, 1:1). δH (500 MHz) 7.55–7.50 (2H, m,
Ph), 7.42–7.26 (8H, m, Ph), 5.86–5.76 (1H, m, CH=CH2), 5.56
(1H, s, PhCH), 5.03–4.92 (3H, m, PhCH2, CH=CH2), 4.73 (1H,
A of AB, J 11.3, PhCH2), 4.40 (1H, d, J1,2 7.7, H1), 4.34 (1H,
dd, J6,6 12.4, J5,6 1.5, H6), 4.41 (1H, dd, J6,6 12.4, J5,6 1.9, H6),
7-Octen-1-yl 2-O-Benzyl-3-O-(4,6-O-benzylidene-3-O-
pivaloyl-β-D-galactopyranosyl)-4,6-O-benzylidene-
β-D-galactopyranoside 22
A solution of the diol 21 (2.7 g, 3.76 mmol) in pyridine (50 mL)
was treated with trimethylacetal chloride (0.69 mL, 5.64 mmol)

RESEARCH FRONT
570
P. J. Meloncelli and T. L. Lowary
and the solution was stirred. A further addition of trimethy-
lacetal chloride (0.69 mL, 5.64 mmol) was required to ensure
completion.Thesolutionwasconcentratedandsubjectedtoflash
chromatography (EtOAc/hexanes, 1:1) to afford the alcohol 22
as a white solid (2.55 g, 85%). [α] +62.7 (c = 2.2, CH2Cl2).
Rf 0.59 (EtOAc/hexanes, 3:2). δH (500 MHz) 7.57–7.28 (15H,
m, Ph), 5.85–5.76 (1H, m, CH2=CH), 5.56 (1H, s, PhCH), 5.50
(1H, s, PhCH), 5.03–4.92 (3H, m, CH2=CH, PhCH2), 4.82 (1H,
(Ph), 127.14 (Ph), 127.08 (Ph), 127.0 (Ph), 125.9 (Ph),
114.3 (CH2=CH), 103.8 (C1), 101.9, 101.3, 100.4 (3C,
C1ꢀ, PhCH), 96.4 (C1ꢀꢀ), 79.9 (C2), 79.3 (C3), 78.6 (C4ꢀꢀ),
76.7, 76.4, 76.1, 74.3, 73.1 (C2ꢀꢀ, C3ꢀ, C3ꢀꢀ, C4, C4ꢀ), 75.3
(PhCH2), 75.0 (PhCH2), 73.0 (PhCH2), 72.6 (PhCH2), 70.2
(CH=CH2(CH2)5CH2O), 69.03, 68.97 (C6, C6ꢀ), 68.9 (C5ꢀꢀ),
66.52, 66.5, 66.3 (C2ꢀ, C5, C5ꢀ), 38.9 ((CH3)3C), 33.8
(CH=CH2(CH2)5CH2O), 29.8 (CH=CH2(CH2)5CH2O), 29.0
(CH=CH2(CH2)5CH2O), 28.9 (CH=CH2(CH2)5CH2O), 27.1
((CH3)3C), 26.3 (CH=CH2(CH2)5CH2O), 15.89 (C6ꢀꢀ). m/z
(ESI) calc. [C73H86O16]Na+: 1241.5808. Found: 1241.5808.
d, J1 ,2 7.8, H1ꢀ), 4.79 (1H, dd, J2 ,3 10.2, J3 ,4 3.8, H3ꢀ), 4.68
(1H, A of AB, J 10.0, PhCH2), 4.40 (1H, d, J1,2 7.5, H1), 4.35–
4.25 (4H, m, H4, H4ꢀ, H6, H6ꢀ), 4.07–3.99 (4H, m, H2ꢀ, H6,
H6ꢀ, CH=CH2(CH2)5CH2O), 3.92 (1H, dd, J2,3 9.9, J3,4 3.4,
H3), 3.87 (1H, dd, J2,3 9.9, J1,2 7.5, H2), 3.52 (1H, ddd, J 9.2,
7.0, 7.0, CH=CH2(CH2)5CH2O), 3.40–3.37 (2H, m, H5, H5ꢀ),
2.69 (1H, s, OH), 2.08–2.01 (2H, m, CH=CH2(CH2)5CH2O),
1.74–1.62 (2H, m, CH=CH2(CH2)5CH2O), 1.48–1.31 (6H, m,
CH=CH2(CH2)5CH2O), 1.24 (9H, s, (CH3)3C). δC (100 MHz)
178.4 (C=O), 139.0 (CH2=CH), 138.2 (Ph), 137.9 (Ph), 137.8
(Ph), 128.9 (Ph), 128.8 (Ph), 128.7 (Ph), 128.5 (Ph), 128.1
(Ph), 128.0 (Ph), 127.9 (Ph), 126.6 (Ph), 125.9 (Ph), 114.2
(CH2=CH), 103.9 (PhCH), 103.6 (PhCH), 101.2 (C1ꢀ), 100.4
(C1), 78.5 (C3), 76.2 (C2), 75.1 (PhCH2), 73.3, 73.2 (3C,
C3ꢀ, C4, C4ꢀ), 70.1 (CH=CH2(CH2)5CH2O), 69.09, 69.07
(C6, C6ꢀ), 68.9 (C2ꢀ), 66.5 (2C, C5, C5ꢀ), 39.0 ((CH3)3C),
33.7 (CH=CH2(CH2)5CH2O), 29.7 (CH=CH2(CH2)5CH2O),
29.0 (CH=CH2(CH2)5CH2O), 28.8 (CH=CH2(CH2)5CH2O),
27.1 ((CH3)3C), 26.1 (CH=CH2(CH2)5CH2O). m/z (ESI) calc.
[C46H58O12]Na+: 825.3820. Found: 825.3830.
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
7-Octen-1-yl 2-O-Benzyl-3-O-[4,6-O-benzylidene-
2-O-(2,3,4-tri-O-benzyl-α-L-fucopyranosyl)-
β-D-galactopyranosyl]-4,6-O-benzylidene-
β-D-galactopyranoside 25
A stirred solution of 24 (3.21 g, 2.62 mmol) in CH3OH (150 mL)
was treated with catalytic LiOCH3 (200 mg) and the solution
was heated at reflux (5 days). The solution was allowed to cool,
neutralized with Amberlite IR 120 (H+), filtered, and subjected
to flash chromatography (EtOAc/hexanes, 1:3) to afford first
unreacted 24 (350 mg, 11%); further elution (EtOAc/hexanes,
1:2) afforded alcohol 25 as a colourless oil (1.72 g, 58%). [α]
−50.3 (c = 0.4, CH2Cl2). Rf 0.77 (EtOAc/hexanes, 1:1). δH
(500 MHz) 7.56–7.47 (6H, m, Ph), 7.40–7.18 (24H, m, Ph),
5.88–5.78 (1H, m, CH2=CH), 5.58 (1H, d, J1 ,2 3.55, H1ꢀꢀ),
ꢀꢀ ꢀꢀ
5.55 (1H, s, PhCH), 5.53 (1H, s, PhCH), 5.05–4.94 (3H, m,
H1ꢀ, CH2=CH), 4.82, 4.76 (2H, AB, J 11.5, PhCH2), 4.90, 4.64
(2H, AB, J 9.6, PhCH2), 4.61, 4.53 (2H, AB, J 12.0, PhCH2),
4.85, 4.45 (2H, AB, J 11.6, PhCH2), 4.42 (1H, d, J1,2 7.8, H1),
4.31 (1H, d, J3,4 3.4, H4), 4.34–4.18 (3H, m, H5ꢀꢀ, H6, H6ꢀ),
7-Octen-1-yl 2-O-Benzyl-3-O-[4,6-O-benzylidene-2-O-
(2,3,4-tri-O-benzyl-α-L-fucopyranosyl)-3-O-pivaloyl-
β-D-galactopyranosyl]-4,6-O-benzylidene-β-D-
galactopyranoside 24
4.11 (1H, d, J3 ,4 3.8, H4ꢀ), 4.10–3.97 (6H, m, H2ꢀꢀ, H3, H3ꢀꢀ,
ꢀ
ꢀ
H6, H6ꢀ, CH=CH2(CH2)5CH2O), 3.93 (1H, dd, J2 ,3 8.4, J1 ,2
ꢀ
ꢀ
ꢀ
ꢀ
8.2, H2ꢀ), 3.83 (1H, dd, J2,3 9.7, J1,2 7.8, H2), 3.78–3.73 (1H,
m, H3ꢀ), 3.55 (1H, ddd, J 9.1, 6.9, 6.9, CH=CH2(CH2)5CH2O),
3.39 (1H, s, H5), 3.33 (1H, d, J 1.8, H4ꢀꢀ), 3.29 (1H, d, J 7.5, OH),
3.24 (1H, s, H5ꢀ), 2.13–2.03 (2H, m, CH=CH2(CH2)5CH2O),
1.80–1.67 (2H, m, CH=CH2(CH2)5CH2O), 1.55–1.32 (6H,
A solution of the alcohol 22 (1.74 g, 2.16 mmol) in dry
Et2O/CH2Cl2 (9:1, 50 mL) was treated with 4-Å molecular
sieves (1 g) and the mixture stirred (rt, 1 h). The mixture was
then cooled (−10◦C), treated with TMSOTf (100 µL), followed
by dropwise addition of the trichloroacetimidate 23[33] (3.65 g,
6.50 mmol) in dry Et2O (15 mL). The mixture was treated with
Et3N (0.5 mL), filtered, and subjected to flash chromatography
(EtOAc/hexanes, 1:3) to yield the trisaccharide 24 as a colour-
less oil (2.60 g, 98%). [α] −62.7 (c = 0.3, CH2Cl2). Rf 0.17
(EtOAc/hexanes, 1:1). δH (500 MHz) 7.53–7.44 (6H, m, Ph),
7.39–7.13 (24H, m, Ph), 5.87–5.76 (1H, m, CH2=CH), 5.51
m, CH=CH2(CH2)5CH2O), 0.70 (3H, d, J5 ,6 6.4, H6ꢀꢀ). δC
ꢀꢀ ꢀꢀ
(100 MHz) 139.03 (CH2=CH), 138.9 (Ph), 138.5 (Ph), 138.3
(Ph), 137.6 (Ph), 129.1 (Ph), 129.0 (Ph), 128.8 (Ph), 128.4 (Ph),
128.32 (Ph), 128.25 (Ph), 128.22 (Ph), 128.17 (Ph), 128.12
(2C, Ph), 128.09 (Ph), 128.0 (2C, Ph), 127.8 (Ph), 127.41 (Ph),
127.40 (Ph), 127.34 (Ph), 127.29 (Ph), 126.9 (Ph), 126.4 (Ph),
114.3 (CH2=CH), 103.9 (C1), 101.5, 101.4, 101.2 (3C, C1ꢀ,
PhCH), 97.8 (C1ꢀꢀ), 79.8, 79.5 (C2, C3), 78.3 (C4ꢀꢀ), 76.7,
76.2, 75.9, 75.2, 74.8, 74.4 (C2ꢀ, C2ꢀꢀ, C3ꢀ, C3ꢀꢀ, C4, C4ꢀ),
75.0 (PhCH2), 74.8 (PhCH2), 73.0 (PhCH2), 72.8 (PhCH2),
70.1 (CH=CH2(CH2)5CH2O), 69.1, 69.0 (C6, C6ꢀ), 66.8, 66.64,
66.61 (C5, C5ꢀ, C5ꢀꢀ), 33.8 (CH=CH2(CH2)5CH2O), 29.8
(CH=CH2(CH2)5CH2O), 29.0 (CH=CH2(CH2)5CH2O), 28.9
(CH=CH2(CH2)5CH2O), 26.2 (CH=CH2(CH2)5CH2O), 16.14
(C6ꢀꢀ). m/z (ESI) calc. [C68H78O15]Na+: 1157.5233. Found:
1157.5237.
ꢀꢀ ꢀꢀ
(1H, s, PhCH), 5.44 (1H, s, PhCH), 5.46 (1H, d, J1 ,2 3.5,
ꢀ
H1ꢀꢀ), 5.13 (1H, d, J1 ,2 8.0, H1 ), 5.03–4.92 (2H, m, CH2=CH),
ꢀ
ꢀ
4.89 (1H, dd, J2 ,3 9.8, J3 ,4 3.8, H3ꢀ), 4.82 (1H, A of AB,
J 9.6, PhCH2), 4.79 (1H, A of AB, J 12.0, PhCH2), 4.74
(1H, A of AB, J 11.7, PhCH2), 4.63–4.54 (4H, m, PhCH2),
4.43 (1H, d, J1,2 7.7, H1), 4.36–4.24 (7H, m, H2ꢀ, H4, H4ꢀ,
H5ꢀꢀ, H6, H6ꢀ, PhCH2), 4.12–3.94 (6H, m, H2ꢀꢀ, H3, H3ꢀꢀ, H6,
H6ꢀ, CH=CH2(CH2)5CH2O), 3.79 (1H, dd, J2,3 9.9, J1,2 7.7,
H2), 3.57 (1H, ddd, J 9.4, 7.0, 7.0, CH=CH2(CH2)5CH2O),
3.38 (1H, s, H5), 3.23 (1H, s, H5ꢀ), 3.20 (1H, d, J
1.3, H4ꢀꢀ), 2.11–2.02 (2H, m, CH=CH2(CH2)5CH2O), 1.80–
1.69 (2H, m, CH=CH2(CH2)5CH2O), 1.54–1.34 (6H, m,
CH=CH2(CH2)5CH2O), 1.13 (9H, s, (CH3)3C), 0.54 (3H, d,
ꢀ
ꢀ
ꢀ
ꢀ
7-Octen-1-yl 3-O-[3-O-(2-N-Acetyl-2-deoxy-3,4,6-tetra-
O-acetyl-α-D-galactopyranosyl)-4,6-O-benzylidene-
2-O-(2,3,4-tri-O-benzyl-α-L-fucopyranosyl)-β-D-
galactopyranosyl]-2-O-benzyl-4,6-O-benzylidene-
β-D-galactopyranoside 27
J5 ,6 6.4, H6ꢀꢀ). δC (100 MHz) 178.0 (C=O), 139.1 (Ph),
ꢀꢀ ꢀꢀ
139.0 (CH2=CH), 138.9 (Ph), 138.5 (Ph), 137.9 (Ph), 137.6
(Ph), 129.3 (Ph), 129.1 (Ph), 128.8 (Ph), 128.6 (Ph), 128.3
(Ph), 128.21 (Ph), 128.16 (Ph), 128.1 (2C, Ph), 128.0 (Ph),
127.9 (Ph), 127.4 (Ph), 127.34 (Ph), 127.30 (Ph), 127.2
A solution of the acceptor 25 (359 mg, 0.316 mmol) in dry Et2O
(15 mL) was treated with 4-Å molecular sieves (300 mg) and the

RESEARCH FRONT
ABO Histo-Blood Group Type V and VI Antigens
571
mixture stirred (rt, 1 h). The mixture was then cooled (−10◦C),
treated withTMSOTf (10 µL, 0.058 mmol); the trichloroacetim-
idate 26[34] (457 mg, 0.965 mmol) in dry Et2O (15 mL) was then
added dropwise and the mixture allowed to stand (20 min). The
mixture was neutralized with Et3N (0.5 mL), filtered, concen-
trated, and subjected to flash chromatography (EtOAc/hexanes,
1:3) to afford the partially pure tetrasaccharide as a colour-
less oil (270 mg, 65%). The residue was taken up in pyridine
(4 mL) and treated with AcSH (2 mL) and the solution was
stirred (3 days). The solution was concentrated and subjected
to flash chromatography (CH2Cl2/CH3OH, 20:1) to afford 27
as a colourless oil (205 mg, 78%). [α] +11.7 (c = 0.6, CH2Cl2).
Rf 0.38 (EtOAc/hexanes, 3:1). δH (500 MHz) 7.59–7.11 (30H,
m, Ph), 5.89–5.77 (1H, m, CH2=CH), 5.57 (1H, d, JNH 10.8
afford the partially pure tetrasaccharide 29 (270 mg, 60%) as a
colourless oil.
7-Octen-1-yl 4,6-O-Benzylidene-β-D-glucopyranoside 33
A stirred solution of 2,3,4,6-tetra-O-acetyl-α-d-glucopyranosyl
trichloroacetimidate 30[38] (33.9 g, 69 mmol) and 7-octen-1-ol
(11.0 g, 86 mmol) was treated with 4-Å molecular sieves (5 g)
and the mixture stirred (rt, 1 h). The mixture was then cooled
(−40◦C), treated with TMSOTf (0.5 mL) and the mixture was
allowed to warm (rt, 1 h). The reaction was quenched by the
addition of Et3N (2 mL), filtered, and subjected to flash chro-
matography (EtOAc/hexanes, 2:3) to afford a colourless oil. The
oil was taken up in CH3OH (200 mL), treated with a catalytic
amount of NaOCH3 in CH3OH and stirred (rt, 2 h); the NaOCH3
was neutralized with Amberlite IR120 (H+), filtered, and then
concentrated. The residue was subjected to flash chromato-
graphy (EtOAc/hexanes, 5:1) to afford the tetrol 32 as a white
solid (11.3 g, 57%), which was immediately used in the subse-
quent step. A solution of the tetrol 32 (11.3 g, 38.9 mmol) in
dry DMF (200 mL) was treated with benzaldehyde dimethyl
acetal (7.2 mL, 48 mmol), p-TsOH (300 mg), and the solution
was stirred (40◦C, 18 h). The solution was neutralized with Et3N
(1.5 mL), concentrated and subjected to flash chromatography
(EtOAc/hexanes, 1:1) to afford the diol 33 (14.0 g, 95%) as a
white solid. Mp 149–151◦C. [α] −46.8 (c = 0.3, CH2Cl2). Rf
0.82 (EtOAc/hexanes, 7:10). δH (500 MHz) 7.52–7.48 (2H, m,
Ph), 7.41–7.35 (3H, m, Ph), 5.86–5.77 (1H, m, CH=CH2), 5.55
(1H, s, PhCH), 5.03–4.92 (2H, m, CH=CH2), 4.41 (1H, d, J1,2
8.0, H1), 4.35 (1H, dd, J6,6 10.5, J5,6 4.9, H6), 3.93–3.77 (3H,
m, H3, H6, CH=CH2(CH2)5CH2O), 3.61–3.43 (4H, m, H2,
H4, H5, CH=CH2(CH2)5CH2O), 2.71 (1H, d, J 2.2, OH), 2.51
(1H, d, J 2.4, OH), 2.10–2.01 (2H, m, CH=CH2(CH2)5CH2O),
1.71–1.59 (2H, m, CH=CH2(CH2)5CH2O), 1.47–1.28 (6H,
m, CH=CH2(CH2)5CH2O). δC (125 MHz) 139.0 (CH=CH2),
136.9 (Ph), 129.3 (Ph), 128.3 (Ph), 126.3 (Ph), 114.3
(CH=CH2), 103.1 (C1), 101.9 (PhCH), 80.6 (C4), 73.2, 70.5,
64.6 (C2, C3, C5), 68.7 (CH=CH2(CH2)5CH2O), 66.4 (C6),
33.7 (CH=CH2(CH2)5CH2O), 29.5 (CH=CH2(CH2)5CH2O),
28.83(CH=CH2(CH2)5CH2O), 28.77(CH=CH2(CH2)5CH2O),
25.8 (CH=CH2(CH2)5CH2O). m/z (ESI) calc. [C21H30O6]Na+:
401.1935. Found: 401.1934.
NH), 5.51 (1H, d, J1 ,2 3.7, H1ꢀꢀ), 5.55 (1H, s, PhCH), 5.44
ꢀꢀ ꢀꢀ
(1H, s, PhCH), 5.13–5.08 (2H, m, H1ꢀꢀꢀ, PhCH2), 5.07–5.02
(3H, m, H1ꢀ, H4ꢀꢀꢀ, CH=CH2), 4.92–5.01 (3H, m, H3ꢀꢀꢀ, PhCH2,
CH=CH2), 4.90, 4.89 (2H, AB, J 10.0, PhCH2), 4.79 (1H, A
of AB, J 11.4, PhCH2), 4.78 (1H, A of AB, J 12.2, PhCH2),
4.64 (1H, ddd, JNH 10.8, J2
3.6, H2ꢀꢀꢀ), 4.52
ꢀꢀꢀ,3ꢀꢀꢀ
ꢀꢀꢀ,2ꢀꢀꢀ
10.6, J1
(1H, A of AB, J 11.8, PhCH2), 4.45 (1H, d, J1,2 7.8, H1), 4.44–
4.39 (2H, m, H5ꢀꢀ, PhCH2), 4.35–4.22 (5H, m, H3ꢀ, H4, H4ꢀ,
H6, H6ꢀ), 4.18 (1H, dd, J2 ,3 10.2, J1 ,2 3.7, H2ꢀꢀ), 4.13–4.01
(6H, m, H3, H3ꢀꢀ, H5ꢀꢀꢀ, H6, H6ꢀ, CH=CH2(CH2)5CH2O), 3.87–
ꢀꢀ ꢀꢀ
ꢀꢀ ꢀꢀ
3.81 (2H, m, H2, H2ꢀ), 3.71 (1H, dd, J6
ꢀꢀꢀ,6ꢀꢀꢀ
ꢀꢀꢀ,6ꢀꢀꢀ
11.5, J5 7.8,
H6ꢀꢀꢀ), 3.57 (1H, ddd, J 9.1, 7.0, 7.0, CH=CH2(CH2)5CH2O),
3.32 (1H, s, H4ꢀꢀ), 3.40, 3.27 (2H, 2 × s, H5, H5ꢀ), 3.10 (1H,
2.6, H6ꢀꢀꢀ), 2.09, 1.97, 1.78, 1.57 (12H,
ꢀꢀꢀ,6ꢀꢀꢀ
ꢀꢀꢀ,6ꢀꢀꢀ
dd, J6
11.5, J5
4 × s, CH3C=O), 2.12–2.04 (2H, m, CH=CH2(CH2)5CH2O),
1.80–1.67 (2H, m, CH=CH2(CH2)5CH2O), 1.53–1.35 (6H,
m, CH=CH2(CH2)5CH2O), 0.56 (3H, d, J5 ,6 6.2, H6ꢀꢀ). δC
ꢀꢀ ꢀꢀ
(100 MHz) 170.7 (C=O), 170.3 (C=O), 170.1 (C=O), 170.0
(C=O), 139.3 (Ph), 139.0 (CH2=CH), 138.9 (Ph), 138.41 (2C,
Ph), 138.39 (Ph), 137.4 (Ph), 129.4 (Ph), 129.2 (Ph), 128.72
(Ph), 128.71 (Ph), 128.33 (Ph), 128.30 (Ph), 128.26 (Ph),
128.23 (Ph), 128.17 (2C, Ph), 128.0 (Ph), 127.9 (Ph), 127.44
(Ph), 127.38 (Ph), 127.2 (Ph), 127.1 (Ph), 126.9 (Ph), 126.0
(Ph), 114.3 (CH2=CH), 103.8 (C1), 102.0, 101.6, 100.7 (C1ꢀ,
PhCH), 98.1 (C1ꢀꢀ), 92.1 (C1ꢀꢀꢀ), 80.2, 79.8 (C2, C3), 78.2 (C4ꢀꢀ),
75.3 (PhCH2), 75.0 (PhCH2), 74.1 (PhCH2), 72.2 (PhCH2),
76.3, 76.1, 76.0, 75.0, 70.7, 69.9 (C2ꢀ, C2ꢀꢀ, C3ꢀ, C3ꢀꢀ, C4,
C4ꢀ), 70.3 (CH=CH2(CH2)5CH2O), 69.2, 69.0 (C6, C6ꢀ), 68.9
(C3ꢀꢀꢀ), 67.6 (C4ꢀꢀꢀ), 67.3 (C5ꢀꢀ), 66.9 (C5ꢀꢀꢀ), 66.5, 66.2 (C5,
C5ꢀ), 62.5 (C6ꢀꢀꢀ), 46.4 (C2ꢀꢀꢀ), 33.8 (CH=CH2(CH2)5CH2O),
29.8 (CH=CH2(CH2)5CH2O), 29.0 (CH=CH2(CH2)5CH2O),
28.9 (CH=CH2(CH2)5CH2O), 26.2 (CH=CH2(CH2)5CH2O),
22.8 (CH3C=O), 20.74 (CH3C=O), 20.71 (CH3C=O), 20.66
(CH3C=O), 15.91 (C6ꢀꢀ). m/z (ESI) calc. [C82H97NO23]Na+:
1486.6344. Found: 1486.6348.
7-Octen-1-yl 4-O-Acetyl-2,3,6-tri-O-benzyl-β-D-
glucopyranoside 34
A solution of the alcohol 36 (15.8 mg, 0.028 mmol) in pyri-
dine (1.5 mL) was treated with Ac2O (0.5 mL) and DMAP
(2 mg) (rt, 2 h). The solution was then treated with CH3OH
(1 mL), concentrated, and subjected to flash chromatography
(EtOAc/hexanes, 1:3) to afford the ester 34 as a colour-
less oil (15 mg, 88%). [α] +1.7 (c = 0.6, CH2Cl2). Rf 0.73
(EtOAc/hexanes, 3:7). δH (500 MHz) 7.37–7.22 (15H, m,
Ph), 5.85–5.76 (1H, m, CH=CH2), 5.01–4.92 (m, 4H, H4,
CH=CH2, PhCH2), 4.71 (1H, A of AB, J 11.1, PhCH2),
4.82, 4.62 (2H, AB, J 11.6, PhCH2), 4.55, 4.52 (2H, AB,
J 12.1, PhCH2), 4.42 (1H, d, J1,2 7.9, H1), 3.99–3.93
(1H, m, CH=CH2(CH2)5CH2O), 3.60 (dd, J2,3 9.4, J3,4 9.3,
H3), 3.57–3.51 (4H, m, H5, H6, CH=CH2(CH2)5CH2O),
3.48 (1H, dd, J2,3 9.4, J1,2 7.9, H2), 1.83 (3H, s,
CH3C=O), 2.07–2.01 (2H, m, CH=CH2(CH2)5CH2O), 1.71–
1.62 (2H, m, CH=CH2(CH2)5CH2O), 1.45–1.30 (6H, m,
CH=CH2(CH2)5CH2O). δC (125 MHz) 167.2 (C=O), 136.5
(CH=CH2), 135.9 (Ph), 135.8 (Ph), 135.5 (Ph), 125.82
7-Octen-1-yl 2-O-Benzyl-3-O-[4,6-O-benzylidene-3-O-
(2,3,4,6-tetra-O-benzyl-α-D-galactopyranosyl)-2-O-(2,3,4-
tri-O-benzyl-α-L-fucopyranosyl)-β-D-galactopyranosyl]-
4,6-O-benzylidene-β-D-galactopyranoside 29
A solution of the acceptor 25 (310 mg, 0.273 mmol) in dry Et2O
(5 mL) was treated with 4-Å molecular sieves and the mixture
stirred (rt, 1 h). The mixture was then cooled (−10◦C), treated
with TMSOTf (10 µL, 0.058 mmol); the trichloroacetimidate
28[35] (700 mg, 1.02 mmol) in dry Et2O (10 mL) was then added
dropwise and the mixture allowed to stand (20 min). The mix-
ture was neutralized with Et3N (0.5 mL), filtered, concentrated,
and subjected to flash chromatography (EtOAc/hexanes, 1:4) to

RESEARCH FRONT
572
P. J. Meloncelli and T. L. Lowary
(Ph), 125.80 (Ph), 125.79 (Ph), 125.6 (Ph), 125.27 (Ph),
125.26 (Ph), 125.2 (Ph), 125.1 (Ph), 125.0 (Ph), 111.7
(CH=CH2), 101.0 (C1), 79.5, 79.2 (C2, C3), 72.5 (PhCH2),
72.4 (PhCH2), 71.1 (PhCH2), 70.9, 68.6 (C4, C5), 67.7, 67.4
(C6, CH=CH2(CH2)5CH2O), 31.2 (CH=CH2(CH2)5CH2O),
27.3 (CH=CH2(CH2)5CH2O), 26.4 (CH=CH2(CH2)5CH2O),
26.3 (CH=CH2(CH2)5CH2O), 23.5 (CH=CH2(CH2)5CH2O),
18.3 (CH3). m/z (ESI) calc. [C37H46O7]Na+: 625.3138. Found:
625.3136.
3.72 (1H, dd, J6,6 10.4, J5,6 5.4, H6), 3.63–3.52 (2H, m, H4,
CH=CH2(CH2)5CH2O), 3.50–3.40 (3H, m, H2, H3, H5), 2.54
(1H, d, J 2.1, OH), 2.09–2.01 (2H, m, CH=CH2(CH2)5CH2O),
1.72–1.62 (2H, m, CH=CH2(CH2)5CH2O), 1.47–1.30 (6H,
m, CH=CH2(CH2)5CH2O). δC (125 MHz) 139.0 (CH=CH2),
138.7 (Ph), 138.5 (Ph), 138.0 (Ph), 128.5 (Ph), 128.40 (Ph),
128.36 (Ph), 128.1 (Ph), 128.0 (Ph), 127.8 (Ph), 127.71 (Ph),
127.69 (2C, Ph), 114.2 (CH=CH2), 103.7 (C1), 84.1, 81.7
(C2, C3), 75.3 (PhCH2), 74.7 (PhCH2), 74.0 (C4), 73.7
(PhCH2), 71.7 (C5), 70.4, 70.2 (C6, CH=CH2(CH2)5CH2O),
33.7 (CH=CH2(CH2)5CH2O), 29.7 (CH=CH2(CH2)5CH2O),
28.9 (CH=CH2(CH2)5CH2O), 28.8 (CH=CH2(CH2)5CH2O),
26.0 (CH=CH2(CH2)5CH2O). m/z (ESI) calc. [C35H44O6]Na+:
583.3030. Found: 583.3031.
7-Octen-1-yl 4,6-O-Benzylidene-2,3-di-O-benzyl-
β-D-glucopyranoside 35
A stirred solution of the diol 33 (13.0 g, 34.4 mmol) in DMF
(200 mL, −20◦C) was treated with BnBr (12.2 mL, 0.103 mmol)
and NaH (60%, 3.44 g, 86 mmol) and the mixture stirred (rt,
6 h). The mixture was cooled (−20◦C), treated with CH3OH
(10 mL) and allowed to stand (rt, 10 min). The solution was
concentrated, taken up in EtOAc (500 mL) and washed with
water (400 mL), and brine (400 mL). The organic extract was
dried and then concentrated and subjected to flash chromato-
graphy (EtOAc/hexanes, 1:9) to afford the dibenzyl ether 35 as
a white solid (18.8 g, 98%). Mp 49–51◦C. [α] −27.8 (c = 1.2,
CH2Cl2). Rf 0.56 (EtOAc/hexanes, 1:5). δH (500 MHz) 7.52–
7.49 (2H, m, Ph), 7.43–7.26 (13H, m, Ph), 5.86–5.76 (1H, m,
CH=CH2), 5.59 (1H, s, PhCH), 5.04–4.91 (4H, m, PhCH2,
CH=CH2), 4.83 (1H, A of AB, J 10.9, PhCH2), 4.79 (1H, A
of AB, J 11.0, PhCH2), 4.57 (1H, d, J1,2 7.9, H1), 4.37 (1H,
dd, J6,6 10.3, J5,6 5.1, H6), 3.93 (1H, ddd, J 9.4, 6.5, 6.5,
CH=CH2(CH2)5CH2O), 3.81 (1H, dd, J6,6 10.3, J5,6 5.1, H6),
3.77 (1H, dd, J2,3 8.6, J3,4 9.1, H3), 3.71 (1H, dd, J4,5 9.2, J3,4 9.1,
H4), 3.58 (1H, ddd, 1H, J 9.4, 6.9, 9.4, CH=CH2(CH2)5CH2O),
3.48 (1H, dd, J2,3 8.6, J1,2 7.9, H2), 3.43 (1H, ddd, J5,6 9.9, J4,5
9.4, J5,6 5.1, H5), 2.09–2.02 (2H, m, CH=CH2(CH2)5CH2O),
1.72–1.62 (2H, m, CH=CH2(CH2)5CH2O), 1.47–1.31 (6H,
m, CH=CH2(CH2)5CH2O). δC (125 MHz) 139.0 (CH=CH2),
138.6 (Ph), 138.4 (Ph), 137.4 (Ph), 128.9 (Ph), 128.4 (Ph),
128.32 (Ph), 128.27 (Ph), 128.2 (Ph), 128.0 (Ph), 127.7 (Ph),
127.6 (Ph), 126.0 (Ph), 114.3 (CH=CH2), 104.2 (C1), 101.1
(PhCH), 82.2, 81.5, 90.9 (C2, C3, C4), 75.3 (PhCH2), 75.1
(PhCH2), 70.6 (CH=CH2(CH2)5CH2O), 68.8 (C6), 66.0 (C5),
33.7 (CH=CH2(CH2)5CH2O), 29.7 (CH=CH2(CH2)5CH2O),
28.9 (CH=CH2(CH2)5CH2O), 28.8 (CH=CH2(CH2)5CH2O),
26.0 (CH=CH2(CH2)5CH2O). m/z (ESI) calc. [C35H42O6]Na+:
581.2874. Found: 581.2876.
7-Octen-1-yl 4-O-(4,6-O-Benzylidene-β-D-
galactopyranosyl)-2,3,6-tri-O-benzyl-β-D-
glucopyranoside 37
A solution of the acceptor 36 (4.02 g, 7.19 mmol) in dry CH2Cl2
(50 mL) was stirred over 4-Å molecular sieves (rt, 1 h).The solu-
tion was then cooled (−40◦C), treated with BF3·OEt2 (0.5 mL),
followed by dropwise addition of the trichloroacetimidate 19[31]
(8.90 g, 18.0 mmol) and then the mixture was allowed to warm
(0◦C). The mixture was neutralized with Et3N (2 mL), concen-
trated, and subjected to flash chromatography (EtOAc/hexanes,
1:1) to afford a colourless oil, which was immediately used in the
next step. The colourless oil was taken up in CH3OH (100 mL),
treated with a solution of NaOCH3 in CH3OH and stirred (rt,
3 h). The solution was neutralized with Amberlite IR 120 (H+),
filtered, and subjected to flash chromatography (EtOAc/hexanes,
7:3) to afford the diol 37 as a colourless oil (5.3 g, 91%). [α] −3.1
(c = 1.4, CH2Cl2). Rf 0.68 (EtOAc/hexanes, 7:3). δH (500 MHz)
7.50–7.21 (20H, m, Ph), 5.86–5.77 (1H, m, CH2=CH), 5.46
(1H, s, PhCH), 5.03–4.91 (5H, m, PhCH2, CH2=CH), 4.73
(1H, A of AB, J 10.1, PhCH2), 4.74, 4.62 (2H, AB, J 12.3,
PhCH2), 4.58 (1H, d, J1 ,2 8.5, H1ꢀ), 4.40 (1H, d, J1,2 8.1,
H1), 4.06–3.99 (4H, m, H4, H4ꢀ, H6, H6ꢀ), 3.95 (1H, ddd,
J 9.5, 6.4, 6.4, CH=CH2(CH2)5CH2O), 3.80 (1H, dd, J6,6
ꢀ
ꢀ
11.6, J5,6 1.9, H6), 3.75 (1H, dd, J6 ,6 12.5, J5 ,6 1.5, H6ꢀ),
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
3.73–3.68 (2H, m, H3, H5), 3.64 (1H, dd, J2 ,3 9.0, J1 ,2 8.5,
H2ꢀ), 3.54 (1H, ddd, J 9.5, 6.8, 6.8, CH=CH2(CH2)5CH2O),
3.51–3.44 (3H, m, H2, H3ꢀ, OH), 2.87 (1H, s, H5ꢀ), 2.49
(1H, d, J 7.3, OH), 2.10–2.01 (2H, m, CH=CH2(CH2)5CH2O),
1.74–1.61 (2H, m, CH=CH2(CH2)5CH2O), 1.49–1.29 (6H,
m, CH=CH2(CH2)5CH2O). δC (125 MHz) 139.2 (CH2=CH),
139.0 (Ph), 138.4 (Ph), 137.69 (Ph), 137.67 (Ph), 129.1 (Ph),
128.4 (Ph), 128.3 (Ph), 128.2 (Ph), 128.1 (2C, Ph), 128.0
(Ph), 127.8 (Ph), 127.6 (Ph), 127.2 (2C, Ph), 126.4 (Ph), 114.3
(CH2=CH), 103.9, 103.5 (C1, C1ꢀ), 101.3 (PhCH), 83.7 (C3),
82.1 (C2), 77.6 (C4), 75.2 (PhCH2), 75.1, 74.2 (C4ꢀ, C5),
74.9 (PhCH2), 73.5 (PhCH2), 72.7, 72.5 (C2ꢀ, C3ꢀ), 70.10
(CH=CH2(CH2)5CH2O), 68.9, 68.5 (C6, C6ꢀ), 66.7 (C5ꢀ), 33.7
(CH=CH2(CH2)5CH2O), 29.7 (CH=CH2(CH2)5CH2O), 28.9
(CH=CH2(CH2)5CH2O), 28.8 (CH=CH2(CH2)5CH2O), 26.1
(CH=CH2(CH2)5CH2O). m/z (ESI) calc. [C48H58O11]Na+:
833.3871. Found: 833.3872.
7-Octen-1-yl 2,3,6-Tri-O-benzyl-β-D-glucopyranoside 36
A stirred solution of the alkene 35 (7.47 g, 13.3 mmol) in dry
CH2Cl2 (200 mL) was treated with 4-Å molecular sieves (5 g)
and the mixture stirred (rt, 1 h). The mixture was then cooled
(0◦C) and treated with triethylsilane (10.7 mL, 66.9 mmol) and
BF3·OEt2 (3.3 mL, 26.6 mmol) and the mixture stirred (rt, 5 h).
The mixture was neutralized with Et3N (5 mL), diluted with
CH2Cl2 (300 mL), and washed with saturated NaHCO3, water
and then brine. The organic extract was concentrated and sub-
jected to flash chromatography (EtOAc/hexanes, 1:4) to afford
thealcohol 36asacolourlessoil(4.7 g, 64%). [α]−18.0(c = 0.3,
CH2Cl2). Rf 0.73 (EtOAc/hexanes, 3:7). δH (500 MHz) 7.40–
7.26 (15H, m, Ph), 5.87–5.76 (1H, m, CH=CH2), 5.03–4.93
(4H, m, PhCH2, CH=CH2), 4.75 (1H, A ofAB, J 11.4, PhCH2),
4.73 (1H, A of AB, J 10.7, PhCH2), 4.62, 4.58 (2H, AB, J
12.3, PhCH2), 4.43 (1H, d, J1,2 7.2, H1), 3.99–3.93 (1H, m,
CH=CH2(CH2)5CH2O), 3.79 (1H, dd, J6,6 10.4, J5,6 3.9, H6),
7-Octen-1-yl 4-O-(4,6-O-Benzylidene-3-O-pivaloyl-
β-D-galactopyranosyl)-2,3,6-tri-O-benzyl-
β-D-glucopyranoside 38
A stirred solution of the diol 37 (5.93 g, 7.32 mmol) in
pyridine (50 mL) was treated with trimethylacetyl chloride

RESEARCH FRONT
ABO Histo-Blood Group Type V and VI Antigens
573
(1.16 mL, 9.52 mmol) and the solution was stirred. The solu-
tion was concentrated and subjected to flash chromatography
(EtOAc/hexanes, 1:1) to afford the alcohol 38 as a white
solid (6.22 g, 95%). [α] +42.4 (c = 0.5, CH2Cl2). Rf 0.55
(EtOAc/hexanes, 3:2). δH (500 MHz) 7.52–7.18 (20H, m, Ph),
5.86–5.77 (1H, m, CH2=CH), 5.40 (1H, s, PhCH), 5.05–
4.90 (5H, m, CH2=CH, PhCH2), 4.73 (1H, A of AB, J
11.9, PhCH2), 4.72 (1H, A of AB, J 10.9, PhCH2), 4.67–
4.63 (2H, m, H1ꢀ, H3ꢀ), 4.59 (1H, A of AB, J 12.4, PhCH2),
3.41 (1H, dd, J2,3 9.1, J1,2 8.0, H2), 3.31–3.26 (1H, m, H5),
3.13 (1H, s, H5ꢀ), 2.06–2.01 (2H, m, CH=CH2(CH2)5CH2O),
1.72–1.59 (2H, m, CH=CH2(CH2)5CH2O), 1.47–1.29 (6H,
m, CH=CH2(CH2)5CH2O), 1.08 (3H, d, J5 ,6 6.5, H6ꢀꢀ). δC
ꢀꢀ ꢀꢀ
(125 MHz) 139.0 (CH2=CH), 138.8 (Ph), 138.74 (Ph), 138.69
(Ph), 138.6 (Ph), 138.3 (Ph), 138.1 (Ph), 137.5 (Ph), 129.0
(Ph), 128.9 (Ph), 128.6 (Ph), 128.43 (Ph), 128.42 (Ph), 128.32
(2C, Ph), 128.27 (Ph), 128.24 (Ph), 128.19 (Ph), 128.10 (Ph),
128.06 (Ph), 128.0 (Ph), 127.7 (Ph), 127.64 (Ph), 127.60 (Ph),
127.57 (Ph), 127.54 (Ph), 127.43 (Ph), 127.38 (Ph), 126.6 (Ph),
114.2 (CH2=CH), 103.7 (C1), 101.4, 101.2 (C1ꢀ, PhCH), 99.2
(C1ꢀꢀ), 82.9, 81.7 (C2, C3), 79.0, 78.1, 77.6, 77.3, 76.3 (C2ꢀ,
C2ꢀꢀ, C3ꢀꢀ, C4, C4ꢀꢀ), 75.8 (C4ꢀ), 76.0 (PhCH2), 75.11 (PhCH2),
75.07 (C5), 74.8 (PhCH2), 74.1 (PhCH2), 73.4 (PhCH2), 73.0
(PhCH2), 72.9 (C3ꢀ), 70.0 (CH=CH2(CH2)5CH2O), 69.0, 68.1
(C6, C6ꢀ), 67.3, 66.5 (C5ꢀ, C5ꢀꢀ), 33.7 (CH=CH2(CH2)5CH2O),
29.7 (CH=CH2(CH2)5CH2O), 29.0 (CH=CH2(CH2)5CH2O),
28.8 (CH=CH2(CH2)5CH2O), 26.0 (CH=CH2(CH2)5CH2O),
16.8(C6ꢀꢀ). m/z (ESI)calc. [C75H86O15]Na+:1249.5859. Found:
1249.5855.
4.39 (1H, d, J1,2 7.8, H1), 4.17 (1H, d, J3 ,4 3.7, H4ꢀ),
4.04–3.90 (4H, m, H4, H6, H6ꢀ, CH=CH2(CH2)5CH2O),
ꢀ
ꢀ
3.87 (1H, dd, J2 ,3 9.7, J1 ,2 7.9, H2ꢀ), 3.78 (1H, dd, J6,6
11.6, J5,6 2.0, H6), 3.73–3.65 (2H, m, H3, H6ꢀ), 3.49–3.42,
3.60–3.50 (4H, 2 × m, H2, H5, OH, CH=CH2(CH2)5CH2O),
2.81 (1H, s, H5ꢀ), 2.09–2.01 (2H, m, CH=CH2(CH2)5CH2O),
1.72–1.61 (2H, m, CH=CH2(CH2)5CH2O), 1.47–1.31 (6H, m,
CH=CH2(CH2)5CH2O), 1.22 (9H, s, (CH3)3C). δC (125 MHz)
178.3 (C=O), 139.2 (Ph), 139.0 (CH2=CH), 138.4 (Ph), 137.9
(Ph), 137.5 (Ph), 128.6 (Ph), 128.4 (Ph), 128.3 (Ph), 128.2
(Ph), 128.14 (Ph), 128.12 (Ph), 127.92 (Ph), 127.86 (Ph), 127.6
(Ph), 127.1 (Ph), 126.9 (Ph), 126.0 (Ph), 114.3 (CH2=CH),
103.9 (2C, C1, C1ꢀ), 100.4 (PhCH), 83.9 (C3), 82.2 (C2),
77.7 (C4), 75.1 (PhCH2), 74.8 (PhCH2), 74.0, 73.4, 73.1
(C3ꢀ, C4ꢀ, C5), 73.7 (PhCH2), 70.1 (CH=CH2(CH2)5CH2O),
69.5 (C2ꢀ), 68.8 (2C, C6, C6ꢀ), 66.5 (C5ꢀ), 38.7 ((CH3)3C),
33.7 (CH=CH2(CH2)5CH2O), 29.7 (CH=CH2(CH2)5CH2O),
28.9 (CH=CH2(CH2)5CH2O), 28.8 (CH=CH2(CH2)5CH2O),
27.1 ((CH3)3C), 26.0 (CH=CH2(CH2)5CH2O). m/z (ESI) calc.
[C53H66O12]Na+: 917.4446. Found: 917.4449.
ꢀ
ꢀ
ꢀ
ꢀ
7-Octen-1-yl 4-O-[3-O-(2-N-Acetyl-2-deoxy-3,4,6-tetra-
O-acetyl-α-D-galactopyranosyl)-4,6-O-benzylidene-
2-O-(2,3,4-tri-O-benzyl-α-L-fucopyranosyl)-
β-D-galactopyranosyl]-2,3,6-tri-O-benzyl-
β-D-glucopyranoside 41
A solution of the acceptor 40 (365 mg, 0.297 mmol) in dry Et2O
(15 mL) was treated with 4-Å molecular sieves (250 mg) and the
mixture stirred (rt, 1 h). The mixture was then cooled (−10◦C),
treated withTMSOTf (10 µL, 0.058 mmol); the trichloroacetim-
idate 26[34] (457 mg, 0.965 mmol) in dry Et2O (15 mL) was then
added dropwise and the mixture allowed to stand (20 min). The
mixture was neutralized with Et3N (0.5 mL), filtered, concen-
trated, and subjected to flash chromatography (EtOAc/hexanes,
1:3) to afford the partially pure tetrasaccharide as a colourless
oil (330 mg, 67%). The residue was taken up in pyridine (4 mL)
and treated with AcSH (2 mL) and the solution was stirred (3
days).The solution was concentrated and subjected to flash chro-
matography (CH2Cl2/CH3OH, 20:1) to afford 41 as a colourless
oil (230 mg, 70%). [α] −3.4 (c = 0.3, CH3OH). δH (500 MHz)
7.55–7.12 (35H, m, Ph), 5.87–5.75 (1H, m, CH2=CH), 5.47
7-Octen-1-yl 4-O-[4,6-O-Benzylidene-2-O-(2,3,4-tri-
O-benzyl-α-L-fucopyranosyl)-β-D-galactopyranosyl]-
2,3,6-tri-O-benzyl-β-D-glucopyranoside 40
A solution of the alcohol 38 (2.90 g, 3.24 mmol) in dry
Et2O/CH2Cl2 (9:1, 50 mL) was treated with 4-Å molecular
sieves (2 g) and the mixture was stirred (rt, 1 h). The mixture
was then cooled (−10◦C), treated with TMSOTf (100 µL), fol-
lowed by dropwise addition of the trichloroacetimidate 23[33]
(5.20 g, 9.01 mmol) in dry ether (15 mL). The mixture was
treated with Et3N (0.5 mL), filtered, and subjected to flash
chromatography (EtOAc/hexanes, 1:3) to yield the trisaccha-
ride as a colourless oil (3.34 g, 78%). The oil was taken up in
CH3OH (100 mL), treated with catalytic LiOCH3 (150 mg), and
the solution was heated at reflux (5 days). The solution was
allowed to cool, neutralized with Amberlite IR 120 (H+), fil-
tered, and subjected to flash chromatography (EtOAc/hexanes,
1:3) to afford first unreacted starting material (480 mg, 16%);
further elution (EtOAc/hexanes, 1:2) afforded the alcohol 40 as
a colourless oil (1.96 g, 68%). [α] −40.8 (c = 0.4, CH2Cl2). Rf
0.44 (EtOAc/hexanes, 3:2). δH (500 MHz) 7.58–7.09 (35 H, m,
Ph), 5.87–5.76 (1H, m, CH2=CH), 5.58 (1H, s, PhCH), 5.16
(1H, d, J1 ,2 3.9, H1ꢀꢀ), 5.43 (1H, s, PhCH), 5.42 (1H, d, J 9.7,
ꢀꢀ ꢀꢀ
3.7, H1ꢀꢀꢀ),
ꢀꢀꢀ,2ꢀꢀꢀ
NH), 5.23–5.17 (2H, m, PhCH2), 5.10 (1H, d, J1
5.03–4.93 (6H, m, H3ꢀꢀꢀ, H4ꢀꢀꢀ, PhCH2, CH=CH2), 4.89 (1H,
A of AB, J 10.6, PhCH2), 4.74 (1H, A of AB, J 10.5, PhCH2),
4.74 (1H, A of AB, J 11.8, PhCH2), 4.70–4.57 (7H, m, H1ꢀ,
H2ꢀꢀꢀ, PhCH2), 4.40–4.34 (2H, m, H5ꢀꢀ, H6ꢀ), 4.35 (1H, d, J1,2
8.0, H1), 4.29 (1H, d, J3 ,4 3.8, H4ꢀ), 4.25 (1H, dd,ꢀ J2 ,3 10.1,
ꢀ
ꢀ
ꢀꢀ ꢀꢀ
ꢀꢀ
ꢀꢀ ꢀꢀ
ꢀ
ꢀ
ꢀ
ꢀ
J1 ,2 3.9, H2 ), 4.21 (1H, dd, J2 ,3 9.6, J1 ,2 8.1, H2 ), 4.12 (1H,
dd, J3,4 9.1, J4,5 9.1, H4), 4.14–4.07 (1H, m, H5ꢀꢀꢀ), 4.02–3.94
(2H, m, H6ꢀ, CH=CH2(CH2)5CH2O), 3.90 (1H, dd, J6,6 11.5,
(1H, A of AB, J 10.4, PhCH2), 5.05 (1H, d, J1 ,2 3.4, H1ꢀꢀ),
J5,6 3.7, H6), 3.86 (1H, dd, J2 ,3 10.1, J3 ,4 2.6, H3ꢀꢀ), 3.84
ꢀꢀ ꢀꢀ
ꢀꢀ ꢀꢀ
ꢀꢀ ꢀꢀ
(1H, dd, J2 ,3 9.4, J3 ,4 3.8, H3ꢀ), 3.71–3.64 (3H, m, H4ꢀꢀ, H6,
H6ꢀꢀꢀ), 3.59 (1H, ddd, J 9.5, 6.8, 6.8, CH=CH2(CH2)5CH2O),
3.50 (1H, dd, J2,3 9.0, J3,4 9.1, H3), 3.49 (1H, dd, J2,3 9.0,
J1,2 8.0, H2), 3.20–3.14 (2H, m, H5, H5ꢀ), 3.04 (1H, dd,
ꢀ
ꢀ
ꢀ
ꢀ
5.03–5.01, 4.97–4.93 (3H, m, PhCH2, CH2=CH), 4.82 (1H, A
of AB, J 11.6, PhCH2), 4.81 (1H, A of AB, J 12.1, PhCH2),
4.76–4.70 (4H, m, PhCH2), 4.89, 4.64 (2H, AB, J 10.9, PhCH2),
4.67, 4.43 (2H, AB, J 12.4, PhCH2), 4.42 (1H, d, J1 ,2 7.9, H1ꢀ),
ꢀ
ꢀ
4.35 (1H, d, J6 ,6 12.4, H6ꢀ), 4.34 (1H, d, J1,2 7.9, H1), 4.14
11.5, J5
3.6, H6ꢀꢀꢀ), 2.09, 1.97, 1.81, 1.46 (12H,
ꢀ
ꢀ
ꢀꢀꢀ,6ꢀꢀꢀ
J6
ꢀꢀꢀ,6ꢀꢀꢀ
(1H, d, J3 ,4 3.6, H4ꢀ), 4.07 (1H, dd, J2 ,3 6.8, J1 ,2 3.4, H2ꢀꢀ),
4 × s, CH3C=O), 2.10–2.01 (2H, m, CH=CH2(CH2)5CH2O),
ꢀ
ꢀ
ꢀꢀ ꢀꢀ
ꢀꢀ ꢀꢀ
4.09–4.00 (2H, m, H4, H4ꢀꢀ), 3.98 (1H, dd, J6 ,6 12.4, J5 ,6 1.5,
H6ꢀ), 3.97–3.87(4H, m, H3ꢀꢀ, H5ꢀꢀ, H6, CH=CH2(CH2)5CH2O),
1.74–1.66 (2H, m, CH=CH2(CH2)5CH2O), 1.48–1.38 (6H,
ꢀ
ꢀ
ꢀ
ꢀ
m, CH=CH2(CH2)5CH2O), 1.16 (3H, d, J5 ,6 6.6, H6ꢀꢀ). δC
ꢀꢀ ꢀꢀ
3.81 (1H, dd, J2 ,3 9.7, J1 ,2 7.9, H2ꢀ), 3.69–3.57 (3H, m,
H3ꢀ, H6, CH=CH2(CH2)5CH2O), 3.54–3.46 (2H, m, H3, OH),
(125 MHz) 170.4 (C=O), 170.3 (C=O), 170.1 (C=O), 170.0
ꢀ
ꢀ
ꢀ
ꢀ
(C=O), 139.4 (Ph), 139.0 (CH2=CH), 138.6 (Ph), 138.52

RESEARCH FRONT
574
P. J. Meloncelli and T. L. Lowary
(Ph), 138.50 (Ph), 138.4 (Ph), 138.3 (Ph), 137.7 (Ph), 129.1
(Ph), 129.0 (Ph), 128.42 (Ph), 128.36 (Ph), 128.32 (3C, Ph),
128.29 (Ph), 128.25 (Ph), 128.20 (Ph), 128.19 (Ph), 127.8 (Ph),
127.7 (Ph), 127.55 (Ph), 127.53 (Ph), 127.40 (2C, Ph), 127.36
(Ph), 127.3 (Ph), 126.4 (Ph), 126.3 (Ph), 114.3 (CH2=CH),
103.8 (C1), 101.3, 100.8 (C1ꢀ, PhCH), 98.3 (C1ꢀꢀ), 92.1 (C1ꢀꢀꢀ),
83.0, 71.7 (C2, C3), 79.9, 77.2, 76.5, 75.8, 75.5, 75.5, 71.3,
70.6 (C2ꢀ, C2ꢀꢀ, C3ꢀ, C3ꢀꢀ, C4, C4ꢀ, C4ꢀꢀ, C5), 76.2 (PhCH2),
75.3 (PhCH2), 74.7 (PhCH2), 7.36 (PhCH2), 73.4 (PhCH2),
72.1 (PhCH2), 70.1 (CH=CH2(CH2)5CH2O), 69.0, 67.9 (C6,
C6ꢀ), 68.8, 67.7, 67.4 (C3ꢀꢀꢀ, C4ꢀꢀꢀ, C5ꢀꢀꢀ), 66.7, 66.4 (C5ꢀ,
C5ꢀꢀ), 63.0 (C6ꢀꢀꢀ), 46.5 (C2ꢀꢀꢀ), 33.8 (CH=CH2(CH2)5CH2O),
29.8 (CH=CH2(CH2)5CH2O), 29.0 (CH=CH2(CH2)5CH2O),
28.9 (CH=CH2(CH2)5CH2O), 26.1 (CH=CH2(CH2)5CH2O),
22.6 (CH3C=O), 20.69 (CH3C=O), 20.66 (CH3C=O), 20.6
(CH3C=O), 16.7 (C6ꢀꢀ). m/z (ESI) calc. [C89H105NO23]Na+:
1578.6970. Found: 1578.6986.
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A solution of the acceptor 40 (320 mg, 0.261 mmol) in dry Et2O
(5 mL) was treated with 4-Å molecular sieves and the mixture
stirred (rt, 1 h). The mixture was then cooled (−10◦C), treated
with TMSOTf (10 µL, 0.058 mmol); the trichloroacetimidate
28[35] (700 mg, 1.02 mmol) in dry Et2O (10 mL) was then added
dropwise and the mixture was allowed to stand (20 min). The
mixture was neutralized with Et3N (0.5 mL), filtered, concen-
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as a colourless oil.
Acknowledgements
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The present work was supported by the Natural Sciences and Engineering
Research Council of Canada, the Canadian Institutes of Health Research,
and the Alberta Ingenuity Centre for Carbohydrate Science.
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