Glycosylidene carbenes: Part 32: Reaction of glycosylidene diaziridines with acylating and sulfonylating agents

Article abstract of DOI:10.1002/hlca.200390202

Acylation and sulfonylation of the N,N'-unsubstituted glucosylidenespirodiaziridines 1A/1B 95:5 with Ac₂O, BzCl, FmocCl, TsCl, (naphthalen-2-yl)sulfonyl, and (2,4,6-triisopropylphenyl)sulfonyl chloride, and concomitant rearrangement gave the ac

Full text of DOI:10.1002/hlca.200390202

2490
Helvetica Chimica Acta Vol. 86 (2003)
Glycosylidene Carbenes
Part 32
Reaction of Glycosylidene Diaziridines with Acylating and Sulfonylating Agents
by Sissi E. Mangholz, Karin Briner, Bruno Bernet, and Andrea Vasella*
Laboratorium f¸r Organische Chemie, ETH-Hˆnggerberg, CH-8093 Z¸rich
¬
Dedicated to the memory of Jorge F. Lopez-Herrera
Acylation and sulfonylation of the N,N'-unsubstituted glucosylidenespirodiaziridines 1A/1B 95 :5 with
Ac2O, BzCl, FmocCl, TsCl, (naphthalen-2-yl)sulfonyl, and (2,4,6-triisopropylphenyl)sulfonyl chloride, and
concomitant rearrangement gave the acylated and sulfonylated gluconolactone hydrazones 2B 2G in 40 83%
yield (Scheme 2). Similarly, the galacto and manno analogues 3A/3B 95 :5 and 5A/5B 55 :45 and the
mannofuransoylidene-diaziridine 30 were acetylated and tosylated to give 4A, 4B, 6, 31A, and 31B (55 73%
yield; Schemes 2 and 5). 15N-Labelling of 11A/11B and 14A/14B showed that the pseudoequatorial NH of the
gluco diaziridines 1 and the pseudoaxial NH of the galacto diaziridines 3 were preferentially acetylated and
tosylated (Scheme 3). Sulfonylation of the N-methylated diaziridines 19A/19B 72 :28, 22A/22B 85 :15, 25A/25B
85 :15, 28A/28B 80:20, and 33A/33B/33C/33D 76 :4 :12 :8 yielded the N-methyl-N-tosylglyconolactone
hydrazones 20, 23, 26, 29, and 34 (44 66%; Schemes 4 and 5). The methylated N-atom of the diaziridines
proved more reactive, irrespective of the configuration at C(2) and C(4). The products were readily hydrolysed
to glyconolactones.
Introduction. The reactivity of glycosylidene diaziridines has not been well-
explored. Apart from an investigation of their formation [1], with special emphasis on
the stereoselectivity of the addition of NH3 and MeNH2 to the precursor glycono-
lactone oxime sulfonates [2], only the oxidation of these diaziridines with iodine and
Et3N or Me3N in MeOH, Et2O, or CH2Cl2 [3] to N-unsubstituted-glycosylidene
diazirines was investigated. These diazirines have been studied as precursors of
glycosylidene carbenes [3 5].
The reactivity of 3-alkyldiaziridines has been explored more extensively. Their
reaction with electrophiles is strongly influenced by the nature of the electrophile and
by the N-substituents. Attack of electrophiles on the diaziridines I leads to
diaziridinium ions II (Scheme 1). For R3 ˆ H, deprotonation of II afforded substituted
diaziridines III [6 10]. Alternatively, diaziridine ring opening of II led to the
hydrazonium ions IV, which were transformed into hydrazones V (R4 ˆ H) [11][12]
and into azomethine imines VI (R3 ˆ H) [13]. Hydrolysis of IV afforded ketones VII
and hydrazines VIII [13a][14][15]. This transformation to hydrazines constitutes a
valuable method for the selective preparation of otherwise hardly accessible N-alkyl-
and N,N'-dialkylhydrazines [16]. The reaction of 1,3,3-trimethyldiaziridine with AcCl
led to a 4 :1 mixture of N-methyl-N'-isopropylidene-acethydrazide and 2-acetyl-1,3,3-
trimethyldiaziridine [17].
Except for the oxidation with I2, we found no reaction of glycosylidene diaziridines,
nor of any other 3-alkoxydiaziridine with electrophiles. We have examined the

Helvetica Chimica Acta Vol. 86 (2003)
2491
‡
Scheme 1. Products Obtained from Diaziridines I (R1 R4 ˆ alkyl or H) upon Reaction with Electrophiles E
E
R3
R3
E
E+
R3 = H
R1
R2
R1
R2
R1
R2
N
N
N+
N
N
N
C
C
C
R4
R4
R4
I
II
III
R1
R1
R2
C
C
N
E
C
O
R2
N
R3
R
4 = H
R1
R4
V
VII
C
N+
+
E
R2
N
R1
R2
E
R4
N–
R
3 = H
HN
N
E
R3
N+
IV
R3
R4
VI
VIII
reactions of glycosylidene-diaziridines with acylating and sulfonylating reagents, and
describe the results of these experiments.
Results and Discussion. 1. Acylation and Sulfonylation of N,N'-Unsubstituted
Pyranosylidene-diaziridines. Scouting experiments showed that thermolysis of the d-
gluco diaziridines 1A/1B 95 :5 [2] at 808 in toluene led to a mixture of the N-
unsubstituted lactone hydrazone 2A, the corresponding glyconolactone, and traces of
side products (Scheme 2). This lactone hydrazone decomposed during an attempted
isolation, and we focused our investigation on the formation and rearrangement of N-
acyl- and N-sulfonyldiaziridines.
Acetylation of 1A/1B 95 :5 with one equiv. Ac2O in CH2Cl2 at 0 258 gave the N-
acetylhydrazone 2B in 70 80% yield. Similar results were obtained upon acetylation
either with Ac2O and pyridine (1 equiv. each) in CH2Cl2, or in a 1:1 mixture of Ac2O
and pyridine. With stoichiometric amounts of Ac2O, the reaction was typically
terminated within 12 h, while the use of excess Ac2O reduced the reaction time to 1 h.
Acetylation of the d-galacto diaziridines 3A/3B 95 :5 [2] with excess Ac2O in
CH2Cl2 for 90min at room temperature proceeded similarly, yielding 83% of the N-
acetylhydrazone 4A and 5% of the 1,3,4-oxadiazole 9. Prolonging the reaction time to
3 h reduced the yield of 4A to 65% and increased that of 9 to 8%. Acetylation of 3A/
3B 95 :5 with 1.07 equiv. of Ac2O provided 73% of 4A and 6% of the 1,4-dihydro-
1,2,4,5-tetrazine 10.
Benzoylation of 1A/1B 95 :5 with 1.1 equiv. Bz2O in pyridine for 20.5 h gave 61% of
the N-benzoylhydrazone 2C and 8% of the oxadiazole 7 (Scheme 2), whereas
benzoylation with 1 equiv. BzCl in pyridine afforded only 14% of 2C besides 10% of
the 1,3,4-oxadiazole 7 and 27% of its benzoate 8. Similarly, treatment of 1A/1B 95 :5
with 1.2 equiv. FmocCl and Na2CO3 ¥ 10 H O in dioxane [18] yielded 40% of the
2
hydrazone 2D.

2492
Helvetica Chimica Acta Vol. 86 (2003)
Scheme 2
OBn
O
OBn
O
H
O
H
BnO
BnO
BnO
BnO
N
N
+
NHR
BnO
BnO
N
N
N
2A R = H
2B R = Ac
2C R = Bz
2D R = Fmoc
2E R = Ts
H
H
95 : 5
1A
1B
2F R = (naphthalen-2-yl)sulfonyl
2G R = (2,4,6-triisopropylphenyl)sulfonyl
BnO
BnO
BnO
BnO
OBn
O
OBn
O
H
O
H
N
N
+
NHR
BnO
BnO
N
N
N
H
H
95 : 5
4A R = Ac
4B R = Ts
3A
3B
BnO
BnO
OBn
O
OBn
O
H
O
H
BnO
BnO
BnO
BnO
N
N
+
NHTs
N
N
N
H
6
5A H
55 : 45
5B
N
NH
N
BnO
OBn
OBn
BnO
BnO
OBn
OR
OBn
OH
BnO
BnO
O
O
Ph
Me
HN
BnO
HO
BnO
BnO
OBn BnO
N
N
N N
OH
7 R = H
8 R = Bz
9
10
BnO
OBn
Sulfonylations were performed with 1.1 1.2 equiv. of the sulfonylating agent in
pyridine at ambient temperature. Sulfonylation of 1A/1B 95 :5 with TsCl, naphthalene-
2-sulfonyl chloride, and 2,4,6-triisopropylbenzenesulfonyl chloride gave 81% of 2E
[19], 83% of 2F, and 64% of 2G, respectively. Similarly, the d-galacto diaziridines 3A/
3B 95 :5 and of the d-manno analogues 5A/5B 55 :45 [2] yielded 4B and 6 in 63 and
55%, respectively.
No diacylated or disulfonylated glycosylidene-diaziridines or hydrazones were
obtained, even when 1A/1B 95 :5 was treated with large excesses of Ac2O, BzCl, or
TsCl1). This evidences a facile rearrangement of monoacetylated and monosulfonyl-
ated 3-alkoxydiaziridines. The acylated hydrazones 2B, 2C, 2D, and 4A are the major
products, although the rearrangement of the acylated pyranosylidene-diaziridines is
less selective than that of the corresponding sulfonylated diaziridines. The minor 1,3,4-
oxadiazoles 7, 8, and 9 are formed by a 1,5-electrocyclic ring closure of an intermediate
1
)
For the N,N'-diacylation of 3,3-dialkyldiaziridines, see [20 22].

Helvetica Chimica Acta Vol. 86 (2003)
2493
N-acyl azomethine imine (corresponding to VI in Scheme 1)2). The 1,4-dihydro-1,2,4,5-
tetrazine 10 is the product of (AcOH-catalyzed?) rearrangement of 3A/3B to 4
(R ˆ H), followed by dimerisation (cf. [24]).
At 258, the acetylated lactone hydrazones 2B and 4A are mixtures of diaster-
eoisomers resulting from rotation about the NHÀC(O)Me bond3). A single
diastereoisomer was observed in the NMR spectra of the benzoylated lactone
hydrazones 2C and 4B, and of the Fmoc analogue 2D. The (Z)/(E) ratio was 7:3 for 2B
in CDCl3, 9 :1 for 2B in C6D6, 11:9 for 2B in (D6)DMSO, 4 :1 for 4A in CDCl3, and
4
10:1 for 4A in C6D6 ). In CDCl3, the NH of the major diastereoisomer resonates at
higher field (2B: 8.70 vs. 8.80ppm; 4A: 8.76 vs. 9.05 ppm); C(1) resonates at higher
field (2B: 143.7 vs. 146.8 ppm; 4A: 144.4 vs. 146.5 ppm), Me also at higher field (2B:
19.9 vs. 21.7 ppm; 4A: 19.9 vs. 21.2 ppm), but CˆO at lower field (2B: 171.9 vs.
165.6 ppm; 4A: 171.6 vs. 165.5 ppm; Tables 2 and 3, and Exper. Part). As expected, a
single set of signals was observed for 2B and 4A at 758 in CDCl3 and for 2B at 1008 in
(D6)DMSO (see Exper. Part).
The pyranose ring of the glucosylidene hydrazides 2B 2G adopts a 1S5 conforma-
tion as evidenced by J(2,3) ˆ 1.8 2.5, J(3,4) ˆ 4.2 5.0, and J(4,5) ˆ 9.6 10.2 Hz
(Table 2 in Exper. Part). This same conformation had been observed for protected
gluconolactone oximes and hydrazones [19][26][27]. The pyranose ring of the
galactosylidene hydrazides 4A 4B (J(2,3) ˆ 3.8 6.5, J(3,4) ˆ 2.7 3.7, and J(4,5) ˆ
2.2 2.6 Hz) and of the mannosylidene hydrazide 6 (J(2,3) ˆ 3.1, J(3,4) ˆ J(4,5) ˆ
4
8.9 Hz) is a flattened C1. The (Z) configuration of the CˆN bond of 2B 2G is
revealed by the chemical-shift value of C(1) resonating at 143.7 152.9 ppm (Table 3 in
Exper. Part)5).
The OH groups of 7, 9, and 10 in CDCl3 resonate at 2.41 2.78 ppm (Table 4 in
Exper. Part). The values of J(4,OH) of the arabinitol 7 and the lyxitols 9 and 10 (5.6 vs.
7.6 8.4 Hz) reveal the presence of unequal intramolecular H-bonds. Typical chemical
shifts were observed for C(2) and C(4) of the 1,3,4-oxadiazole moiety of 7 9 (163.7
165.1 ppm; cf. [31][32]), and for C(3) and C(6) of the 1,4-dihydro-1,2,4,5-tetrazine
nucleus of 10 (149.7 ppm; cf. [2][33 35]). The NH signal of 10 is hidden by the signals
of the Ph groups. The IR spectrum corroborates the structure of 10 (OH band at
3550cm À1 and NH band at 3370cm À1).
The nucleophilic properties of the pseudoequatorial and pseudoaxial NH groups of
N-unsubstituted glycosylidene diazirines should differ. To explore the difference, we
acetylated and sulfonylated isotopomeric mixtures of the 15N labelled d-gluco and d-
galacto diaziridines 11 and 14 [2] (Scheme 3). Treatment of 11A/11B 75 :25 with excess
2
)
For the formation of 2,3-dihydro-1,3,4-oxadiazoles from N-acyl-3,3-dialkyl-diaziridines, see
[13d][20][21][23].
For (E)/(Z) diastereoisomers of carbohydrate-derived acetamides, see [25] and refs. cit. therein.
After one week at ambient temperature, (Z)-2B/(E)-2B 7:3 in CDCl3 was completely transformed into
(Z)-2B, suggesting that (E)-2B is preferred in the solid state.
The chemical shift for C(1) of glycosylidene imines is strongly influenced by the configuration of the
double bond (d(E) d(Z) ˆ 17 ppm for lactone hydrazones [28] and 8 12 ppm for lactone oximes
[26][29][30]), the substituents at C(2) and at N, the ring size (d(furanosylidene) d(pyranosylidene) ˆ 4
5.5 ppm for lactone hydrazones [19][28] and 3 5 ppm for lactone oximes [26]), and the conformation of
the ring. C(1) of (Z)- and (E)-N'-(2,3,5-tri-O-benzyl-d-ribofuranosylidene)toluene-4-sulfonohydrazide
resonates at 152.6 and 169.5 ppm, respectively [28].
3
4
)
)
5
)

2494
Helvetica Chimica Acta Vol. 86 (2003)
Ac2O gave a 1:1 mixture of the isotopomers 12A and 12B (77%), evidencing that the
pseudoequatorial and the pseudoaxial NH groups were acetylated to the same extent.
Repetition of the reaction with a 78 :22 mixture of 11A and 11B, and equimolar
amounts of Ac2O afforded 12A/12B 55 :45, evidencing a slightly higher nucleophilicity
of the pseudoequatorial NH (60%). An even higher nucleophilicity of this NH (75%)
was observed upon tosylation that transformed 11A/11B 78 :22 into 13A/13B 65 :35.
Scheme 3
OBn
O
OBn
O
OBn
O
H
O
H
BnO
BnO
BnO
BnO
BnO
15N
N
N
15N
BnO
15NHR
+
+
NHR
15N
BnO
BnO
BnO
N
H
H
75 : 25
78 : 22
78 : 22
12A R = Ac
12A
13A R = Ts
50 : 50
55 : 45
65 : 35
12B R = Ac
12B
13B R = Ts
11A
11B
BnO
BnO
BnO
BnO
OBn
O
OBn
O
BnO
BnO
OBn
O
H
O
H
15N
N
15N
15NHR
+
+
NHR
BnO
BnO
15N
BnO
N
N
H
H
85 : 15
75 : 25
75 : 25
15A R = Ac
15A
16A R = Ts
30 : 70
30 : 70
35 : 65
15B R = Ac
15B
16B R = Ts
14A
14B
15N NH
6'
N
15NH
OBn
BnO
OBn
BnO
1
3'
Y
BnO
BnO
OBn
O
HX
HX
Y
BnO
HO
OBn
OH
BnO
HO
OBn
OH
O
OBn BnO
OBn BnO
BnO
NH2
18
BnO
BnO
OBn
OBn
17A X = N, Y = 15
17B X = 15N, Y = N
N
17C X = N, Y = 15
17D X = 15N, Y = N
N
Acetylation of the galacto-configured 14A/14B 85 :15 with excess Ac2O yielded
83% of a 3 :7 mixture of the isotopomers 15A and 15B, evidencing a higher reactivity
(ca. 80%) of the pseudoaxial NH group. Acetylation of 14A/14B 75 :25 with equimolar
amounts of Ac2O afforded 80% of 15A/15B 3 :7 and 5% of a 3 :1 mixture of 17A 17D,
and 18. Again, the pseudoaxial NH group proved more nucleophilic (90%). Tosylation
of 14A/14B 75 :25 with an equimolar amount of TsCl gave 16A/16B 35 :65, evidencing
that 80% of the pseudoaxial NH was sulfonylated.
Remarkably, the gluco diaziridines 11A/11B are preferentially acetylated or
tosylated at the pseudoequatorial NH group and the galacto diaziridines 14A/14B at
the pseudoaxial NH group. This difference shows that the diastereoselectivity is
determined by the orientation of BnOÀC(4), an equatorial orientation of BnOÀC(4)
enhancing the reactivity of the pseudoequatorial NH and an axial orientation of
BnOÀC(4) the reactivity of the pseudoaxial NH. The interpretation of this selectivity is

Helvetica Chimica Acta Vol. 86 (2003)
2495
difficult. It is not clear if acylation and rearrangement are concerted, or not. If
concerted, then breaking of the C(1)ÀN bond will be strongly influenced by the kinetic
anomeric effect, i.e., the donor properties of the ring O-atom. In the glucose
1
derivatives, this may be enhanced by a conformational change towards, e.g., a S3,
where OÀC(4) and C(5)ÀO are no longer in an app orientation, as in the ground-state
4C1 conformer, so that the ring O-atom should be a better donor and the originally
1
pseudoequatorial NH will become pseudoaxial. In such a S3 conformer, breaking of
the C(1)ÀN bond to the pseudoaxial N, interacting with the acylating agent, will lead,
after proton transfer, to the observed major acetylhydrazone 12A. In the galactose
derivatives, there is no app interaction between two CÀO bonds, and the conforma-
1
tional change to a S3 is disfavoured by the axial orientation of BnOÀC(4)6). Again,
the pseudoaxial C(1)ÀN bond is broken upon interaction with the acylating agent.
The 15N-labelled tosylhydrazones 13A/13B and 16A/16B were each mixtures of a
single pair of isotopomers, and the acetylhydrazones 12A/12B and 15A/15B mixtures of
two diastereoisomeric pairs of isotopomers. 15N in 12A/12B, 13A/13B, 15A/15B, and
16A/16B leads to a splitting of the NH signals, whereas the other 1H-NMR signals are
identical to those of the unlabelled 2B, 2E, 4A, and 4B, respectively. Labelling of the
amino N-atom led to a large splitting of the NH signal (1J(15N,H) ˆ 92.9 94.4 Hz for
1
the acetylhydrazones 12A and 15A and J(15N,H) ˆ 83.5 84.4 Hz for the tosylhydra-
zones 13A and 16A; Table 1), whereas labelling of the imino N-atom led to a small
splitting or to only line broadening (2J(15N,H) ꢀ 1.7 Hz). The same couplings were
observed in the 15N-NMR spectra, where the d of the amino-labelled isotopomer
resonates at lower field (À222 to À224 ppm for the acetylhydrazones 12A and 15A and
À230to À232 ppm for the tosylhydrazones 13A and 16A) than the slightly broadened s
of the imino-labelled isotopomer (À119 to À134.7 ppm). In the 13C-NMR spectra,
labelling of the imino N-atom leads to a splitting of the signals of C(1) (1J(15N,C) ˆ 5.3
6.2 Hz) and C(2) (2J(15N,C) ˆ 9.3 11.3 Hz), whereas labelling of the amino N-atom
gives rise to line broadening or to a small splitting of the C(2) signals (2J(15N,C) ˆ 0and
3J(15N,C) ꢀ 1.6 Hz). Only the well-resolved CˆO signals of (Z)-12A, (Z)-12B, and
(Z)-15A, and the Me signals of (Z)-12A and (Z)-12B allow us to assign the 15N-
couplings to the Ac group (Table 1). As expected, 1J(15N,CˆO) (6.6 Hz) is larger than
2J(15N,CˆO) (ꢀ2.5 Hz). The antiperiplanar arrangement of the 15NÀN and the
C(O)ÀMe bond of (Z)-12B is evidenced by the 3J(15N,Me) of (Z)-12B (7.2 Hz), which
is distinctly larger than 2J(15N,Me) of (Z)-12A (1.4 Hz). This confirms the (Z)-
configuration of the major diastereoisomers of the acetylhydrazones 12A/12B and 15A/
15B.
The 15N-NMR spectrum of a 3 :1 mixture of the 1,4-dihydro-1,2,4,5-tetrazine 17 and
the galactonamide 18 shows two d's of equal intensity at À252.63 ppm (1J(15N,H) ˆ
86.7 Hz) and at À125.26 ppm (1J(15N,H) ˆ 5.7 Hz). The coupling constants are typical
for 1,4-dihydro-1,2,4,5-tetrazines [37]. Since 17 is formally a dimer of 14A/14B, two
15N-atoms must be present in 17, either in a 1,3- (17B or 17C) or in a 1,4-position (17A
or 17D). No long-range couplings between the 15N-atoms was detected. The 1:1 ratio
of the 15N-signals indicates that the amino and imino N-atoms are labelled to the same
Ampac calculations (AM1, gas phase [36]) indicate that the 1S3 conformer of the galacto diaziridine 3A is
more strongly disfavoured than the 1S3 conformer of gluco analogue 1A (8.6 vs. 7.75 kcal/mol).
6
)

2496
Helvetica Chimica Acta Vol. 86 (2003)
Table 1. Chemical Shifts [ppm] of HÀN, C(1), C(2), CˆO, Me, and 15N of the Isotopomeric Acetylhydrazones
12A/12B and 15A/15B and Chemical Shifts [ppm] of HÀN, C(1), C(2), and 15N of the Isotopomeric
Tosylhydrazones 13A/13B and 16A/16B (in parentheses, J(15N,H ), J(15N,C) [Hz], or the shape of the signal)
H
N
H
N
H
H
O
O
O
O
15N
15N
O
Me
O
Me
N
15N
15N
N
OBn
OBn
OBn
OBn
Me
O
Me
O
(Z)-12A
(E)-12A
(Z)-12B
(E)-12B
CDCl3
Ratio
35
15
35
15
d(NH)
C6D6
8.74 (93.5)
8.78 (94.4)
8.74 (0)
8.78 (0)
Ratio
49.5
5.5
40.5
4.5
d(NH)
d(C(1))
d(C(2))
8.98 (92.9)
143.96 (0)
75.20(1.6)
8.59 (92.9)
not assigned
74.2 (not assigned)
164.46 (br. s)
20.54 (br. q)
À 224 (ca. 92)
(E)-15A
8.98 (1.7)
143.38 (6.2)
75.20(10.8)
171.03 (2.5)
20.20 (7.2)
À 130.43 (br. s)
(Z)-15B
8.59 (br. s)
not assigned
74.2 (not assigned)
164.46 (br. s)
20.54 (br. q)
À 132 (br. s)
d(CˆO) 170.96 (6.6)
d(Me)
d(15N)
20.20 (1.4)
À 222.95 (92.4)
(Z)-15A
(E)-15B
CDCl3
Ratio
d(15N)
C6D6
18
12
42
28
À 221.5 (97.3)
À 225 (ca. 97)
À 128.9 (br. s)
À 123.5 (br. s)
Ratio
27
3
64
6
d(NH)
d(C(1))
d(C(2))
9.29 (93.2)
144.11 (0)
75.90(0)
9.07 (93.2)
not assigned
not assigned
not assigned
not assigned
not assigned
9.29 (1.7)
9.07 (br. s)
not assigned
not assigned
not assigned
not assigned
À 118.98 (br. s)
144.09 (5.9)
75.90(9.3)
171.22 (br. s)
20.39 (br. q)
À 124.72 (br. s)
d(CˆO) 171.22 (6.6)
d(Me)
d(15N)
20.39 (br. q)
À 222.08 (93.0)
H
O
H
O
15N
N
15N
Ts
Ts
N
OBn
13A
OBn
13B
16A
16B
CDCl3
C6D6
Ratio
65
35
35
65
d(NH)
d(C(1))
d(C(2))
d(15N)
7.96 (83.5)
147.55 (0)
74.02 (< 1.5)
À 232.05 (83.9)
7.96 (br. s)
8.76 (84.4)
147.81 (0)
75.48 (< 1.5)
À 230.00 (84.5)
8.76 (br. s)
147.81 (6.2)
75.48 (9.7)
À 125.02 (br. s)
147.54 (5.3)
74.02 (11.3)
À 134.74 (br. s)
extent, but is does not allow us to assign the ratio of the isotopomers 17A 17D. There
is no signal for 18 in the 15N-NMR spectrum of 17A 17D/18 3 :1, evidencing that the
amino group of 18 is introduced by substitution of the labelled hydrazino group. C(1) of
17A 17D resonates as d at 75.00 ppm (2J(15N,H) ꢁ 5 Hz). Assuming that only

Helvetica Chimica Acta Vol. 86 (2003)
2497
Scheme 4
1J(15N,C) couplings are visible7), one expects six overlapping signals for C(3) and C(6)
of the 1,4-dihydro-1,2,4,5-tetrazine nucleus of 17A 17D (a d for each 17A and 17D,
and a dd and an s for each 17B and 17C) at ca. 150ppm. Only two sharp peaks in a ratio
of 3 :2 are visible at 149.67 and 149.64 ppm, which could be assigned either to two s×s or
to an s at 149.67 ppm and a d at 149.655 ppm (1J(15N,H) ꢁ 4.5 Hz).
2. Sulfonylation of N-Methylated Pyranosylidene-Diaziridines. Sulfonylation of the
gluco N-methyldiaziridines 19A/19B 72 :28 [2] with 1.1 equiv. of TsCl and purification
of the products by flash chromatography gave 78% of a 3 :1 mixture of the N-tosylated
lactone hydrazone 20 and the lactone 21 [40][41] (Scheme 4). Similarly, the galacto
diaziridines 22A/22B 85 :15 and the manno diaziridines 25A/25B 85 :15 and 28A/28B
80:20[2] were treated with TsCl. Workup with dry solvents afforded exclusively the N-
tosylated lactone hydrazones 23, 26, and 29 in yields of 56, 66, and 60%, respectively.
The N-methyl-N-tosylhydrazones 20, 23, and 26 are very moisture-sensitive. Upon
standing in wet solution, they decomposed within a few hours to the lactones 21, 24
[42], and 27 [43]. This indicates that 21 is the hydrolysis product of 20, although it could
also, in part, result from hydrolysis of the intermediate hydrazonium chloride that is
formed upon sulfonylation of the NH group of 19A/19B. Only the MeN group of 19A/
To the best of our knowledge, no 13C-NMR data are available for 15N labelled 1,4-dihydro-1,2,4,5-
tetrazines. No J(15N,C) values of a 15N-labelled pyrazole were reported [38]. 1J(15N,C) and 2J(15N,C) values
of 5 19 Hz were observed in the 13C-NMR spectra of 15N-labelled hydrazones [39].
7
)

2498
Helvetica Chimica Acta Vol. 86 (2003)
19B, 22A/22B, 25A/25B, and 28A/28B is attacked by TsCl8), irrespective of the
configuration at C(4) or at C(2).
The MeN groups of 20, 23, 26, and 29 in C6D6 resonate at 2.50 3.04 ppm ( Table 2 in
Exper. Part). The vicinal couplings J(2,3), J(3,4), and J(4,5) of 20 and 26 (in C6D6) are
similar to those of 2E and 6 (in CDCl3), respectively. They indicate a 1S5 conformation
4
of 20 and a flattened C1 conformation of 26. However, J(2,3) ˆ 1.2, J(3,4) ˆ 7.1, and
J(4,5) < 1 Hz of 23 are distinctly different from those of 4B (5.7, 3.6, and 2.6 Hz, resp.)
and evidence a change from a flattened 4C1 to a 1S5 upon formal N-methylation. J(2,3),
J(3,4), and J(4,5) values of 29 are similar to those of the starting diaziridines 28A/28B
and reveal a OH5 conformation. Formal N-methylation of 2E and 6 leads to a downfield
shift of 8.1 8.3 ppm for C(1) of 20 and 26 (Table 3 in Exper. Part). Formal N-
methylation of 4B leads to stronger downfield shift of 10.9 ppm for C(1) of 23,
probably due to the conformational change of the pyranose ring.
3. Acetylation and Sulfonylation of Furanosylidene-Diaziridines. Acetylation of the
mannofuranosylidene-diaziridine 30 [2] with Ac2O gave 63% of the N-acetylhydrazone
31A and 8% of the 1,2,4,5-tetrazine 32 (Scheme 5). Sulfonylation of 30 led to a similar
result, namely to 61% of the N-tosylhydrazone 31B and 11% of 32. The tetrazine 32 is
probably formed by oxidation of the expected 1,4-dihydro-1,2,4,5-tetrazine. Tosylation
of the N-methylated ribofuranosylidene-diaziridines 33A/33B/33C/33D 76 :4 :12 :8 [2]
with TsCl and chromatographic separation of the products yielded 44% of a 2 :1 (E)/
(Z)-mixture of the N-methyl-N-tosylhydrazone 34 and 30% of the ribonolactone 35
[44][45].
Scheme 5
In CDCl3, the (Z)-acetylhydrazone 31A is a 85 :15 (E)/(Z)-mixture of the
diastereoisomers obtained by rotation about the NHÀC(O)Me bond. The (Z)-
configuration of the CˆN bond of 31A und 31B is evidenced by the chemical-shift
8
)
For a 2-sulfonylation of a 1,3,3-trialkyldiaziridine, see [13e]. For examples of a 2-acylation of 1,3,3-
trialkyldiaziridines, see [10][16][20].

Helvetica Chimica Acta Vol. 86 (2003)
2499
value of C(1) (149.5 153.5 ppm; Table 3 in Exper. Part). Relative to C(1) of 31, C(1) of
the N-methyl-N-tosylhydrazone (Z)-34 resonates downfield (165.8 ppm) by ca.
10ppm, as expected, and C(1) of the corresponding ( E)-isomer downfield
(180.7 ppm) by an additional 15 ppm.
The structure of the 1,2,4,5-tetrazine 32 is evidenced by the pink colour, the OH
band at 3450cm À1, the absence of a NH band, and the typical chemical shift for C(3)
and C(6) of the tetrazine nucleus at 168.5 ppm [33][35][46] (Table 4 in Exper. Part).
We thank the Swiss National Science Foundation and F. Hoffmann-La Roche AG, Basel, for generous
support.
Experimental Part
General Procedure for the Treatment of the Diaziridines with Acylating or Sulfonylating Agents. At 08, a
soln. of the diaziridine in dry CH2Cl2 or pyridine was treated with a soln. of the acylating or sulfonylating agent
in pyridine and stirred for the indicated period at r.t., and evaporated. A soln. of the residue in AcOEt was
washed with sat. NaHCO3 soln. and brine (2Â), dried (MgSO4), and evaporated.
(Z)-N'-(2,3,4,6-Tetra-O-benzyl-d-glucopyranosylidene)acetohydrazide (2B). a) The reaction of 1A/1B
95 :5 (1.50g, 2.71 mmol) in Ac 2O (5 ml; 3 h at 258), workup (dilution with CH2Cl2 and washing with 5%
NaHCO3 soln.), and FC (hexane/AcOEt 2 :1 ! 1 :1) gave 2B (1.26 g, 79%).
b) The reaction of 1A/1B 95 :5 (410mg, 0.74 mmol) in CH 2Cl2/pyridine 5 :1 (12 ml) with Ac2O (75 ml,
0.79 mmol; 4 h) and FC (hexane/AcOEt 1:1) gave 2B (320mg, 73%). Colourless oil. Rf (hexane/AcOEt 1 :1)
0.20. [a]2D5 ˆ ‡33.1 (c ˆ 0.49, CHCl3). IR (CHCl3): 3380w (sh), 3350w, 3060w, 3020w (sh), 2995m, 2920w (br.),
2870m, 1690m (sh), 1665s, 1495m, 1450m, 1360m, 1320m, 1250m, 1190w (sh), 1070s, 1025m, 990w (sh), 910w,
850w, 815w. 1H-NMR (600 MHz, CDCl3, 298 K, 2 diastereoisomers in the ratio 7:3, assignment based on a
1H,1H-COSY spectrum): Table 2; additionally, 7.50 7.14 ( m, 20arom. H); 4.75 ( d, J ˆ 12.0, 0.7 H), 4.74 (d, J ˆ
12.0, 0.3 H) (PhCH); 4.68 4.53 (m, 5 PhCH); 4.48 (d, J ˆ 11.8, 0.7 H), 4.45 (d, J ˆ 11.8, 0.7 H), 4.42 (d, J ˆ 11.9,
0.3 H), 4.39 (d, J ˆ 12.0, 0.3 H) (2 PhCH); 2.28 (s, 2.1 H), 2.05 (s, 0.9 H) (AcN). 1H-NMR (400 MHz, C6D6,
298 K, 2 diastereoisomers in the ratio 9 :1): Table 2, additionally for the major isomer, 7.28 7.04 (m, 20ar-
om. H); 4.57 (d, J ˆ 11.6), 4.56 (d, J ˆ 12.0) (2 PhCH); 4.43 (d, J ˆ 11.6, PhCH); 4.33 (br. d, J ꢁ 11.3, 2 PhCH);
4.26 (d, J ˆ 12.5), 4.23 (d, J ˆ 12.4), 4.17 (d, J ˆ 11.6) (3 PhCH); 2.23 (s, Ac); additionally for the minor isomer:
8.56 (s, NH); 4.77 (br. d, J ˆ 12.0), 4.68 (br. d, J ˆ 11.2), 4.08 (br. d, J ˆ 11.2) (3 PhCH); 4.01 (br. s, HÀC(2));
1
3.58 (br. s, 2 HÀC(6)). H-NMR (300 MHz, C6D6, 348 K): 8.74 (br. s, NH); 7.28 7.05 (m, 20arom. H); 4.595
(d, J ˆ 12.0), 4.590 (d, J ˆ 11.7) (2 PhCH); 4.51 4.47 (m, HÀC(5)); 4.45 (d, J ˆ 11.8, PhCH); 4.40( d, J ˆ 11.8,
2 PhCH); 4.31 (s, PhCH2); 4.27 (d, J ˆ 11.8, PhCH); 4.17 (br. s, HÀC(2)); 3.97 (dd, J ˆ 2.5, 4.9, HÀC(3)); 3.86
(dd, J ˆ 4.9, 9.9, HÀC(4)); 3.56 (d, J ˆ 3.1, 2 HÀC(6)); 2.18 (br. s, AcN). 1H-NMR (400 MHz, (D6)DMSO,
298 K, 2 diastereoisomers in the ratio 55 :45): 10.13 (s, 0.45 H), 9.63 (s, 0.55 H) (NH); 7.40 7.20 (m, 18 ar-
om. H); 7.20 7.13 ( m, 2 arom. H); 4.72 4.37 (m, 8 PhCH, HÀC(5)); 4.27 (d, J ˆ 2.3, 0.55 H), 4.19 (d, J ˆ 3.0,
0.45 H) (HÀC(2)); 3.95 (t, J ꢁ 3.5, 0.55 H), 3.93 (t, J ꢁ 3.5, 0.45 H) (HÀC(3)); 3.83 (br. d, J ˆ 11.1, HÀC(6));
1
3.78 3.67 (m, HÀC(4), H'ÀC(6)); 2.10( s, 1.35 H), 1.92 (s, 1.65 H) (AcN). H-NMR (400 MHz, (D6)DMSO,
370K): 9.35 9.05 (br. s, NH); 7.38 7.20( m, 20arom. H); 4.71 ( d, J ˆ 11.1), 4.62 (d, J ˆ 11.8), 4.61 (d, J ˆ 10.7)
(3 PhCH); 4.60 4.50 ( m, 5 PhCH); 4.50( ddd, J ˆ 2.4, 4.5, 10.0, HÀC(5)); 4.22 (d, J ˆ 3.0, HÀC(2)); 3.97
(t, J ˆ 3.3, HÀC(3)); 3.86 (dd, J ˆ 2.4, 11.2, HÀC(6)); 3.78 (dd, J ˆ 4.5, 11.2, H'ÀC(6)); 3.76 (dd, J ˆ 3.5, 9.8,
HÀC(4)); 2.03 (br. s, AcN). 13C-NMR (50.3 MHz, CDCl3, 298 K, 2 diastereoisomers in the ratio 7:3): Table 3,
additionally, for the major isomer: 171.86 (s, CˆO); 137.46, 137.37, 137.02, 136.83 (4s); 128.57 127.38 (several
d); 73.28, 72.91, 71.70, 70.73 (4t, 4 PhCH2); 19.98 (q, Me); additionally, for the minor isomer: 165.64 (s, CˆO);
137.28 (s); 73.08, 72.38, 71.38, 70.79 (4t, 4 PhCH2); 21.67 (q, Me). CI-MS (NH3): 597 (8), 596 (42), 595 (100,
‡
[M ‡ 1] ). Anal. calc. for C36H38N2O6 (594.70): C 72.71, H 6.44, N 4.71; found: C 72.65, H 6.64, N 4.84.
Benzoylation of 1A/1B 95 :5. a) A soln. of 1A/1B 95 :5 (2.00 g, 3.62 mmol) in pyridine (4.0 ml) was treated
at r.t. with a soln. of benzoic anhydride (0.90 g, 3.98 mmol) in pyridine (1.7 ml), stirred for 6 h, diluted with
CH2Cl2, washed with 1m aq. NaHCO3 soln., dried (MgSO4), and evaporated. FC (hexane/AcOEt 3 :1) gave 7
(191 mg, 8%) and 2C (1.45 g, 61%).

2500
Helvetica Chimica Acta Vol. 86 (2003)
Table 2. Selected 1H-NMR Chemical Shifts [ppm] and Coupling Constants [Hz] of the Glucosylidene Hydrazides 2, 12, 13, and 20, the
Galactosylidene Hydrazides 4, 15, 16, and 23, the Galactonamide 18, the Mannosylidene Hydrazides 6, 26, 29, and 31, and the
Ribosylidene Hydrazides 34 (measured at 298 K)
2Ba)b)
Solvent CDCl3
2Bb)c)
C6D6
2C
CDCl3
2D
CDCl3
2E [19]
CDCl3
2F
CDCl3
2G
CDCl3
12A/12Bd) 13A/13B
C6D6
CDCl3
Ratio
7
:
3
9 : 1
55 : 45
65 : 55
HÀC(2) 4.11
HÀC(3) 3.94
HÀC(4) 3.81
HÀC(5) 4.57
HÀC(6) 3.77
H'ÀC(6) 3.72
4.43
4.00
3.77
4.71
3.82
3.73
4.16
3.96
3.91
4.49
4.47
4.00
4.34
3.96
4.08
3.83
3.61
4.04
3.79
3.56
4.44
3.51
3.64
3.94
3.81
3.69
4.48
3.73
3.67
4.16
3.97
3.91
4.50
4.08
3.84
3.61
4.46
3.84 3.77 3.78
4.70 4.60 4.59 4.52 4.46
3.503.803.803.72
3.45
3.71
3.72
5
3.72
3.66
8.0 7.98
3.71
3.48
3.66
7.96 (83.5)/
HNe)
or MeN
J(2,3)
J(3,4)
J(4,5)
J(5,6)
J(5,6')
J(6,6')
8.708.808.94
9.39
8.27
7.94
8.98 (92.9)/
8.98 (1.7) 7.96 (<1.5)
2.5
4.7
10.1
2.3
4.2
11.1
1.8
4.3
10.1
2.2
4.4
2.01.8
5.04.5
10.1
3.5
2.1
2.02.02.1
4.2
1.9
2.10.8
4.4
10.0
4.7
4.7
10.1
2.02.02.1
4.4
11.0 11.1
5.40.7
f
)
9.6
1.9
4.5
10.2
4.3
10.1
2.04.5
10.2
2.2
4.6
3.5
1.9
4.5
11.1
11.011.1
11.011.011.1
11.1
20
4Ab)
CDCl3
4Aa)b)c) 4B
15A/15Bd) 16A/16B 18g)
23
C6D6
Solvent C6D6
C6D6
10: 1
C6D6
C6D6
C6D6
CDCl3
Ratio
8
:
2
3 : 7
35 : 65
HÀC(2) 4.26
HÀC(3) 3.94
HÀC(4) 3.91
HÀC(5) 4.64
HÀC(6) 3.54
H'ÀC(6) 3.54
4.38
3.85
4.13
4.30
3.68
3.65
8.76
4.41
3.97
4.41
3.64
4.33
3.63 3.56 3.66
3.87 3.97
4.11 4.08 4.09
3.63 3.56 3.64
3.63 3.56 3.62
4.405
4.33
3.603.96
3.89
4.12
3.64
3.603.49
4.55
4.18 4.17
3.91
3.34
4.30 4.26 3.96
4.70 4.42 4.08
3.91
3.78
9.05
3.90
4.13
3.57
4.35
4.07
3.42
3.64
3.64
9.42
HNe)
or MeN
J(2,3)
J(3,4)
J(4,5)
J(5,6)
J(5,6')
J(6,6')
3.04
8.68
9.29 (93.2)/ 8.76 (84.4)/ 5.39 (2 H) 2.50
9.29 (1.7) 8.76 (<1.5)
1.9
4.8
9.8
2.6
2.6
6.5
2.7
2.2
6.3
6.3
9.7
3.8
6.2
5.7
6.5
5.7
7.1
3.2
2.7
1.0
1.2
3.03.03.6
2.8
3.08.2
f
)
2.6
6.4
6.4
2.6
2.8
< 1.0
f
8.9
3.5
10.9
)
)
)
6.07.4
6.7
9.7
6.6
6.3
f
f
5.4
10.2
6.5
9.4
7.0
9.3
f
f
)
)
6 [19]
26a)
29
31Aa)
31B
(E)-34/(Z)-34
Solvent CDCl3
C6D6
C6D6
CDCl3
CDCl3
C6D6
Ratio
85
:
15
2
:
1
HÀC(2) 4.18
HÀC(3) 3.67
HÀC(4) 4.18
4.30
4.22
5.12
4.91
4.33
4.46
4.15
4.05
8.34
5.19
4.89
4.39
5.06
4.79
4.28
6.06
4.33
4.33
3.44
5.31
4.13
4.33
3.37
3.55 3.52 4.11
4.27
3.92
3.26
HÀC(5) 3.97 3.93 3.87
4.50 4.45 4.42
4.13 4.05 4.11
4.13 4.05 3.98
HÀC(6) 3.72
H'ÀC(6) 3.68
3.55 3.52 3.74
3.55 3.52 3.62
2.75h)
2.57h)
HN
8.17
8.31
7.42
MeN
J(2,3)
J(3,4)
J(4,5)
J(5,6)
3.03
2.1
10.2
8.4
4.05.8
2.82
8.1
6.6
3.00
6.2
0
3.01
5.8
0
3.1
8.9
8.9
4.6
5.8
3.8
7.5
5.7
3.9
6.8
5.6
3.6
7.5
6.1
4.1
9.011.1
10.3
2.6
2.6
f
6.2
)
)
)
f
f
J(5,6') .043.1.04.100
J(6,6') 11.2
2.0i)
1.8i)
10.7j)
f
j
)
11.09.0
)
a) Assignment based on the 1H,1H-COSY spectrum. b) Two diastereoisomers at 298 K; for data of a single diastereoisomer of 2B and 4A
at 348 K in C6D6, see Exper. Part. c) Data for the major diastereoisomer at 298 K. For some values of the minor diastereoisomer, see
Exper. Part. d) Mixture of two isotopomeric pairs of diastereoisomers (12: 9 : 1, 15: 10: 1); data for the major isotopomeric pair given.
For values of the minor isotopomeric pair, see Exper. Part. e) In parentheses, 1J(15N,H ) or 2J(15N,H ) . f) Not assigned. g) d(HOÀC(5)) ˆ
i
j
2.48 ppm, J(5,OH) ˆ 8.0Hz. h) Values of d(H'ÀC(5)). ) Values of J(4,5'). ) Values of J(5,5').

Helvetica Chimica Acta Vol. 86 (2003)
2501
Table 3. Selected 13C-NMR Chemical Shifts [ppm] of the Glucosylidene Hydrazides 2, 12, 13, and 20, the Galactosylidene Hydrazides 4,
15, 16, and 23, the Galactonamide 18, the Mannosylidene Hydrazides 6, 26, 29, and 31, and the Ribosylidene Hydrazides 34 (measured at
298 K)
2B
2C
2D
2E [19]
2F
2G
12A/12Ba) 13A/13B
Solvent CDCl3
CDCl3
CDCl3
CDCl3
CDCl3
CDCl3
C6D6
CDCl3
Ratio
7
:
3
55 : 45
65 : 35
C(1)b) 143.73
146.84
148.04
74.15
145.23
147.58
147.81
152.87
143.96 (0)/ 147.55 (0)/
143.38 (6.2) 147.54 (5.3)
74.02 (<1.5)/
C(2)b) 74.16
74.29
7047.38.097047.03.25
(1.67)5/.20
75.20(10.8) 74.02 (11.3)
C(3)
C(4)
C(5)
C(6)
MeN
81.28
77.00
76.1075.78
67.98
80.48
77.17
80.57
77.00
75.35
67.94
81.92
77.84
81.28
77.00
76.3076.31
81.06
77.00
75.96
67.92
80.83
77.03
76.63
67.64
82.50
77.78
76.31
67.74
81.30
77.05
75.85
68.18
67.87
68.00
68.04
20
4A
4B
15A/15Ba) 16A/16Bc) 18
23
Solvent C6D6
CDCl3
C6D6
3 : 7
C6D6
C6D6
CDCl3
C6D6
Ratio
8
:
2
35 : 65
d
C(1)b) 155.67
C(2)b) 74.38
144.38
146.50148.32
74.74
14)4/.11 (0
147.81 (0)/
)
157.36
73.22
144.09 (5.9) 147.81 (6.2)
74.98
75.55
75.90(0)/
75.90(9.3)
78.96
75.48 (<1.5)/ 75.13
75.48 (9.7)
C(3)
C(4)
C(5)
C(6)
MeN
81.33
77.09
76.4077.6076.36
67.41
37.74
79.3078.11
72.26
79.29
72.07
79.78
81.16 .47
80
72.94
73.20
72.95
68.73
77.22
77.79
78.44
68.83
78.21
748.60 69.0 69.1
68.41
67.78
68.64
71.28
70.9
38.26
6 [19]
26c)
29
31Aa)
31Bc)
(E)-34/(Z)-34
Solvent CDCl3
C6D6
C6D6
CDCl3
CDCl3
C6D6
Ratio
85
:
15
2
:
1
C(1)
C(2)
C(3)
C(4)
C(5)
C(6)
MeN
147.02
71.61
79.2079.57
72.96
80.56
68.46
155.31
73.15
158.20
149.47
152.59
76.29e)
77.56e)
82.18
153.49
77.26
77.37
83.3086.5086.64
72.60 63.94
180.72
77.73
79.35
165.78
71.83e)
77.00e)
79.27e)
79.85e)
e
77.53
8
77.0
)
73.95
80.78
69.1061.62
38.63
72.59e)
68.05
81.84
72.25
72.40
63.60
38.73
65.91
38.75
65.66
66.17
41.08
a) Mixture of two isotopomeric pairs of diastereoisomers (12: 9 : 1, 15: 10: 1); data for the major isotopomeric pair
b
given. For values of the minor isotopomeric pair, see Exper. Part. ) In parentheses, J(15N,C ) . c) Assignment based on
the H,13C-COSY spectrum. d) Not assigned. e) Assignments may be interchanged.
1
b) A soln. of 1A/1B 95 :5 (500 mg, 0.91 mmol) in pyridine (0.5 ml) was treated at 08 with benzoyl chloride
(0.156 ml, 0.9 mmol), stirred at r.t. for 5.5 h, diluted with CH2Cl2, washed with H2O (3Â), dried (MgSO4), and
evaporated. FC (hexane/AcOEt 4 :1 ! 3 :1) gave 8 (186 mg, 27%), 7 (59 mg, 10%), and 2C (83 mg, 14%).
(Z)-N'-(2,3,4,6-Tetra-O-benzyl-d-glucopyranosylidene)benzohydrazide (2C). Rf (hexane/AcOEt 3 :1) 0.21.
IR (CHCl3): 3400w, 3350w (sh), 3110w, 3090w, 3070m, 3030m (sh), 3000s 2910m, 2870m, 1685s, 1655s, 1605m,
1585m, 1510s, 1500s, 1490s, 1455s, 1360s, 1340m (sh), 1290m (sh), 1255s, 1140s, 1090s (br.), 1075s, 1030s, 1000m,
900m. 1H-NMR (200 MHz, CDCl3): Table 2; additionally, 7.78 (d, J ˆ 7.0, 2 arom. H); 7.57 7.13 (m, 23 ar-
om. H); 4.78 4.53 (m, 4 PhCH); 4.54 (s, PhCH2); 4.42 (d, J ˆ 11.4), 4.38 (d, J ˆ 11.6) (2 PhCH). 13C-NMR
(50.3 MHz, CDCl3): Table 3; additionally, 163.18 (s, CˆO); 137.32, 137.13, 136.88, 136.63, 133.35 (5s); 131.42
(d); 128.63 126.70(several d); 73.00, 72.40, 71.31, 70.72 (4t, 4 PhCH2).
(1R)-1,2,3,5-Tetra-O-benzyl-1-C-(5-phenyl-1,3,4-oxadiazol-2-yl)-d-arabinitol (7). Rf (hexane/AcOEt 3 :1)
0.32. IR (CHCl3): 3570w, 3110w, 3090w, 3070w, 3040w (sh), 3005m, 2920w (br.), 2875m, 1960w (br.), 1885w
(br.), 1815w, 1610w, 1590w, 1565w (sh), 1555m (sh), 1545w (sh), 1495m, 1455m, 1395w, 1365m, 1220s (sh) 1200s,

2502
Helvetica Chimica Acta Vol. 86 (2003)
1090s, 1070s, 10 3s0, 960w, 930m, 910m (sh). 1H-NMR (200 MHz, CDCl3): Table 4 ; additionally, 7.95
(m, 2 arom. H); 7.55 7.06 (m, 3 arom. H); 4.86 (d, J ˆ 11.2), 4.75 (d, J ˆ 11.2), 4.68 (d, J ˆ 11.5), 4.61 (d, J ˆ
11.6), 4.51 (d, J ˆ 11.5), 4.45 (d, J ˆ 11.3), 4.43 (d, J ˆ 11.7), 4.29 (d, J ˆ 11.3) (8 PhCH). 13C-NMR (50.3 MHz,
CDCl3): Table 4; additionally, 137.67, 137.59, 137.44, 136.63 (4s); 131.58 (d); 128.84 126.84 (several d); 123.45
(s); 75.21, 73.42, 73.17, 72.81 (4t, 4 PhCH2).
Table 4. Selected 1H- and 13C-NMR Chemical Shifts [ppm] and Coupling Constants [Hz] of the 1-C-Aryl-
pentitols 7 10, 17, and 32
7
8
9
10a)
17A 17D
32a)
Solvent
CDCl3
CDCl3
CDCl3
CDCl3
CDCl3
CDCl3
HÀC(1)
HÀC(2)
HÀC(3)
HÀC(4)
HÀC(5)
H'ÀC(5)
HOÀC(4)
J(1,2)
J(2,3)
J(3,4)
J(4,5)
J(4,5')
5.22
4.32
3.63
4.03
3.62
3.55
2.78
7.3
3.7
7.3
3.5
4.7
5.15
4.304.19
4.04
5.56
3.97
3.82
5.00
4.43
3.91
3.88
4.14
3.55
3.45
2.41
2.0
8.4
0.8
6.8
6.4
4.43
5.90
3.92
4.92
3.81
4.11
3.56
3.49
2.61
5.01.8
7.6
1.7
6.3
6.4
7.6
3.87
4.13
3.54
3.44
2.41
3.29
4.01
3.95
3.70
2.32
7.2
4.2
5.7
3.4
5.1
7.4
8.3
1.1
6.7
6.4
8.2
9.4
0.9
7.7
6.2
5.1
8.8
8.5
J(4,OH)
J(5,5')
5.6
9.7
8.2
9.3
11.1
9.4
C(1)
C(2)
C(3)
C(4)
73.74
79.86b)
77.37b)
70.27
70.67
165.05
163.94
73.73
79.60b)
77.79b)
72.98
67.91
165.13
163.74
73.67
79.97
77.11
74.91
80.54
761.9077.0
68.81
75.00 (ca. 5)
80.62
76.82b)
77.58b)
68.32
69.23
68.88
71.33
75.66b)
66.57
C(5)
71.01
71.26
C(2) of Ar
C(5) of Ar
C(3)/C(6) of Ar
164.47b)
164.27b)
c
149.68
)
168.51
a) Assignment of 1H-NMR data based on a 1H,1H-COSY spectrum. b) Assignments may be interchanged.
c) Two peaks at 149.67 and 149.64 ppm in the ratio of 3 : 2.
(1R)-4-O-Benzoyl-1,2,3,5-tetra-O-benzyl-1-C-(5-phenyl-1,3,4-oxadiazol-2-yl)-d-arabinitol (8). Rf (hexane/
AcOEt 3 :1) 0.46. IR (CHCl3): 3090w, 3070w, 3030w, 3010w, 2960w, 2930w, 2880w, 1720s, 1610w, 1605w, 1590w,
1555m, 1500w, 1455s, 1395w, 1375m, 1365m, 1320m, 1270s, 1250s, 1180w, 1115s, 1100s, 1070s, 1030s, 915w.
1H-NMR (200 MHz, CDCl3): Table 4; additionally, 8.03 7.93 (m, 4 arom. H); 7.61 7.10( m, 26 arom. H); 4.79
(d, J ˆ 10.9), 4.70 (d, J ˆ 10.7), 4.64 (d, J ˆ 10.8), 4.63 (d, J ꢁ 10.5, 2 H), 4.55 (d, J ˆ 11.0), 4.52 (d, J ˆ 12.2), 4.42
(d, J ˆ 12.1) (8 PhCH). 13C-NMR (50.3 MHz, CDCl3): Table 4; additionally, 165.39 (s, CˆO); 137.71, 137.61,
137.53, 136.54 (4s); 132.96 (d); 131.66 (d); 129.88 (s); 129.64 126.93 (several d); 123.52 (s); 75.60, 74.42, 73.06,
72.98 (4t, 4 PhCH2).
(Z)-N-[(2,3,4,6-Tetra-O-benzyl-d-glucopyranosylidene)amino] O-[(9H-Fluoren-9-yl)methyl]carbamate
(2D). According to [18], a soln. of 1A/1B 95 :5 (1.0g, 1.8 mmol) in dioxane (10ml) was treated with
Na2CO3 ¥ 10 H2O (1.0g, 9 mmol) and a soln. of FmocCl (570mg, 2.2 mmol) in dioxane (10ml) and stirred for
12 h at r.t. After filtration, the filtrate was diluted with Et2O, washed with H2O (2Â) and brine, dried (MgSO4),
and evaporated. FC (hexane/AcOEt 4 :1) and crystallisation from Et2O/hexane gave 2D (564 mg, 40%).
Colourless crystals. Rf (hexane/AcOEt 1:1) 0.67. M.p. 97 1008. [a]2D5 ˆ ‡20.6 (c ˆ 1.0, CHCl3). IR (KBr):
3380w (br.), 3060w, 3025w, 2950w, 2860w, 1740s, 1655m, 1510m, 1495m (sh), 1450m, 1405w, 1360m, 1350m,
1
1320w, 1290m, 1250m, 1210s, 1145m, 1125m, 1090s, 1070s, 1040m, 1030m, 1010m, 990m, 90 5w, 850w. H-NMR

Helvetica Chimica Acta Vol. 86 (2003)
2503
(400 MHz, CDCl3): Table 2 ; additionally, 7.78 (d, J ˆ 7.3, 2 arom. H); 7.66 (br. s, 2 arom. H); 7.42 7.27
(m, 22 arom. H); 7.18 7.14 (m, 2 arom. H); 4.74 (br. d, J ꢁ 10.3, PhCH); 4.63 4.60( m, CO2CH2); 4.62
(d, J ˆ 11.7, PhCH); 4.59 4.51 (m, 4 PhCH); 4.44 (d, J ˆ 11.4), 4.39 (d, J ˆ 11.8) (2 PhCH); 4.37 4.34
(m, HÀC(9')). 13C-NMR (50.3 MHz, C6D6): Table 3; additionally, 153.69 (br. s, CˆO); 144.43 (2s); 141.71
(2s); 138.41 (2s); 137.77 (2s); 128.66 127.32 (several d); 125.63 (br. d, 2 C); 120.14 (2d); 73.11, 72.96, 71.51,
70.84 (4t, 4 PhCH2); 67.51 (br. t, CO2CH2); 47.55 (d, C(9')). Anal. calc. for C49H46N2O7 (774.91): C 75.95, H 5.98,
N 3.62; found: C 76.17, H 5.90, N 3.58.
N'-(2,3,4,6-Tetra-O-benzyl-d-glucopyranosylidene)-4-toluenesulfonohydrazide (2E). The reaction of 1A/
1B 95 :5 (515 mg, 0.93 mmol) in CH2Cl2 (20ml) with TsCl (214 mg, 1.12 mmol) in pyridine (5 ml; 1.5 h), FC
(CH2Cl2), and crystallisation from MeOH gave 2E [19] (532 mg, 81%).
N'-(2,3,4,6-Tetra-O-benzyl-d-glucopyranosylidene)naphthalene-2-sulfonohydrazide (2F). The reaction of
1A/1B 95 :5 (201 mg, 0.36 mmol) and naphthalene-2-sulfonyl chloride (107 mg, 0.47 mmol) in pyridine (2.5 ml;
1.5 h), FC (CH2Cl2), and crystallisation from AcOEt/hexane gave 2F (225 mg, 83%). Fine needles. Rf (hexane/
AcOEt 1:1) 0.65. M.p. 1548. [a]2D5 ˆ À9.5 (c ˆ 0.81, CHCl3). IR (KBr): 3220m, 3060w, 3025w, 2930m, 2860m,
1730m, 1660m, 1585w, 1555w, 1540w, 1495w, 1455m, 1390m, 1360m, 1340s, 1265w, 1205w, 1170s, 1090m (br.),
1070s, 10 3s0, 90 w5, 865w, 850w, 820w. 1H-NMR (400 MHz, CDCl3): Table 2 ; additionally, 7.93 7.82
(m, 4 arom. H); 7.63 7.53 (m, 2 arom. H); 7.40 7.19 ( m, 16 arom. H); 7.13 7.07 (m, 3 arom. H); 6.97 6.94
(m, 2 arom. H); 4.55 (d, J ˆ 12.0), 4.51 (d, J ˆ 12.0), 4.46 (d, J ˆ 11.4), 4.40( d, J ˆ 11.8), 4.32 (d, J ˆ 11.4), 4.22
(d, J ˆ 11.5), 4.19 (d, J ˆ 11.3), 4.11 (d, J ˆ 11.9) (8 PhCH). 13C-NMR (50.3 MHz, CDCl3): Table 3; additionally,
137.52, 137.40, 136.90, 136.62, 135.12, 134.92, 132.01 (7s); 129.54 127.39 (several d); 122.83 (d); 73.32, 72.90,
‡
71.40, 70.21 (4t, 4 PhCH2). CI-MS (C4H10): 746 (14), 745 (22), 744 (33), 743 (100, [M ‡ 1] ), 553 (10).
N'-(2,3,4,6-Tetra-O-benzyl-d-glucopyranosylidene)-2,4,6-triisopropylbenzenesulfonohydrazide (2G). The
reaction of 1A/1B 95 :5 (225 mg, 0.41 mmol) in pyridine (2.5 ml; 1.5 h) with 2,4,6-triisopropylbenzenesulfonyl
chloride (152 mg, 0.47 mmol) in pyridine (2.5 ml; 3.5 h) and FC (CH2Cl2) gave 2G (211 mg, 64%). Yellow oil. Rf
(hexane/AcOEt 1 :1) 0.74. [a]2D5 ˆ À0.4 (c ˆ 1.25, CHCl3). IR (CHCl3): 3290w (br.), 3060m (sh), 3010m, 2960s,
2930s, 2870m, 1730m, 1660m, 1600m, 1560w, 1495m, 1455s, 1425m, 1385m (sh), 1365s, 1330m, 1285m, 1255m,
1165s, 1155m (sh), 1105s (sh), 1070s, 1030s, 940w, 885m. 1H-NMR (400 MHz, CDCl3): Table 2; additionally,
7.42 7.26 (m, 14 arom. H); 7.14 7.09 (m, 8 arom. H); 4.54 (s, PhCH2); 4.53 (d, J ˆ 11.9), 4.41 (d, J ˆ 11.5), 4.38
(d, J ˆ 11.8) (3 PhCH); 4.28 4.21 (m, irrad. at 1.26 or 1.22 ! change, 2 Me2CH); 4.27 (d, J ˆ 11.9), 4.22 (d, J ˆ
12.1), 4.07 (d, J ˆ 11.9) (3 PhCH); 2.82 (sept., J ˆ 6.9, irrad. at 1.16 ! s, Me2CH); 1.26 (d, J ˆ 6.7), 1.22 (d, J ˆ
6.8), 1.16 (d, J ˆ 6.9) (3 Me2CH). 13C-NMR (50.3 MHz, CDCl3): Table 3; additionally, 150.99 (2s); 146.14,
137.61, 137.40, 136.85, 136.52, 131.23 (6s); 128.37 127.73 (several d); 123.50(2 d); 72.99, 72.72, 71.18, 69.87 (4t, 4
PhCH2); 33.93 (d, Me2CH); 29.71 (d, 2 Me2CH); 24.75 (q, Me2CH); 24.72 (q, Me2CH); 23.34, 23.31
‡
(2q, Me2CH). CI-MS (C4H10): 821 (24), 820 (59), 819 (100, [M ‡ 1] ), 605 (16), 604 (36), 554 (15), 91 (13).
Treatment of 3A/3B 95 :5 with Ac2O. a) The reaction of 3A/3B 95 :5 (500 mg, 0.9 mmol) in CH2Cl2 (15 ml)
with Ac2O (2 ml at start and 1 ml after 2 h; 3 h at r.t.), workup (concentrated to 5 ml, dilution with CH2Cl2,
washing with 1m aq. NaHCO3 soln., drying (MgSO4), and evaporation), and FC (hexane/AcOEt 7:3) gave 9
(43 mg, 8%) and 4A (358.5 mg, 65%).
b) The reaction of 3A/3B 95 :5 (420mg, 0.76 mmol) in CH 2Cl2 (10ml) with Ac 2O (80 ml, 0.81 mmol; 1.5 h)
and FC (hexane/AcOEt 2 :1) gave 10 (25 mg, 6%) and 4A (331 mg, 73%).
(Z)-N'-(2,3,4,6-Tetra-O-benzyl-d-galactopyranosylidene)acetohydrazide (4A). Colourless oil. Rf (hexane/
AcOEt 1:1) 0.16. [a]2D5 ˆ À13.9 (c ˆ 0.55, CHCl3). IR (CHCl3): 3360w, 3060w, 3020w (sh), 2990m, 2920w,
2860m, 1665s, 1495m, 1450s, 1360m, 1325m, 1245m (br.), 1195w, 1090s (br.), 1060s (sh), 1025m, 910w, 850w,
815w. 1H-NMR (400 MHz, CDCl3, 298 K, 2 diastereoisomers in the ratio 4 :1): Table 2; additionally, for the
major isomer: 7.39 7.25 (m, 20arom. H); 4.91 ( d, J ˆ 11.4), 4.86 (d, J ˆ 11.5), 4.72 (d, J ˆ 12.0), 4.64 (d, J ˆ
12.1), 4.63 (d, J ˆ 11.4), 4.58 (d, J ˆ 11.6), 4.50( d, J ˆ 11.8), 4.45 (d, J ˆ 11.8) (8 PhCH); 2.29 (s, AcN);
1
additionally, for the minor isomer: 1.91 (s, AcN). H-NMR (300 MHz, C6D6, 298 K, 2 diastereoisomers in the
ratio 10:1): Table 2; additionally, for the major isomer: 7.39 7.03 (m, 20arom. H); 4.81 ( d, J ˆ 11.6), 4.62
(d, J ˆ 11.5), 4.45 (d, J ˆ 12.1), 4.40( d, J ˆ 11.8), 4.36 (d, J ˆ 11.5), 4.33 (d, J ˆ 12.1), 4.26 (d, J ˆ 11.9), 4.20
(d, J ˆ 11.9) (8 PhCH); 2.23 (s, AcN); additionally for the minor isomer: 9.09 (br. s, NH); 4.87 (d, J ˆ 11.0), 4.82
(d, J ˆ 10.8) (2 PhCH). 1H-NMR (300 MHz, C6D6, 348 K): 8.84 (s, NH); 7.30( d, J ˆ 8.3, 2 arom. H); 7.23 7.05
(m, 18 arom. H); 4.78 (d, J ˆ 11.7), 4.59 (d, J ˆ 11.7), 4.49 (d, J ˆ 12.0), 4.47 (d, J ˆ 11.7), 4.39 (d, J ˆ 12.4), 4.37
(d, J ˆ 11.4) (6 PhCH); 4.36 (d, J ˆ 5.8, HÀC(2)); 4.30( d, J ˆ 12.0), 4.25 (d, J ˆ 12.0) (2 PhCH); 4.22 4.17
(m, HÀC(5)); 4.01 (t, J ꢁ 3.1, HÀC(4)); 3.72 (dd, J ˆ 2.9, 5.6, HÀC(3)); 3.65 (br. d, J ˆ 5.7, 2 HÀC(6)); 2.13
(br. s, AcN). 13C-NMR (50.3 MHz, CDCl3, 298 K, 2 diastereoisomers in the ratio 4 :1): Table 3; additionally, for
the major isomer: 171.60( s, CˆO); 137.46 (2 C), 137.19, 137.11 (3s); 128.21 127.16 (several d); 73.61, 73.11,

2504
Helvetica Chimica Acta Vol. 86 (2003)
72.39, 72.26 (4t, 4 PhCH2); 19.87 (q, Me); additionally for the minor isomer: 165.52 (s, CˆO); 137.31 (s); 72.86,
‡
72.39, 71.71, 71.18 (4t, 4 PhCH2); 21.22 (q, Me). CI-MS (NH3): 596 (48), 595 (100, [M ‡ 1] ). Anal. calc. for
C36H38N2O6 (594.70): C 72.71, H 6.44, N 4.71; found: C 72.68, H 6.67, N 4.60.
(1R)-1,2,3,5-Tetra-O-benzyl-1-C-(5-methyl-1,3,4-oxadiazol-2-yl)-d-lyxitol (9). Rf (hexane/AcOEt 3 :2) 0.8.
IR (CHCl3): 3550w, 3090w, 3060w, 3020w, 3000w, 2960w, 2930w (br.), 2860m, 1665w, 1590w, 1555w, 1495w,
1450w, 1390w, 1350w, 1250m, 1230 1200 m, 1090s, 1020s, 950w. 1H-NMR (300 MHz, CDCl3): Table 4;
additionally, 7.37 7.21 (m, 18 arom. H); 7.13 7.09 (m, 2 arom. H); 4.71 (d, J ˆ 11.1), 4.63 (d, J ˆ 11.7), 4.57
(d, J ˆ 11.1), 4.52 (d, J ˆ 11.9), 4.45 (d, J ˆ 11.7), 4.43 (d, J ˆ 11.9), 4.38 (d, J ˆ 11.4), 4.29 (d, J ˆ 11.4)
(8 PhCH); 2.29 (s, Me). 13C-NMR (50.3 MHz, CDCl3): Table 4; additionally, 137.85 137.59 (2 C), 136.65 (3s);
128.49 127.38 (several d); 74.97, 73.37, 73.24, 72.39 (4t, 4 PhCH2); 10.73 (s, Me).
1,4-Dihydrobis[(1S)-1,2,3,5-tetra-O-benzyl-d-lyxitol-1-yl]-1,2,4,5-tetrazine (10). Rf (hexane/AcOEt 1 :1)
0.40. [a]2D5 ˆ À9.2 (c ˆ 0.22, CHCl3). UV (c ˆ 3.9 ¥ 10À4, EtOH): 229 (3.74), 252 (2.22), 258 (2.49), 263 (2.30). IR
(CHCl3): 3550m, 3370m, 3050m, 2990m, 2900m, 2860m, 1645m, 1495m, 1450s, 1395s, 1330m, 1305m, 1240m,
1090s (br.), 1065s, 1025s, 955m, 90 5m, 865w, 830w, 820w. 1H-NMR (400 MHz, CDCl3): Table 4; additionally,
7.41 7.26 (m, 18 arom. H, NH); 7.12 7.10( m, 2 arom. H); 4.83 (d, J ˆ 10.1), 4.72 (d, J ꢁ 11.9, 2 H), 4.53 (d, J ˆ
12.0), 4.45 (d, J ˆ 11.9), 4.36 (d, J ˆ 11.6), 4.30( d, J ˆ 10.5), 4.28 (d, J ˆ 11.4) (8 PhCH). 13C-NMR (50.3 MHz,
CDCl3): Table 4; additionally, 137.87, 137.73, 137.38, 136.56 (4s); 128.50 127.57 (several d); 75.00, 73.87, 73.14,
‡
‡
71.50(4 t, 4 PhCH2). ESI-MS: 1143 (15, [M ‡ K] ), 1127 (100, [M ‡ Na] ).
(Z)-2'-(2,3,4,6-Tetra-O-benzyl-d-galactopyranosylidene)toluene-4-sulfonohydrazide (4B). The reaction of
3A/3B 95 :5 (141 mg, 0.25 mmol) in pyridine (2.5 ml) with TsCl (67 mg, 0.30 mmol) in pyridine (2.5 ml; 1.5 h)
and FC (CH2Cl2) gave 4B [19] (111 mg, 63%). 1H-NMR (400 MHz, C6D6): Table 2; additionally, 7.99 (d, J ˆ 8.2,
2 arom. H); 7.27 7.06 (m, 20arom. H); 6.68 ( d, J ˆ 8.2, 2 arom. H); 4.60( d, J ˆ 11.4), 4.43 (d, J ˆ 11.6), 4.38
(d, J ˆ 12.1), 4.26 (d, J ˆ 11.9), 4.24 (d, J ˆ 11.8), 4.23 (d, J ˆ 12.4), 4.21 (d, J ˆ 11.7), 4.14 (d, J ˆ 11.9, 8 PhCH);
1.77 (s, Me). 13C-NMR (50.3 MHz, C6D6): Table 3; additionally, 143.34, 138.45 (2 C), 138.30(2 C), 136.81 (4 s);
129.57 (d, 2 C); 128.64 127.51 (several d); 73.72, 73.38, 72.48, 72.36 (4t, 4 PhCH2); 21.08 (q, Me).
(Z)-2'-(2,3,4,6-Tetra-O-benzyl-d-mannopyranosylidene)toluene-4-sulfonohydrazide (6 [19]). The reaction
of 5A/5B 55 :45 (179 mg, 0.32 mmol) in pyridine (6 ml) with TsCl (68 mg, 0.36 mmol) in pyridine (4 ml; 1.5 h)
and FC (hexane/AcOEt 4 :1) gave 6 [22] (124 mg, 55%).
(Z)-2'-(2,3,4,6-Tetra-O-benzyl-d-glucopyranosylidene)aceto(1'-15N)- and -(2'-15N)hydrazide (12A/12B). a)
The reaction of 11A/11B 75 :25 (45 mg, 0.08 mmol) in CH2Cl2 (4 ml) with Ac2O (200 ml, 1.11 mmol; 1 h) and FC
(hexane/AcOEt 2 :1 ! 1:1) gave 12A/12B 1:1 (37.5 mg, 77%).
b) The reaction of 11A/11B 78 :22 (300 mg, 0.54 mmol) in CH2Cl2 (10ml) with Ac 2O (55 ml, 0.58 mmol;
3 h) and FC (hexane/AcOEt 2 :1) gave 12A/12B 55 :45 (272 mg, 85%). 1H-NMR (300 MHz, CDCl3, 298 K, 7:3
mixture of 2 isotopomeric pairs of diastereoisomers, 12A/12B 1:1): 8.78 (d, J ˆ 94.4, exchanged with D2O,
0.15 NH); 8.78 (s, exchanged with D2O, 0.15 NH); 8.74 (d, J ˆ 93.5 exchanged with D2O, 0.35 NH); 8.74
(s, exchanged with D2O, 0.35 NH); 7.40 7.25 (m, 18 arom. H); 7.19 7.15 (m, 2 arom. H); 4.76 4.36
(m, 8 PhCH); 4.11 (d, J ˆ 2.4, 0.7 HÀC(2)); 3.99 (dd, J ˆ 1.8, 3.8, 0.3 H), 3.93 (dd, J ˆ 2.6, 4.7, 0.7 H)
(HÀC(3)); 3.83 3.68 (m, 3 H); 2.30( s, 2.1 H), 2.07 (s, 0.9 H) (Ac). 1H-NMR (600 MHz, C6D6, 298 K, 9 :1
mixture of 2 isotopomeric pairs of diastereoisomers, 12A/12B 55 :45): Table 2; additional values for the major
isotopomeric pair: 7.28 7.24 (m, 6 arom. H); 7.17 7.05 (m, 14 arom. H); 4.58 (d, J ˆ 11.5), 4.56 (d, J ˆ 11.9),
4.44 (d, J ˆ 11.5), 4.345 (d, J ˆ 11.7), 4.340( d, J ˆ 11.9), 4.27 (d, J ˆ 12.3), 4.25 (d, J ˆ 12.2), 4.18 (d, J ˆ 11.9)
(6 PhCH); additional values for the minor isotopomeric pair: 8.59 (d, 1J(15N,H) ˆ 92.9, 0.5 H), 8.59 (br. s, 0 .5 H)
(NH); 4.77 (d, J ˆ 11.9), 4.69 (d, J ˆ 12.2), 4.09 (d, J ˆ 11.2) (3 PhCH); 4.02 (br. s, HÀC(2)); 3.61 3.59
(m, 2 HÀC(6)). 13C-NMR (150.9 MHz, C6D6, 298 K, 9 :1 mixture of 2 isotopomeric pairs of diastereoisomers,
12A/12B 55 :45): Table 3; additional values for the major isotopomeric pair: 171.03 (d, 2J(15N,C) ˆ 2.5, 0.45 C),
170.96 (d, 1J(15N,C) ˆ 6.6, 0.55 C) (CˆO); 138.49, 138.42, 137.89, 137.68 (4s); 129.40 127.56 (several d); 73.34,
73.24, 71.84, 70.84 (4t, 4 PhCH2); 20.20 (d, 2J(15N,C) ˆ 1.4, 0.55 C), 20.20 (d, 3J(15N,C) ˆ 7.2, 0.45 C) (Me);
additional values for the minor isotopomeric pair: 164.46 (br. s, CˆO); 81.46 (d, C(3)); 77.97 (d, C(4)); 76.63
(d, C(5)); 74.2 (2 overlapping dd, C(2)); 73.26, 72.70, 71.47, 71.06 (4t, 4 PhCH2); 68.59 (t, C(6)); 20.54
(br. q, Me). 15N-NMR (60.8 MHz, C6D6, 9 :1 mixture of 2 isotopomeric pairs of diastereoisomers, 12A/12B
55 :45): À224 (d, J ꢁ 92, 0.05 N), À222.95 (d, J ˆ 92.4, 0.5 N) (15N of 12A); À132 (br. s, 0 .0 4 N),À130.43
(br. s, 0.41 N) (15N of 12B).
(Z)-2'-(2,3,4,6-Tetra-O-benzyl-d-glucopyranosylidene)toluene-4-sulfono(1'-15N)- and -(2'-15N)hydrazide
(13A/13B). The reaction of 11A/11B 78 :22 (100 mg, 0.18 mmol) in CH2Cl2 (8 ml) with TsCl (38 mg,
0.20 mmol) in pyridine (2 ml; 3 h), FC (hexane/AcOEt 4 :1), and crystallisation from MeOH gave 13A/13B
65 :35 (98 mg, 77%) as fine needles. Rf (hexane/AcOEt 1:1) 0.59. M.p. 132 132.58. 1H-NMR (600 MHz, CDCl3,

Helvetica Chimica Acta Vol. 86 (2003)
2505
13A/B 65 :35): Table 2; additionally, 7.82 (d, J ˆ 8.3, 2 arom. H); 7.39 7.12 (m, 22 arom. H); 4.54 (d, J ˆ 11.9),
4.53 (d, J ˆ 11.5), 4.51 (d, J ˆ 12.0), 4.48 (d, J ˆ 11.7), 4.40( d, J ˆ 11.4), 4.31 (d, J ˆ 11.7), 4.29 (d, J ˆ 11.5), 4.22
(d, J ˆ 11.9) (8 PhCH); 2.30( s, Me). 13C-NMR (150.9 MHz, CDCl3, 13A/13B 65 :35): Table 3; additionally,
143.79, 137.54, 137.45, 137.02, 136.83, 135.35 (6s); 129.46 127.85 (several d); 73.39, 73.00, 71.53, 70.37
(4t, 4 PhCH2); 21.49 (q, Me). 15N-NMR (60.8 MHz, CDCl3, 13A/13B ca. 7:3): À232.05 (d, J ˆ 83.9, 0.7 N, N of
13A); À134.74 (br. s, 0.3 N, N' of 13B).
Treatment of 14A/14B with Ac2O. a) The reaction of 14A/14B 85 :15 (100 mg, 0.18 mmol) in CH2Cl2 (3 ml)
with Ac2O (0.4 ml; 90 min) and FC (hexane/AcOEt 2 :1) gave 15A/15B 3 :7 (89 mg, 83%).
b) The reaction of 14A/14B 3 :1 (230mg, 0.42 mmol) in CH 2Cl2 (10ml) with Ac 2O (55 ml, 0.42 mmol; 3 h)
and FC (hexane/AcOEt 2 :1) gave 17A 17D/18 3 :1 (10mg, 5%) and 15A/15B 3 :7 (204 mg, 81%).
(Z)-2'-(2,3,4,6-Tetra-O-benzyl-d-galactopyranosylidene)aceto(1'-15N)- and -(2'-15N)hydrazide (15A/15B):
Rf (hexane/AcOEt 1:1) 0.18. 1H-NMR (600 MHz, C6D6, 298 K, 10:1 mixture of 2 isotopomeric pairs of
diastereoisomers, 15A/15B 3 :7): Table 2; additional values for the major isotopomeric pair: 7.33 (d, J ˆ 7.4,
2 arom. H); 7.26 (d, J ˆ 7.4, 2 arom. H); 7.21 7.06 (m, 16 arom. H); 4.81 (d, J ˆ 11.6), 4.62 (d, J ˆ 11.5), 4.46
(d, J ˆ 12.0), 4.41 (d, J ˆ 12.1), 4.36 (d, J ˆ 11.5), 4.35 (d, J ˆ 12.0), 4.26 (d, J ˆ 11.8), 4.22 (d, J ˆ 11.9)
(8 PhCH); 2.24 (s, AcN); additional values for the minor isotopomeric pair: 9.07 (d, 1J(15N,H) ˆ 93.2, 0.3 H),
9.07 (br. s, 0.7 H) (NH); 4.86 (d, J ˆ 11.2), 4.53 (d, J ˆ 11.7) (2 PhCH); 4.49 (br. s, HÀC(2)); 4.29 (d, J ˆ 11.7),
4.19 (d, J ˆ 11.5), 4.17 (d, J ˆ 11.7) (3 PhCH); 4.15 4.13 (m, HÀC(5)); 3.99 3.97 (m, HÀC(4)); 3.88 3.84
(m, HÀC(3)); 3.78 (dd, J ˆ 1.2, 10.5, HÀC(6)). 13C-NMR (150.9 MHz, C6D6, 298 K, 10:1 mixture of
2
isotopomeric pairs of diastereoisomers, 15A/15B 3 :7): Table 3; additional values for the major isotopomeric
pair: 171.22 (s, 0.7 C), 171.22 (d, 1J(C,N) ˆ 6.6, 0.3 C) (CˆO); 138.50(2 C), 138.41, 138.32 (3 s); 128.59 127.76
(several d); 74.01, 73.57, 72.80, 72.62 (4t, 4 PhCH2); 20.39 (br. q, Me); additional values for the minor
isotopomeric pair: 78.79 (d, C(3)); 77.55 (d, C(5)); 73.27 (t, PhCH2); 72.93 (d, C(4)); 71.89 (t, PhCH2); 69.77
(t, C(6)). 15N-NMR (40.6 MHz, CDCl3, 298 K, 3 :2 mixture of 2 isotopomeric pairs of diastereoisomers, 15A/
15B 3 :7): À221.5 (d, J ˆ 97.3, 0.18 N), À221.5 (d, J ꢁ 115, 0.12 N) (15N of 15A); À128.9 (s, 0.42 N), À123.5
(s, 0.28 N) (15N of 15B). 15N-NMR (60.8 MHz, C6D6, 298 K, 10:1 mixture of 2 isotopomeric pairs of
diastereoisomers, 15A/15B ca. 1:2): À222.08 (d, J ˆ 93.00.3 N, 15N of 15A); À124.72 (s, 0.6 N), À118.98
(s, 0 .0 7 N) 1(5N of 15B); d for minor diastereoisomer (0.03 N) hidden by the noise.
Data of 1,4-Dihydrobis[(1S)-2,3,4,6-tetra-O-benzyl-d-lyxitol-1-yl](1,4- and -1,6-15N2)-1,2,4,5-tetrazine and
1,2,3,5-Tetra-O-benzyl-d-galactonamide (17A 17D and 18). Rf (hexane/AcOEt 1:1) 0.40. 1H-NMR (600 MHz,
CDCl3, 17A 17D/18 3 :1): Tables 1 and 3; additionally for 17A 17D: 7.42 7.10( m, 20aro m. H, NH); 4.83
(d, J ˆ 10.1), 4.71 (d, J ˆ 10.2), 4.70 (d, J ˆ 11.4), 4.52 (d, J ˆ 12.0), 4.44 (d, J ˆ 12.3), 4.35 (d, J ˆ 11.3), 4.32
(d, J ˆ 11.3), 4.28 (d, J ˆ 11.3) (8 PhCH); additionally for 18: 4.77 (d, J ˆ 10.7), 4.60 (d, J ˆ 10.9), 4.59 (d, J ˆ
11.4), 4.54 (d, J ˆ 12.0), 4.46 (d, J ꢁ 12.5), 4.41 (d, J ˆ 11.4), 4.37 (d, J ꢁ 11.5), 4.28 (d, J ˆ 11.3) (8 PhCH).
13C-NMR (150.9 MHz, CDCl3, 17A 17D/18 3 :1): Tables 2 and 3, additionally for 17A 17D: 137.91, 137.76,
137.42, 136.60(4 s); 128.51 127.59 (several d); 75.03, 73.91, 73.21, 71.56 (4t, 4 PhCH2); additionally for 18: 137.84,
137.60, 137.42, 136.45 (4s); 75.16, 74.06, 73.33, 71.89 (4t, 4 PhCH2). 15N-NMR (60.8 MHz, C6D6, 298 K): À252.63
(d, J ˆ 86.7, NH); À125.26 (d, J ˆ 5.7, CˆN).
(Z)-2'-(2,3,4,6-Tetra-O-benzyl-d-galactopyranosylidene)toluene-4-sulfono(1'-15N)- and -(2'-15N)hydrazide
(16A/16B). The reaction of 14A/14B 4 :1 (100 mg, 0.18 mmol) in CH2Cl2 (8 ml) with TsCl (38 mg, 0.20 mmol)
in pyridine (5 ml; 3 h) and FC (hexane/AcOEt 4 :1) gave 16A/16B 35 :65 (100 mg, 78%). Yellowish oil. Rf
(hexane/AcOEt 2 :1) 0.33. 1H-NMR (600 MHz, C6D6, 16A/16B 35 :65): Table 2; additionally, 8.00 (d, J ˆ 8.2,
2 arom. H); 7.27 7.06 (m, 20arom. H); 6.69 ( d, J ˆ 8.1, 2 arom. H); 4.62 (d, J ˆ 11.4), 4.46 (d, J ˆ 11.6), 4.39
(d, J ˆ 12.1), 4.28 (d, J ˆ 10.9), 4.24 (d, J ˆ 12.2, 2 H), 4.23 (d, J ˆ 11.6), 4.16 (d, J ˆ 11.8) (8 PhCH); 1.79
(s, Me). 13C-NMR (150.9 MHz, C6D6, 16A/16B 35 :65, assignment based on a 1H,13C-COSY spectrum): Table 3;
additionally, 143.24, 138.42, 138.41, 138.31, 138.23, 137.02 (6s); 129.52 (2d); 128.71 127.69 (several d); 73.55,
73.45, 72.59, 72.16 (4t, 4 PhCH2); 21.10( q, Me). 15N-NMR (60.8 MHz, C6D6, 16A/16B ca. 2 :3): À230.00 (d, J ˆ
84.5, 0.4 N, 15N of 16A); À125.02 (br. s, 0 .6 N,15N of 16B).
1'-Methyl-2'-[(Z)-2,3,4,6-tetra-O-benzyl-d-glucopyranosylidene]toluene-4-sulfonohydrazide (20) and
2,3,4,6-Tetra-O-benzyl-d-glucono-1,5-lactone (21 [40][41]). The reaction of 19A/19D 72 :28 (600 mg,
1.06 mmol) in CH2Cl2/pyridine 5 :1 (30ml) with TsCl (222 mg, 1.17 mmol; 3.5 h) and FC (hexane/AcOEt
4 :1) gave 20/21 3 :1 (600 mg, 79%). Colourless oil. Rf (hexane/AcOEt 1:1) 0.67. IR (CHCl3, 20/21 3 :1): 3060w
(sh), 3020w (sh), 3000w, 2920m, 2870m, 1750m, 1645m, 1595w, 1495m, 1455m, 1350s, 1305m, 1280m, 1260m
1
(br.), 1185m, 1160s, 1090s (sh), 1070s, 1025s, 995m (sh), 910m, 860w, 810m. H-NMR (400 MHz, C6D6, 20/21
3 :1): Table 2 ; additionally for 20, 8.0 2 d(, J ˆ 8.2, 2 arom. H); 7.45 (d, J ˆ 7.2, 2 arom. H ) ; 7.32 7.02
(m, 18 arom. H); 6.82 (d, J ˆ 8.0, 2 arom. H); 4.71 (d, J ˆ 12.1), 4.59 (d, J ˆ 12.1), 4.52 (d, J ˆ 11.6), 4.39

2506
Helvetica Chimica Acta Vol. 86 (2003)
(d, J ˆ 11.6), 4.34 (d, J ˆ 12.4), 4.26 (d, J ˆ 12.1), 4.22 (d, J ˆ 11.7), 4.06 (d, J ˆ 11.8) (8 PhCH); 1.88 (s, Me);
characteristic signals of 21: 4.27 (dt, J ꢁ 8.5, 2.8, HÀC(5)); 4.07 (d, J ˆ 6.5, HÀC(2)); 3.92 (d, J ˆ 8.7, 6.8,
HÀC(4)); 3.81 (t, J ˆ 6.6, HÀC(3)); 3.46 (dd, J ˆ 11.1, 2.4, HÀC(6)); 3.42 (dd, J ˆ 11.1, 3.2, H'ÀC(6)).
13C-NMR (50.3 MHz, C6D6, 20/21 3 :1): Table 3; additionally for 20, 142.85, 138.01, 137.89, 137.26, 137.06, 132.35
(6s); 129.38 127.02 (several d); 72.78, 72.61, 70.97, 70.26 (4t, 4 PhCH2); 20.71 (q, Me); characteristic signals of
21: 169.23 (s, C(1)); 80.91 (d, C(3)); 78.12 (d, C(4)); 77.35 (d, C(2)); 76.03 (d, C(5)); 68.23 (t, C(6)). CI-MS
‡
(NH3): 723 (11), 722 (36), 721 (81, [M ‡ 1] of 20), 614 (19), 613 (54), 506 (14), 505 (48), 351 (10), 203 (100),
174 (21), 139 (15), 108 (17).
1'-Methyl-2'-[(Z)-2,3,4,6-Tetra-O-benzyl-d-galactopyranosylidene]toluene-4-sulfonohydrazide (23) and
2,3,4,6-Tetra-O-benzyl-d-galactono-1,5-lactone (24 [42]). The reaction of 22A/22B 85 :15 (427 mg, 0.75 mmol)
in CH2Cl2/pyridine 4 :1 (25 ml) with TsCl (158 mg, 0.83 mmol; 3 h) and FC (dry hexane/AcOEt 4 :1) gave 23
(305 mg, 56%). Colourless oil. Upon standing for 10 h at r.t., 23 mostly decomposed to 24 [42] ( ! 23/24 1 :3). Rf
1
(hexane/AcOEt 1 :1) 0.67. H-NMR (600 MHz, C6D6, 23/24 1:3): Table 2; additionally for 23, 7.62 (d, J ˆ 8.2,
2 arom. H); 7.23 (d, J ˆ 7.0, 2 arom. H); 7.20 7.01 (m, 18 arom. H); 6.79 (d, J ˆ 8.3, 2 arom. H); 4.69 (d, J ˆ
11.6), 4.55 (d, J ˆ 11.3), 4.54 (d, J ˆ 11.5), 4.26 (d, J ˆ 11.9), 4.23 (d, J ˆ 11.2), 4.18 (d, J ˆ 12.0) (6 PhCH); 1.95
(s, Me); characteristic signals of 24: 4.43 (d, J ˆ 9.6, HÀC(2)); 3.95 (ddd, J ˆ 7.6, 5.9, 1.0, HÀC(5)); 3.86
(br. d, J ˆ 1.6, HÀC(4)); 3.57 (d, J ˆ 9.5, 1.7, HÀC(3)); 3.54 (dd, J ˆ 8.8, 7.6, HÀC(6)); 3.46 (dd, J ˆ 9.2, 5.6,
H'ÀC(6)). 13C-NMR (50.3 MHz, C6D6, 23/24 1:3): Table 3; additionally for 23, 143.35, 138.50(2 C), 138.42,
132.89 (4s); 74.51, 73.47 (2t, 2 PhCH2); 72.73 (t, 2 PhCH2); 21.20( q, Me); characteristic signals of 24: 169.73
(s, C(1)); 80.86 (d, C(3)); 78.16 (d, C(5)); 77.32 (d, C(2)); 72.96 (d, C(4)); 67.80( t, C(6)).
1'-Methyl-2'-[(Z)-2,3,4,6-Tetra-O-benzyl-d-mannopyranosylidene]toluene-4-sulfonohydrazide (26) and
2,3,4,6-Tetra-O-benzyl-d-manno-1,5-lactone (27 [43]). The reaction of 25A/25B 85 :15 (390mg, 0.69 mmol)
in CH2Cl2/pyridine 4 :1 (25 ml) with TsCl (146 mg, 0.76 mmol; 1.5 h) and FC (dry hexane/AcOEt 4 :1) gave 26
(326 mg, 66%). Colourless oil. Upon standing for 10h at r.t., 26 partially decomposed to 27 [43] ( ! 26/27 1 :1).
Rf (hexane/AcOEt 1:1) 0.67. IR (CHCl3): 3060w, 3020m (sh), 3000m, 2920m, 2870m, 1770m, 1640m, 1595w,
1495m, 1450m, 1395w (sh), 1350m, 1305w, 1285m, 1255m, 1185m, 1160s, 1080s (br.), 1025s, 90 5m, 880w, 810w.
1H-NMR (600 MHz, C6D6, 30 0 K2;6/27 1:2, assignment based on a 1H,1H-COSY spectrum): Table 2;
additionally for 26: 8.02 (d, J ˆ 8.2, 2 arom. H); 7.25 7.01 (m, 20arom. H); 6.86 ( d, J ˆ 8.0, 2 arom. H); 4.74
(d, J ˆ 12.3), 4.70( d, J ˆ 11.6), 4.48 (d, J ˆ 12.3), 4.37 (d, J ˆ 11.6); 4.34 (d, J ˆ 12.1) (5 PhCH); 4.27 (s, PhCH2);
4.14 (d, J ˆ 11.6, PhCH); 1.89 (s, Me); characteristic signals of 27: 4.23 (d, J ˆ 2.7, HÀC(2)); 4.11 (ddd, J ˆ 7.0,
5.5, 3.8, HÀC(5)); 4.05 (t, J ꢁ 2.2, HÀC(3)); 3.83 (d, J ˆ 7.1, 1.8, HÀC(4)); 3.53 (dd, J ˆ 10.7, 3.9, HÀC(6)); 3.48
(dd, J ˆ 10.9, 5.5, H'ÀC(6)). 13C-NMR (50.3 MHz, C6D6, 297 K; 26/27 1:1 assignment based on a 1H,13C-COSY
spectrum): Table 3; additionally for 26/27: 138.60 137.67 (several s); 129.89 127.51 (several d); additionally for
26: 143.52, 132.85 (2s); 74.06, 73.28, 71.78, 70.88 (4t, 4 PhCH2); 21.18 (q, Me); characteristic signals of 27: 168.77
(s, C(1)); 78.66 (d, C(5)); 77.62 (d, C(3)); 76.72 (d, C(4)); 76.36 (d, C(2)); 69.67 (t, C(6)).
1'-Methyl-2'-[(Z)-(2,3:4,6-Di-O-isopropylidene)-d-mannopyranosylidene]toluene-4-sulfonohydrazide
(29). The reaction of 28A/28B 1:1 (368 mg, 1.28 mmol) in CH2Cl2/pyridine 4 :1 (25 ml) with TsCl (268 mg,
1.41 mmol; 2 h) and FC (dry hexane/AcOEt 3 :1) gave 29 (336 mg, 60%). Colourless foam. Rf (hexane/AcOEt
1:1) 0.37. [a]2D5 ˆ ‡114.8 (c ˆ 0.45, CHCl3). IR (CHCl3): 2990w, 2985w (sh), 2930w 2910w (br.), 1640m, 1595w,
1450w (br.), 1385m, 1375m, 1350m, 1305w, 1240m (br.), 1205w, 1185m, 1160s, 1105s, 1085s, 1065s, 1025s, 940w,
920w, 870w. IR (KBr): 2980m, 2920m, 2880m (sh), 1640m, 1595m, 1490w, 1455m, 1380m (sh), 1370s, 1345s,
1305m, 1240s, 1220s, 1195s, 1185s, 1160s, 1105s, 1085s, 1065s, 1010m, 945m, 915w, 880m, 815m. 1H-NMR
(400 MHz, C6D6): Table 2; additionally, 8.04 (d, J ˆ 8.3, 2 arom. H); 6.85 (d, J ˆ 8.1, 2 arom. H); 1.87 (s, Me);
1.60, 1.34, 1.19, 1.08 (4s, 2 Me2C). 13C-NMR (50.3 MHz, C6D6): Table 3; additionally, 143.61, 132.26 (2s); 129.96,
129.24 (2d, 4 C); 112.24, 99.77 (2s, 2 Me2C); 28.84, 27.41, 25.81, 18.66 (4q, 2 Me2C); 21.19 (q, Me). CI-MS (NH3):
‡
442 (25), 441 (100, [M ‡ 1] ). Anal. calc. for C20H28N2O7S (440.51): C 54.53, H 6.41, N 6.36, S 7.28; found: C
54.69, H 6.37, N 6.35, S 7.49.
Treatment of 30 with Ac2O. The reaction of crude 30 (324 mg, ca. 1.2 mmol) in CH2Cl2 (10ml) with Ac 2O
(150 ml, 1.57 mmol; 12 h) and FC (hexane/AcOEt 1:1) gave 32 (27 mg, 8%) and 31A (237 mg, 63%).
Treatment of 30 with TsCl. The reaction of crude 30 (493 mg, ca. 1.8 mmol) in pyridine (5 ml) with TsCl
(369 mg, 1.9 mmol) in pyridine (5 ml; 20min) and FC (CH 2Cl2) gave 32 (55 mg, 11%) and 31B (467 mg, 61%).
(Z)-2'-(2,3:5,6-Di-O-isopropylidene-d-mannofuranosylidene)acetohydrazide (31A). Colourless oil. Rf
(hexane/AcOEt 1:2) 0.07. [a]2D5 ˆ ‡114.4 (c ˆ 0.66, CHCl3). UV (c ˆ 8.27 ¥ 10À4, EtOH): 232 (3.295). IR
(CHCl3): 3390w, 3360w, 2980m, 2930w, 2880w, 1700m (sh), 1670s, 1500w, 1455m, 1380s, 1370s, 1315m, 1250m,
1195m, 1155m, 1115m, 1070s, 1030m, 990w, 970m, 940w, 860m, 840m, 815w. 1H-NMR (400 MHz, CDCl3, 298 K,
2 diastereoisomers in the ratio 85 :15): Table 2; additionally, for the major isomer, 2.23 (s, AcN); 1.47, 1.46, 1.42,

Helvetica Chimica Acta Vol. 86 (2003)
2507
1.39 (4s, 2 Me2C); additionally, for the minor isomer, 2.05 (s, AcN); 1.46, 1.45, 1.41, 1.39 (4s, 2 Me2C). 13C-NMR
(50.3 MHz, CDCl3, 298 K, 2 diastereoisomers in the ratio 85 :15): Table 3; additionally, for the major isomer,
172.22 (s, CˆO); 113.79, 109.30 (2s, 2 Me2C); 26.59, 26.30, 25.19, 24.63 (4q, 2 Me2C); 19.61 (q, Me); additionally
for the minor isomer, 113.69, 109.17 (2s, 2 Me2C); 26.41, 25.70, 24.95, 24.84 (4q, 2 Me2C); 20.11 (q, Me). CI-MS:
‡
‡
(NH3): 332 (41, [M ‡ NH4] ), 316 (14), 315 (100, [M ‡ 1] ). Anal. calc. for C14H22N2O6 (314.34): C 53.49, H 7.05,
N 8.91; found: C 53.29, H 7.04, N 8.73.
(Z)-2'-(2,3:5,6-Di-O-isopropylidene-d-mannofuranosylidene)toluene-4-sulfonohydrazide (31B). Yellowish
crystals. Rf (hexane/AcOEt 1:1) 0.31. M.p. 76 778. [a]2D5 ˆ ‡145.4 (c ˆ 0.32, CHCl3). UV (c ˆ 1.88 ¥ 10À4
,
EtOH): 206 (2.202), 216 (2.231). IR (KBr): 3210w, 3070w, 2990m, 2960m, 2940m, 2870w, 1730m, 1695m, 1600w,
1540w, 1495w, 1455m, 1385m, 1375m, 1345m, 1290m, 1255m, 1220s, 1185m, 1170s, 1120m, 1090m, 1070m, 1040m
(br.), 975m, 945w, 845m, 810m. 1H-NMR (400 MHz, CDCl3): Table 2; additionally, 7.85 (d, J ˆ 8.2, 2 arom. H);
7.30( d, J ˆ 8.2, 2 arom. H); 2.41 (s, Me); 1.45, 1.37, 1.35, 1.18 (4s, 2 Me2C). 13C-NMR (150.9 MHz, CDCl3,
assignment based on a 1H,13C-COSY spectrum): Table 3; additionally, 143.89, 135.25 (2s); 129.48, 128.00
(2d, 4 C); 114.16, 109.67 (2s, 2 Me2C); 26.90, 26.42, 25.86, 24.94 (4q, 2 Me2C); 21.53 (q, Me). 15N-NMR
(40.6 MHz, CDCl3): À230.9 (d, 1J(15N,H) ˆ 83.6, NH); À144.8 (s, CˆN). CI-MS (C4H10): 428 (22), 427 (100,
‡
[M ‡ 1] ), 273 (14), 259 (31), 157 (10). Anal. calc. for C19H26N2O7S (426.48): C 53.51, H 6.14, N 6.57, S 7.52;
found: C 53.34, H 5.95, N 6.42, S 7.75.
Bis[(1R)-1,2:4,5-di-O-isopropylidene-d-arabinitol-1-yl]-1,2,4,5-tetrazine (32). Pink foam. Rf (hexane/
AcOEt 1:1) 0.38. [a]2D5 ˆ À16.9 (c ˆ 0.34, CHCl3). UV (c ˆ 8.1 ¥ 10À5, EtOH): 216 (0.729), 264 (0.139), 522
(0.031). IR (KBr): 3450m, 2985m, 2935m, 1730w, 1630w, 1455w, 1380m, 1370m (sh), 1250s, 1215s, 1160m, 1120m,
1095m, 1070s, 1010m, 975w, 885w, 850w. 1H-NMR (400 MHz, CDCl3): Table 4; additionally, 1.82, 1.59, 1.36, 1.32
(4s, 2 Me2C). 13C-NMR (50.3 MHz, CDCl3): Table 4; additionally, 111.41, 109.47 (2s, 2 Me2C); 26.68, 26.25,
‡
25.35, 25.15 (4q, 2 Me2C). EI-MS: 542 (2, M ), 499 (21), 301 (25), 272 (18), 243 (16), 185 (29), 141 (44), 139
‡
(15), 127 (16), 126 (20), 113 (15), 101 (100, C5H9O2 ), 100 (20), 99 (29), 98 (40), 97 (28), 85 (32), 83 (15), 81
(28), 73 (21), 72 (22), 71 (24), 70(27), 69 (31), 60(78), 58 (19), 56 (23), 44 (74), 43 (16), 42 (35). Anal. calc. for
C24H38N4O10 (542.58): C 53.13, H 7.06, N 10.33; found: C 53.14, H 7.22, N 10.07.
Treatment of 33A 33D with TsCl. The reaction of 33A/33B/33C/33D 76 :4 :12 :8 (413 mg, 0.90 mmol) in
CH2Cl2/pyridine 4 :1 (25 ml) with TsCl (189 mg, 0.99 mmol; 1.5 h) and FC (hexane/AcOEt 4 :1) gave (E/Z)-34
2 :1 (242 mg, 44%) and 35 [44][45] (116 mg, 30%).
1'-Methyl-2'-[(E/Z)-2,3-O-Isopropylidene-5-O-triphenylmethyl-d-ribofuranosylidene]toluene-4-sulfonohy-
drazide ((E/Z)-34). Colourless foam. Rf (hexane/AcOEt 1:1) 0.61. M.p. 115 1168. [a]2D5 ˆ À120.6 (c ˆ 0.57,
CHCl3). IR (KBr): 3040w, 3010w, 2975m, 2920m, 2860w, 1660s, 1595m, 1485m, 1445m, 1370m, 1345s, 1245m,
1225s, 1180m, 1160s, 1085s, 1020m, 995s, 930w, 895w, 870w, 845w, 810m. 1H-NMR (400 MHz, C6D6, (E)/(Z)
2 :1): Table 2; additionally for (E)-34, 7.95 (d, J ˆ 8.2, 2 arom. H); 7.566 (d, J ˆ 8.1, 4 arom. H); 7.409 (d, J ˆ 7.2,
2 arom. H); 7.22 6.97 (m, 9 arom. H); 6.82 (d, J ˆ 7.9, 2 arom. H); 1.88 (s, Me); 1.30, 1.04 (2s, Me2C);
additionally, for (Z)-34, 8.10( d, J ˆ 8.2, 2 arom. H); 7.570( d, J ˆ 8.5, 4 arom. H); 7.407 (d, J ˆ 7.9, 2 arom. H);
7.22 6.97 (m, 9 arom. H); 6.82 (d, J ˆ 7.9, 2 arom. H); 1.85 (s, Me); 1.43, 1.12 (2s, Me2C). 13C-NMR (50.3 MHz,
C6D6, (E)/(Z) 2 :1): Table 3; additionally, for (E)-35, 143.81 (3s); 143.39, 131.65 (2s); 130.11 127.51 (several d);
112.88 (s, Me2C); 87.98 (s, Ph3C); 26.74, 25.17 (2q, Me2C); 21.25 (q, Me); additionally, for (E)-35, 143.53 (4s);
132.39 (s); 113.15 (s, Me2C); 87.98 (s, Ph3C); 27.16, 25.93 (2q, Me2C); 21.25 (q, Me). CI-MS (NH3): 613 (6, [M ‡
‡
‡
1] ), 460(14), 459 (40), 430(15), 372 (14), 371 (65), 370(10), 243 (100, Tr
(612.73): C 68.61, H 5.92, N 4.57, S 5.23; found: C 68.34, H 6.07, N 4.82, S 5.50.
). Anal. calc. for C35H36N2O6S
2,3-O-Isopropylidene-5-O-triphenylmethyl-d-ribono-1,4-lactone [45] (35). Colourless crystals. Rf (hexane/
AcOEt 2 :1) 0.44. M.p. 112 1138 ([47]: 115 1168). 1H-NMR (CDCl3): see [45]. 13C-NMR (50.3 MHz, CDCl3):
174.30( s, C(1)); 142.87 (3s); 128.42 127.17 (several d); 113.17 (s, Me2C); 87.83 (s, Ph3C); 81.33 (d, C(4)); 78.54
(d, C(3)); 75.74 (d, C(2)); 62.80( t, C(5)); 26.74, 25.58 (2q, Me2C).
REFERENCES
[1] K. Briner, A. Vasella, Helv. Chim. Acta 1989, 72, 1371.
[2] B. Bernet, S. E. Mangholz, K. Briner, A. Vasella, Helv. Chim. Acta 2003, 86, 1488.
[3] A. Vasella, C. Witzig, C. Waldraff, P. Uhlmann, K. Briner, B. Bernet, L. Panza, R. Husi, Helv. Chim. Acta
1993, 76, 2847.
[4] A. Vasella, in −Bioorganic Chemistry: Carbohydrates×, Ed. S. M. Hecht, Oxford University Press, New
York, 1999, p. 56.

2508
Helvetica Chimica Acta Vol. 86 (2003)
[5] A. Vasella, B. Bernet, M. Weber, W. Wenger, in −Oligosaccharides in Chemistry and Biology; A
Comprehensive Handbook×, Ed. B. Ernst, J. Wiley, New York, 2000, p. 156.
[6] E. Schmitz, D. Habisch, Rev. Chim. Acad. Rep. Populaire Roumaine 1962, 7, 1281.
[7] J. W. Lown, J. Chem. Soc. C 1969, 1338.
[8] H. W. Heine, T. R. Hoye, P. G. Williard, R. C. Hoye, J. Org. Chem. 1973, 38, 2984.
[9] A. Nalieya, Y. Tamura, T. Kodema, Y. Iwakura, J. Org. Chem. 1973, 38, 3758.
[10] V. N. Yandovskii, L. B. Koroleva, P. M. Adrov, J. Org. Chem. USSR 1976, 12, 428.
[11] E. Schmitz, D. Habisch, C. Gr¸ndemann, Chem. Ber. 1967, 100, 142.
[12] V. N. Yandovskii, T. K. Klindukhova, J. Org. Chem. USSR 1974, 10, 1520.
[13] a) H. W. Heine, R. Hemrie, L. Heitz, S. R. Kovvali, J. Org. Chem. 1974, 39, 3187; b) H. W. Heine, L. Heitz,
J. Org. Chem. 1974, 39, 3192; c) H. W. Heine, L. S. Lehman, A. P. Glaze, A. W. Douglas, J. Org. Chem. 1980,
45, 1317; d) H. W. Heine, L. M. Baclawski, S. M. Bonser, G. D. Wachob, J. Org. Chem. 1976, 41, 3229;
e) L. S. Lehman, L. M. Baclawski, S. Harris, H. W. Heine, J. P. Springer, W. J. A. van den Heuvel, B. H.
Arison, J. Org. Chem. 1981, 45, 320.
[14] E. Schmitz, D. Habisch, Chem. Ber. 1962, 95, 680.
[15] H. W. Heine, P. G. Williard, T. R. Hoye, J. Org. Chem. 1972, 37, 2980.
[16] E. Schmitz, Angew. Chem. 1964, 76, 197.
[17] G. V. Shustov, S. N. Denisenko, M. A. Shokhen, R. G. Kostyanovskii, Bull. Acad. Sci. USSR Div. Chem. Sci.
1988, 1665.
[18] L. A. Carpino, G. Y. Han, J. Org. Chem. 1972, 37, 3404.
[19] S. E. Mangholz, A. Vasella, Helv. Chim. Acta 1991, 74, 2100.
[20] D. Roberto, H. Alper, J. Chem. Soc., Chem. Commun. 1987, 212.
[21] S. D. Isaev, G. G. Zhalnina, Z. N. Murzinova, T. V. Ivzhenko, A. G. Yurchenko, J. Org. Chem. USSR 1988,
24, 2358.
[22] G. V. Shustov, G. K. Kadorkina, S. V. Varlamov, A. V. Kachanov, R. G. Kostyanovskii, A. Rauk, J. Am.
Chem. Soc. 1992, 114, 1616.
[23] L. Somogyi, Chem. Ber. 1986, 119, 2963.
[24] S. Fritschi, A. Vasella, Helv. Chim. Acta 1991, 74, 2024.
[25] P. Fowler, B. Bernet, A. Vasella, Helv. Chim. Acta 1996, 79, 269.
[26] D. Beer, A. Vasella, Helv. Chim. Acta 1985, 68, 2254.
[27] D. R. Wolk, A. Vasella, F. Schweikart, M. G. Peter, Helv. Chim. Acta 1992, 75, 323.
[28] S. E. Mangholz, A. Vasella, Helv. Chim. Acta 1995, 78, 1020.
[29] Y. Takahashi, A. Vasella, Helv. Chim. Acta 1992, 75, 1563.
¬
[30] C. Di Stefano, G. Descotes, J.-P. Praly, Tetrahedron Lett. 1994, 35, 93.
[31] L. Somsak, G. Batta, I. Farkas, Carbohydr. Res. 1983, 124, 43.
[32] M. L. Fascio, N. B. D×Accorso, J. Heterocycl. Chem. 1995, 32, 815; C. E. Cannizzaro, I. M. E. Thiel, N. B.
D×Accorso, J. Heterocycl. Chem. 1998, 35, 481.
[33] G. Maier, A. Schick, I. Bauer, R. Boese, M. Nussbaumer, Chem. Ber. 1992, 125, 2111.
[34] C. M. Asselin, G. C. Fraser, H. K. Hall, W. E. Lindsell, A. B. Padias, P. N. Preston, J. Chem. Soc., Dalton
Trans. 1997, 3765.
[35] M. Girardot, R. Nomak, J. K. Snyder, J. Org. Chem. 1998, 63, 10063.
[36] Semichem, −AMPAC 6.0×, 7128 Summit, Shawnee, KS 66216, 1998.
[37] F. A. Neugebauer, R. Siegel, Chem. Ber. 1985, 118, 2157.
[38] J. Elguero, N. Jagerovic, C. Foces-Foces, F. H. Cano, M. V. Roux, F. Aguilar-Parrilla, H. H. Limbach, J.
Heterocycl. Chem. 1995, 32, 451.
[39] A. Lycka, D. Snobl, V. Machacek, M. Vecera, Org. Magn. Reson. 1981, 15, 390; A. Lycka, Collect. Czech.
Chem. Commun. 1984, 49, 2801.
[40] M. H¸rzeler, B. Bernet, A. Vasella, Helv. Chim. Acta 1993, 76, 995.
[41] M. D. Lewis, J. K. Cha, Y. Kishi, J. Am. Chem. Soc. 1982, 104, 4976.
[42] T. D. Heightman, P. Ermert, D. Klein, A. Vasella, Helv. Chim. Acta 1995, 78, 514.
[43] B. M. Aebischer, H. W. Hanssen, A. T. Vasella, W. B. Schweizer, J. Chem. Soc., Perkin Trans. 1 1982, 2139.
[44] M. S. P. Gonzalez, R. M. D. Aciego, F. J. L. Herrera, Tetrahedron 1988, 44, 3715.
[45] J. B. Rodriguez, Tetrahedron 1999, 55, 2157.
[46] A. Counotte-Potman, H. C. van der Plas, B. van Veldhuizen, C. A. Landheer, J. Org. Chem. 1981, 46, 5102.
Received March 26, 2003