Highly diastereoselective Henry reaction of nitro compounds with chiral derivatives of glyoxylic acid

Article abstract of DOI:10.1016/j.tet.2004.04.005

N-Glyoxyloyl-(2R)-bornane-10,2-sultam and (1R)-8-phenylmenthyl glyoxylate react stereoselectively with simple nitro compounds giving diastereoisomeric nitroalcohols with high asymmetric induction. N-Glyoxyloyl-(2R)-bornane-10,2- sultam 1a is shown to be a

Full text of DOI:10.1016/j.tet.2004.04.005

Tetrahedron 60 (2004) 4807–4820
Highly diastereoselective Henry reaction of nitro compounds with
chiral derivatives of glyoxylic acid
a
a,c
,
Iwona Kudyba,a Jerzy Raczko,a,b Zofia Urbanczyk-Lipkowska and Janusz Jurczak
*
´
aInstitute of Organic Chemistry, Polish Academy of Sciences, Kasprzaka 44/52, 01-224 Warsaw, Poland
bZD CHEMIPAN, Institute of Physical Chemistry, Polish Academy of Sciences, Kasprzaka 44/52, 01-224 Warsaw, Poland
cDepartment of Chemistry, Warsaw University, Pasteura 1, 02-093 Warsaw, Poland
Received 12 January 2004; revised 12 March 2004; accepted 1 April 2004
Abstract—N-Glyoxyloyl-(2R)-bornane-10,2-sultam and (1R)-8-phenylmenthyl glyoxylate react stereoselectively with simple nitro
compounds giving diastereoisomeric nitroalcohols with high asymmetric induction. N-Glyoxyloyl-(2R)-bornane-10,2-sultam 1a is shown
to be a highly efficient chiral inducer, superior to (1R)-8-phenylmenthyl glyoxylate 1b. In all cases, the absolute (2S) configuration at the
center bearing the hydroxy group and the relative syn configuration for the major diastereoisomers were determined.
q 2004 Elsevier Ltd. All rights reserved.
1. Introduction
2. Results and discussion
The nitroaldol addition is one of the basic methods for the
construction of carbon–carbon bonds.1 The nitroalcohols
formed in this reaction offer an easy access to a variety of
interesting intermediates such as 2-aminoalcohols, 2-nitro-
ketones and nitroalkenes,2 which are useful for the synthesis
of biologically important compounds.3 Currently, there is a
substantial interest in the development of a stereocontrolled
version of the Henry reaction. The chiral building block
approach has been widely investigated,4 however, particular
attention was paid to application of chiral catalysts,
providing nitroalcohols in good yield and with high
enantioselectivity.5 On the other hand, there are only two
examples of the diastereoselective Henry reaction using
substrates containing a chiral auxiliary, namely (1R)-8-
phenylmenthol, in the literature.6
Initial investigations on the reaction of 1a with nitro-
methane (2), carried out under conditions described by
6
´
Solladie-Cavallo et al. for glyoxylate 1b failed completely
giving only products from fragmentation of bornane-10-2-
sultam despite the temperature of the reaction. Due to these
results, we excluded potassium fluoride, common mediator
of the nitroaldol reaction. To overcome this problem, we
resolved to check two other procedures using either neutral
Al2O3 (Method A) or tetrabutylammonium fluoride tri-
hydrate (TBAF·3H2O, Method B).
As revealed in Table 1, only moderate yields were obtained
for the reactions promoted by both Al2O3 and TBAF·3H2O
(Table 1, entries 1 and 3), and substantial amounts of sultam
auxiliary were found in reaction mixtures. However, these
reactions proceeded with high diastereoselectivity. Encour-
aged by these results, we decided to improve the reaction
yields by using Al2O3 activated by heating at 120 8C under
reduced pressure (Method A00) or anhydrous TBAF dried at
80 8C in vacuum (Method B ).
In the course of our search for synthetic applications of
chiral derivatives of a-oxo acids, we have synthesised
N-glyoxyloyl-(2R)-bornane-10,2-sultam
(1a)7
and
examined its applicability in a number of diastereoselective
reactions.8 High asymmetric induction obtained during
these studies prompted us to extend our investigations on
addition of 1a to nitromethane (2) and five other simple
nitro compounds of type 3, and to compare the efficiency of
1a with that of the glyoxylic ester of (1R)-8-phenylmenthol
(1b) (Scheme 1).
Indeed, we obtained much better yields for the reactions
under investigation. We also checked the influence of high
pressure on the reaction course. Unfortunately, we did not
observed an increase of the chemical yield as we expected
(entry 5). At the next stage of our studies, we studied
five other nitro compounds, namely 1-nitrohexane (3a),
2-nitroacetaldehyde diethyl acetal (3b), 1-nitro-1-phenyl-
methane (3c), 2-nitro-1-phenylethane (3d) and ethyl
nitroacetate (3e). We have chosen them among others as a
representative group made of simple aliphatic, benzylic or
Keywords: Nitroalcohols; Nitroaldol reaction; Asymmetric induction; Nitro
compounds; Chiral auxiliary.
*
Corresponding author. Tel.: þ48-22-6320578; fax: þ48-22-6326681;
e-mail address: jurczak@icho.edu.pl
0040–4020/$ - see front matter q 2004 Elsevier Ltd. All rights reserved.
doi:10.1016/j.tet.2004.04.005

4808
I. Kudyba et al. / Tetrahedron 60 (2004) 4807–4820
Scheme 1.
having functional groups, which open routes to further
functionalisation of the obtained products. Four diastereo-
isomeric nitroalcohols were formed upon their reaction with
1a (Scheme 1, Table 2).
product 6ab which was detected to be a single diastereo-
isomer (entries 8–10). The reactions of 3b and 3c carried
out under high pressure provided the nitroalcohols with
much higher yields (entries 10 and 15). As regards
diastereoselectivity, we observed formation of four possible
diastereoisomers; in most cases we were able to isolate and
characterise them in a chromatographically pure form. The
best results were obtained for the reaction of 1a with 3b,
when a single diastereoisomer was formed (entry 9).
Similarly to the reactions of 1a with 2 (Table 1), application
of the activated catalysts highly improved the yield of
reactions of 3a-e with 1a, although unfortunately were
accompanied by a slight decrease of diastereoselectivity
(Table 2, Methods A0 and B0). The only exception is the
The second chiral auxiliary applied by us was (1R)-8-
phenylmenthol which earlier proved to be very effective in
many other processes, especially in aldol condensations
which is similar to the Henry reaction.9 Its glyoxylate 1b,
being an ester, was supposed to be more stable than
glyoximide 1a under the reaction conditions. Presumably
for the initial reactions of glyoxylate 1b with
nitromethane (2) we did not notice any influence of the
way of preparing catalysts on the chemical yield; the ester
moiety did not hydrolyse. Both TBAF and Al2O3 led to the
desired nitroalcohols in high yields, however, the use of
activated catalysts improved slightly their efficiency
(Table 3).
Table 1. Reactions of chiral aldehyde 1a with 2
Entry Methoda Time (h) Yieldb (%) Diastereoisomeric ratioc 4a:5a
1
2
3
4
5
A
A0
B
B0
C
48
4
2
8
2.5
30
80
38
50
28
83:17
77:23
97:3
98:2
90:10
a
Method A: Al2O3, rt; A0: activated Al2O3, rt, B: TBAF·3H2O, 278 8C; B0:
anhydrous TBAF, 278 8C; C: TBAF·3H2O, 10 kbar, 0 8C.
Yield given for isolated products.
b
c
Calculated by both HPLC and 1H NMR analysis

I. Kudyba et al. / Tetrahedron 60 (2004) 4807–4820
Table 2. Reactions of chiral aldehyde 1a with nitro compounds 3a-e
4809
Entry
Nitro compound
Methoda used
Time (h)
Yieldb (%)
Diastereoisomeric ratioc 6:7:8:9
1
2
3
4
5
6
7
8
3a
3a
3a
3a
3a
3b
3b
3b
3b
3b
3c
3c
3c
3c
3c
3d
3d
3d
3e
3e
3e
3e
3e
A
A0
B
26
8
2
2,5
2.5
26
1
5
2.5
3
2.5
0.5
2.5
1.5
3
1
1
8
24
1.5
2
2
2
5
74:26:0:0
68:14:12:6
90:10:0:0
54:33:7:7
88:12:0:0
—
64:16:15:5
.99:1:0:0
.99:1:0:0
.99:1:0:0
84:16:0:0
75:20:5:0
93:7:0:0
88:7:5:0
92:8:0:0
59:19:16:6
—
57:20:13:10
38:30:21:11
39:26:23:12
34:26:25:15
35:30:21:14
31:23:28:18
93
29
38
28
0
78
45
80
70
46
90
42
82
60
91
6
B0
C
A
A0
B
B0
C
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
A
A0
B
B0
C
A0
B
B0
A0
A
B
50
55
83
43
70
41
B0
C
a
Method A: Al2O3, RT; A0: activated Al2O3, rt, B: TBAF·3H2O, 278 8C; B0: anhydrous TBAF, 278 8C; C: TBAF·3H2O, 10 kbar, 0 8C.
Calculated by both HPLC and H NMR analysis.
Yield given for isolated products.
b
c
1
The same relationships were observed for reactions of 1b
An X-ray analysis was made for the major adduct 6aa,
showing the absolute (2S) configuration at the center
bearing the hydroxy group, and the relative syn configur-
ation of hydroxy and nitro groups (Fig. 1).
with other nitro compounds 3a-e (Table 4). As far as
diastereoselectivity is concerned, we found that (1R)-8-
phenylmenthol is a less efficient chiral auxiliary compared
to (2R)-bornane-10,2-sultam. In most cases, we observed
formation of four possible diastereoisomers. Additionally,
the reactions catalysed by TBAF provided the products in
lower diastereoselectivity than the corresponding reactions
catalysed by Al2O3. Similarly to the reactions of 1a,
application of activated Al2O3 resulted in a slight decrease
of diastereoselectivity (Table 4, Method A0). Lowering the
temperature of the above processes resulted in formation of
nitroalcohols with better chiral induction as well as high
chemical yields (entries 16–18). In general, the use of 1a, as
compared with 1b, led to better stereochemical results.
The configuration of the minor diastereoisomer 7aa was
estimated by comparison of optical rotations and NMR
spectra of two nitrodiols 11a and 11b obtained by reductive
hydrolysis of sultam from diastereoisomerical diols (2S)-
6aa and 7aa (Scheme 3). Nitrodiols 11a and 11b were in
diastereoisomeric relationship, that is, the relative configur-
ation of compound 7aa is anti.
The configuration of major adduct 6ab, was determined by
the X-ray crystal structure. As revealed in Figure 2, it has
the absolute (2S)-hydroxy-(3R)-nitro configuration, which
constitutes a relative syn relation (Fig. 2).
The configuration of major diastereoisomer 4a was
established on the basis of correlation between optical
rotations of nitrodiol 10, the product of reductive removal of
chiral auxiliary, and the analogous nitrodiol of known
stereochemistry, which was obtained from reduction of
adduct 4b (Scheme 2). The configuration of compound 4b
was set up as (2S) via its chemical correlation to L-isoserine,
as described later.
In the case of the adduct obtained in the reaction of 1a with
1-nitro-1-phenylmethane (3c), the major diastereoisomer
6ac shows the (2S)-hydroxy-(3R)-nitro absolute configur-
ation and the relative syn configuration as established earlier
by X-ray analysis.10 Configurations of minor products were
assigned on analogous way as in the case of nitroalcohols
6aa and 7aa (Scheme 3).
Table 3. Reactions of chiral aldehyde 1b with 2
The configuration of compound 4b was established as (2S)
from its chemical correlation to (2)-isoserine (14)
(Scheme 4).6 Nitroalcohol 4b, after protecting its hydroxy
group with t-butyldimethylsilyl chloride, was catalytically
reduced to give amine 13, which was converted to (2)-14
by simultaneous hydrolysis of chiral auxiliary and protect-
ing group.
Entry Methoda Time (h) Yieldb (%) Diastereoisomeric ratioc 4b:5b
1
2
3
4
5
A
A0
B
B0
C
17
24
5.5
2.5
3
78
90
43
86
75
85:15
73:27
53:47
75:25
73:27
a
Method A: Al2O3, rt; A0: activated Al2O3, rt, B: TBAF·3H2O, 278 8C; B0:
anhydrous TBAF, 278 8C; C: TBAF·3H2O, 10 kbar, 0 8C.
Yield given for the isolated products.
The configuration of two major products formed in the
reaction of 1b with 1-nitrohexane (3a) were estimated by
measurements of NOE for H-2 and H-3 hydrogens of
b
c
1
Calculated by both HPLC and H NMR analysis.

4810
I. Kudyba et al. / Tetrahedron 60 (2004) 4807–4820
Table 4. Reactions of chiral aldehyde 1b with nitro compounds 3a-e
Entry
Nitro compound
Methoda used
Time (h)
Yieldb (%)
Diasteroisomeric ratioc 6:7:8:9
1
2
3
4
5
6
7
8
3a
3a
3a
3a
3a
3b
3b
3b
3b
3b
3c
3c
3c
3c
3c
3d
3d
3d
3d
3e
3e
3e
A
A0
B
17
24
22
1
2
17
6
2
1
2
3
60
85
43
90
73
39
96
47
64
62
90
97
90
86
77
60
98
89
97
95
96
98
62:22:10:6
58:24:12:6
34:30:24:12
33:28:23:16
42:24:20:14
88:7:5:0
68:21:8:3
62:17:15:6
66:24:10:0
61:17:15:7
89:8:3:0
B0
C
A
A0
B
B0
C
A
A0
B00
B
9
10
11
12
13
14
15
16
17
18
19
20
21
22
1
83:13:0:0
63:23:14
51:35:14
1.5
20
2
48
7
24
2.5
20
5
C
66:23:11
A0
A
A00
B
A
B
47:32:14:7
62:19:13:6
71:19:6:5
28:27:26:18
54:46:0:0
50:50:0:0
50:50:0:0
C
2
a
Method A: Al2O3, RT; A0: activated Al2O3, RT, A00: activated Al2O3, 220 8C, B: TBAF·3H2O, 278 8C; B0: 0.5 anhydrous TBAF, 278 8C; B00: TBAF·3H2O,
220 8C; C: TBAF·3H2O, 10 kbar, 0 8C.
Calculated by HPLC analysis and 1H NMR.
Yield given for isolated products.
b
c
Scheme 2.
isopropylidene derivatives 18a and 18b, produced from
adducts 6ba and 7ba, respectively (Scheme 5). Positive
NOE was observed for the oxazolidine 18b (10.0% for H-2,
7.6% for H-3) indicating the relative syn configuration of
H-2 and H-3 hydrogens, which determine relative configur-
ation anti for compound 7ba. The positive NOE was not
seen for the oxazolidine 18a, pointing out the relative anti
configuration of H-2 and H-3, which states the relative syn
configuration for compound 6ba.
The same procedure was applied for assignment of the
relative configuration of nitroalcohols 6bb, 7bb and 7bc
(Scheme 5).
Figure 1. X-ray structure of (20R)-N-[(2S)-hydroxy-(3R)-nitrooctanoyl]-
bornane-100,20-sultam (6aa).
In the case of the adduct obtained in the reaction of 1b with
1-nitro-1-phenylmethane (3c), the major diastereoisomer
6bc shows the (2S)-hydroxy-(3R)-nitro configuration and
the relative syn configuration for these groups established
earlier by X-ray analysis.10 That compound was used in the
total synthesis of Taxoterew side chain.11
In the case of the adduct obtained in the reaction of 1b with
2-nitro-1-phenylethane (3d), the configuration of the major
diastereoisomer 6bd was established as (2S,3R) by total
synthesis of (2)-bestatin.11 The configuration of the minor
diastereoisomer 7bd, assigned earlier by X-ray analysis, is
Scheme 3.

I. Kudyba et al. / Tetrahedron 60 (2004) 4807–4820
4811
In summary, we have shown that the derivatives of
glyoxylic acid, bearing (2R)-bornane-10,2-sultam and
(1R)-8-phenylmenthol as chiral auxiliaries, are very con-
venient substrates for preparation of optically pure nitro-
alcohols that could be used as starting materials in the
synthesis of various natural products.
4. Experimental
4.1. General methods
Figure 2. X-ray structure of (20R)-N-[4,4-Diethoxy-(2S)-hydroxy-(3R)-
nitrobutanoyl]-bornane-100,02-sultam (6ab).
All reactions were carried out under argon atmosphere with
anhydrous solvents dried according to standard laboratory
methods. 1H and 13C NMR spectra were measured on
Bruker AM-500 (500 and 125 MHz, respectively) and
Varian Gemini (200 and 50 MHz, respectively) spec-
trometers using residual CHCl3 as internal reference. Mass
spectra were carried out with AMD-604 Intectra instrument.
Optical rotations were measured on a JASCO DIP-360
polarimeter with a thermally jacketed 10 cm cell. Infrared
spectra were recorded on a Perkin–Elmer 1640 FT-IR.
Melting points were determined with Kofler hot stage
apparatus and are uncorrected. Flash-column chromato-
graphy was performed on silica gel (Kieselgel-60, Merck,
200–400 mesh). TLC was performed on Merck aluminum
plates (Kieselgel 60 F254) and compounds were visualized
with a solution of MoO3 and Ce2(SO4)3 in 15% H2SO4. All
high-pressure reactions were carried out in a piston-cylinder
type apparatus with an initial working volume of about
5 mL. The X-ray measurements were run on a Nonius
MACH3 diffractometer using Express software, without
absorption corrections. The structures were solved by the
SHELXS8612 and refined with the SHELXL9313 programs.
The known configuration of the asymmetric centres has
been confirmed by the Flack parameter refinement. Crystal-
lographic data (excluding structure factors) for the
structures in this paper have been deposited with the
Cambridge Crystallographic Data Center as supplementary
publication numbers 6aa: CCDC 228305 and 6ab: CCDC
228306. Copies of the data can be obtained, free of charge,
on application to CCDC, 12 Union Road, Cambridge, CB2
(2S)-hydroxy-(3S)-nitro and the relative configuration of
these groups is anti.10
On the basis of structural analysis referring to relationship
of configurations of new stereogenic centres, we have
noticed the occurrence of some distinct regularities. The
most important one is that the major diastereoisomer
obtained in the above-discussed reactions has the relative
syn configuration of nitro and hydroxy groups, and the
absolute (2S)-hydroxy-(3R)-nitro configuration. The second
diastereoisomer formed also possess the absolute configur-
ation (2S), however the relative relation of C-2 and C-3
substituents was in all cases anti.
3. Conclusions
On the basis of the above-mentioned analyses, we conclude
that the major diastereoisomers 4 and 6 possess the absolute
(2S) configuration of the hydroxy-bearing stereogenic
centre in all cases. The relative configuration of nitro and
hydroxy groups is syn for all major diastereoisomers 6,
contrary to the anti configuration found in products obtained
via the chiral-pool approach. Thus, our methodology seems
to be complementary to the chiral pool as concerns the
relative configuration of newly created stereogenic centres.
Scheme 4. Reagents: (a) TBDMSCl, (b) H2, Raney Ni, (c) HCl, (d) epoxypropane
Scheme 5. Reagents: (a) H2, Raney Ni, (b) Boc2O, (c) DMP, Hþ.

4812
I. Kudyba et al. / Tetrahedron 60 (2004) 4807–4820
1EZ, UK (fax: þ44-1223-336033 or e-mail: deposit@ccdc.
CDCl3): d 169.9 (C-1), 78.3 (C-3), 68.4 (C-2), 65.4 (C-20),
52.80 (C-100), 49.3 (C-10), 48.0 (C-70), 44.4 (C-40),0 37.3
(C-3 ), 32.6 (C-60), 26.3 (C-50), 20.3 (C-80), 19.8 (C-9 ).
cam.ac.uk).
4.2. General procedures for the reactions of 1 with 2 or 3
4.2.5. (20R)-N-[(20R)-Hydroxy-3-nitropropanoyl]-
bornane-100,20-sultam (5a). Selected signals from
4.2.1. General procedure for the neutral Al2O3 (Method
A) or activated Al2O3 (Method A0) catalysed reaction. A
carbonyl compound (1 mmol) and a nitro compound
(2 mmol) were added to a solution of a catalyst (2 mmol)
in THF (5 mL) at rt under argon atmosphere. Activated
Al2O3 was prepared before the reaction by heating at 120 8C
under reduced pressure (0.2 mm Hg) for 2 h. The reaction
was monitored by TLC, and when finished, it was filtered
and evaporated. All products were purified by column
chromatography (hexane/AcOEt 9:1–6:4).
1
differential NMR spectra: H (400 MHz; CDCl3): d 5.33
(ddd, J2,3A¼4.0 Hz, J2,3B¼8.0 Hz, J2,OH¼6.4 Hz, 1H, H-2),
4.90 (ddAB, J3A,3B¼14.0 Hz, J2,3A¼4.0 Hz, 1H, HA-3), 4.69
(ddAB, J3A,3B¼14.0 Hz, J2,3B¼8.0 Hz, 1H, HB-3), 3.93 (dd,
J2 ,3 A¼4.8 Hz, J2 ,3 B¼7.8 Hz, 1H, H-20), 3.84 (d, J2,OH
¼
0
0
0
0
0
0
6.4 Hz, 1H, OH), 3.59 (dAB, J10 A,10 B¼13.9 Hz, 1H, HA-
100), 3.55 (dAB, J10 A,10 B¼13.9 Hz, 1H, HA-100), 1.14 (s,
3H, H-80), 0.93 (s, 3H, H-90); 13C (50 MHz; CDCl3): d 168.8
(C-1), 75.6 (C-3), 68.1 (C-2), 65.2 (C-20), 52.6 (C-1000), 49.5
(C-100), 47.9 (C-700), 44.6 (C-40), 37.4 (C-30), 32.7 (C-6 ), 26.4
(C-5 ), 20.4 (C-8 ), 19.9 (C-90).
0
0
4.2.2. General procedure for the TBAF·3H2O (Method
B) and TBAF (Methods B0 and B00) catalysed reaction. A
catalyst (0.5 mmol) was added to a solution of a carbonyl
compound (1 mmol) in dry THF (5 mL) under argon
atmosphere. The reaction mixture was cooled to 278 8C
and a nitro compound (2 mmol) was added. Anhydrous
TBAF was prepared just before the reaction by heating at
80 8C at reduced pressure (0.2 mm Hg) for 2 h. The reaction
was monitored by TLC, and when finished, it was quenched
by addition of saturated aqueous NaCl and extracted with
AcOEt. The combined organic extracts were dried over
anhydrous MgSO4 and evaporated. All products were
purified by column chromatography (hexane–AcOEt 9:1–
6:4).
4.2.6. (20R)-N-[(2S)-Hydroxy-(3R)-nitrooctanoyl]-
bornane-100,20-sultam
(6aa).
Colourless
crystals,
mp¼79–80 8C (hexane/AcOEt); HRMS-EI: Calcd
C18H31N2O6S (MþH)þ: 403.1902, found 403.1923. Anal
Calcd C. 53.71, H. 7.51, N. 6.96, S. 7.97, found C. 53.71, H.
7.54, N. 7.00, S. 7.89; IR (KBr): 3493, 3291, 2959, 2932,
2877, 1696, 1555, 1334, 1292, 1216, 1136, 1051, 765, 627,
20
536 cm21
;
[a]D ¼266.7 (c¼1.05; CHCl3); Rf¼0.6
(hexane/AcOEt 7:3); 1H NMR d (500 MHz; CDCl3): d
5.02 (ddd, J2,3¼2.4 Hz, J3,4A¼5.9 Hz, J3,4B¼8.4 Hz, 1H,
H-3), 4.91 (dd, J2,3¼2.4 Hz, J2,OH¼7.8 Hz, 1H, H-2), 3.97
(dd, J2 ,3 A¼4.7 Hz, J2 ,3 B¼7.8 Hz, 1H, H-20), 3.55 (dAB
,
0
0
0
0
J10 A,10 B¼13.8 Hz, 1H, HA-100), 3.50 (dAB, J10 A,10 B¼13.8
0
0
0
0
4.2.3. General procedure for the TBAF·3H2O catalysed
reaction under high pressure (10 kbar) (Method C). A
catalyst (0.5 mmol) was added to a precooled (0 8C)
solution of a carbonyl compound (1 mmol) in dry THF
(5 mL), followed by addition of a nitro compound (2 mmol).
The reaction was carried out in high pressure apparatus at
the indicated temperature and time. When finished, it was
quenched by addition of saturated aqueous NaCl and
extracted with AcOEt. The combined organic extracts
were dried over anhydrous MgSO4 and evaporated. All
products were purified by column chromatography
(hexane/AcOEt 9:1–6:4).
Hz, 1H, HB-100), 3.44 (d, J2,OH¼7.8 Hz, 1H, OH), 2.31–
0
0
0
2.23 (m, 2H, H-4), 2.20 (ddd, J2 ,3 A¼4.7 Hz, J3 A,4¼7.8 Hz,
J3 A,3 B¼14.0 Hz, 1H, HA-30), 2.20 (dd, J2 ,3 B¼J3 A,4¼7.8
0
0
0
0
0
Hz, J3 A,3 B¼14.0 Hz, 1H, HB-30), 2.00–1.85 (m, 3H, H-40,
0
0
H-600), 1.51–1.28 (m, 8H, H-5, H-6, H-7, H-50), 1.22 (s, 3H,
H-8 ), 1.00 (s, 3H, H-90), 0.89 (t, 3H, J7,8¼7.0 Hz, H-8); 13
C
NMR (125 MHz; CDCl3): d 170.3(C-1), 89.4 (C-3), 71.4
(C-2), 65.2 (C-20), 52.8 (C-100), 049.1 (C-10), 47.9 (C-70),
44.3 (C-400), 37.3 (C-30), 35.9 (C-6 ), 31.2 (C-4), 29.2 (C-5),
26.7 (C-5 ), 24.9 (C-6), 22.1 (C-7), 20.3 (C-80), 19.8 (C-90),
13.8 (C-8).
4.2.7. (20R)-N-[anti-(2j)-Hydroxy-(3j)-nitrooctanoyl]-
4.2.4. (20R)-N-[(2S)-Hydroxy-3-nitropropanoyl]-
bornane-100,20-sultam (7aa). Colourless oil, [a]D
¼
20
bornane-100,20-sultam
(4a).
Colourless
crystals,
263.6 (c¼0.845; CHCl3); Rf¼0.5 (hexane/AcOEt 7:3); H
NMR (500 MHz; CDCl3): d 5.26 (dd, J2,3¼5.4 Hz, J2,OH
6.3 Hz, 1H, H-2), 4.92 (ddd, J2,3¼5.4 Hz, J3,4A¼3.3 Hz,
1
mp¼160–161 8C (MeOH); HRMS-EI: Calcd for C13H20-
O6N2SNa (MþNa)þ: 355.0939, found 355.0942. Anal
Calcd C. 46.97, H. 6.08, N. 8.42, S. 9.64, found C. 47.18,
H. 6.14, N. 8.33, S. 9.71; IR (KBr): 3492, 2964, 2884, 1694,
1549, 1329, 1296, 1222, 1138, 1101, 1064, 769, 611,
¼
0
0
0
0
J3,4B¼9.1 Hz, 1H, H-3), 3.96 (dd, J2 ,3 A¼4.9 Hz, J2 ,3 B
¼
7.7 Hz, 1H, H-20), 3.58 (dAB, J10 A,10 B¼13.8 Hz, 1H, HA-
0
0
100), 3.51 (dAB, J10 A,10 B¼13.8 Hz, 1H, HB-100), 3.50 (d,
J2,OH¼6.3 Hz, 1H, OH), 2.18–1.70 (m, 7H, H-4, H-30, H-40,
H-600), 1.49–1.23 (m, 8H, H-5, H-6, H-7, H-50), 1.15 (s, 3H,
0
0
533 cm21
;
[a]2D0¼2103.6 (c¼0.90; CHCl3); Rf¼0.5
1
(hexane/AcOEt 6:4); H NMR (400 MHz; CDCl3): d 5.11
(ddd, J2,3A¼3.9 Hz, J2,3B¼4.0 Hz, J2,OH¼5.9 Hz, 1H, H-2),
5.01 (ddAB, J3A,3B¼13.3 Hz, J2,3A¼3.9 Hz, 1H, HA-3), 4.88
(ddAB, J3A,3B¼13.3 Hz, J2,3B¼4.0 Hz, 1H, HB-3), 4.00 (dd,
H-8 ), 1.01 (s, 3H, H-90), 0.87 (t, 3H, J7,8¼6.8 Hz, H-8); 13
C
NMR (125 MHz; CDCl3): d 169.5 (C-1), 87.3 (C-3), 70.8
(C-2), 65.3 (C-20), 52.9 (C-100), 049.2 (C-10), 47.9 (C-70),
44.5 (C-400), 37.9 (C-30), 32.8 (C-6 ), 31.2 (C-4), 27.8 (C-5),
26.3 (C-5 ), 25.1 (C-6), 22.2 (C-7), 20.6 (C-80), 19.8 (C-90),
13.8 (C-8).
J2 ,3 A¼4.7 Hz, J2 ,3 B¼7.8 Hz, 1H, H-20), 3.77 (d, J2,OH
¼
0
0
0
0
0
0
5.9 Hz, 1H, OH), 3.56 (dAB, J10 A,10 B¼13.8 Hz, 1H, HA-
100), 3.52 (dAB, J10 A,10 B¼13.8 Hz, 1H, HA-100), 2.21 (ddd,
0
0
J2 ,3 A¼4.7 Hz, J3 A,3 B¼13.8 Hz, J3 A,4¼7.3 Hz, 1H, HA-30),
0
0
0
0
0
2.09 (dd, J2 ,3 B¼7.8 Hz, J3 A,3 B¼J3 A,4¼13.8 Hz, 1H, HB-
30), 2.00–1.84 (m, 3H, H-40, H-60), 1.51–1.25 (m, 2H, H-50),
1.13 (s, 3H, H-80), 0.99 (s, 3H, H-90); 13C NMR (50 MHz;
4.2.8. (20R)-N-[4,4-Diethoxy-(2S)-hydroxy-(3S)-nitro-
0
0
0
0
0
butanoyl]-bornane-100,02-sultam
(6ab).
Colourless
crystals, mp¼98–100 8C (hexane/Et2O); HRMS-EI: Calcd

I. Kudyba et al. / Tetrahedron 60 (2004) 4807–4820
4813
for C18H30N2O8SNa (MþNa)þ 457.1620, found 457.1608.
Anal Calcd C. 49.76, H. 6.96, N. 6.45, S. 7.38, found C.
49.95, H. 7.25, N. 6.53, S. 7.54; IR (KBr): 3527, 3291, 2966,
(C-1), 130.3 (i-Ar),130.1 (Ar), 129.2 (Ar), 128.8 (Ar), 92.0
(C-3), 72.0 (C-2), 65.1 (C-20), 52.9 (C-1000), 48.9 (C-100), 47.7
(C-700), 44.5 (C-400), 37.4 (C-30), 32.7 (C-6 ), 26.3 (C-5 ), 20.4
(C-8 ), 19.7 (C-9 ).
1686, 1553, 1333, 1142, 1064 cm21; [a]D ¼275.6
20
1
(c¼1.03; CHCl3); Rf¼0.6 (hexane/AcOEt 7:3); H NMR
(200 MHz; CDCl3): d 5.24 (d, J3,4¼8.2 Hz, 1H, H-4), 5.23
4.2.13. (20R)-N-[anti-(2j)-Hydroxy-(3j)-nitro-3-phenyl-
propanoyl]-bornane-100,20-sultam (7ac). Colourless oil,
1H NMR (500 MHz; CDCl3): d 7.46–7.38 (m, 5H, Ar), 5.93
(dd, J2,OH¼8.2 Hz, J2,3¼2.4 Hz, 1H, H-2), 5.08 (dd, J3,4
¼
0
0
8.2 Hz, J2,3¼2.4 Hz, 1H, H-3), 3.95 (dd, J2 ,3 A¼5.1 Hz,
J2 ,3 B¼7.5 Hz, 1H, H-20), 3.79 (q, J5,6¼7.4 Hz, 2H, H-5),
(d, J2,3¼6.7 Hz, 1H, H-3), 5.69 (dd, J2,3¼6.7 Hz, J2,OH
¼
0
0
00
00 00
0
0
0
0
0
0
3.78 (q, J5 ,6 ¼7.1 Hz, 2H, H-5 ), 3.16 (dAB, J10 A,10 B¼13.8
5.8 Hz, 1H, H-2), 3.93 (dd, J2 ,3 A¼4.8 Hz, J2 ,3 B¼8.2 Hz,
Hz, 2H, HA-100), 3.08 (dAB, J10 A,10 B¼13.8 Hz, 2H, HB-
100), 2.15–2.03 (m, 2H, H30), 2.20–1.83 (m, 3H, H-40, H-
60), 1.55-1.32 (m, 2H, H-50), 1.26 (t, J5,6¼7.1 Hz, 3H, H-6),
1H, H-20), 3.38 (d, J2,OH¼6.5 Hz, 1H, OH), 3.61 (dAB
,
0
0
J10 A,10 B¼13.8 Hz, 1H, HA-100), 3.52 (dAB, J10 A,10 B¼13.8
Hz, 1H, HB-100), 2.01–1.50 (m, 6H, H-40, H-60, H-30), 1.46–
1.40 (m, 1H, HA-50), 1.38–1.31 (m, 1H, HB-50), 1.22 (s, 3H,
H-80), 1.01 (s, 3H, H-90); 13C NMR (125 MHz; CDCl3): d
171.2 (C-1), 130.1 (i-Ar),130.0 (Ar), 129.1 (A0r), 128.3 (Ar),
89.2 (C-3), 70.9 (C-2), 64.2 (C-20), 52.8 (C-100), 49.1 (C-100),
47.8 (C-700), 44.6 (C-400), 37.7 (C-30), 32.8 (C-6 ), 26.7 (C-5 ),
20.8 (C-8 ), 19.0 (C-9 ).
0
0
0
0
00
0
00 00
1.18 (t, J5 ,6 ¼7.4 Hz, 3H, H-6 ), 0.99 (s, 3H, H-8 ), 0.93 (s,
3H, H-90); 13C NMR (50 MHz; CDCl3): d 169.8 (C-1), 99.2
(C-4), 89.4 0(C-3), 69.4 (C-2), 65.2 (C-020), 63.3 (C-5, C-500),
52.80 (C-10 ), 49.1 (C-10), 47.9 (C-7 ),0 44.4 (C-40), 37.5
(C-3 ), 32.7 (C-60), 26.4 (C-50), 20.4 (C-8 ), 19.9 (C-90), 15.1
(C-6), 14.9 (C-600).
4.2.9. (20R)-N-[4,4-Diethoxy-(2j)-hydroxy-(3j)-nitro-
butanoyl]-bornane-100,02-sultam (7ab). Selected signals
4.2.14. (20R)-N-[(2R)-Hydroxy-(3S)-nitro-3-phenyl-
propanoyl]-bornane-100,20-sultam (8ac). Colourless oil,
1
20
from differential NMR spectra: H (500 MHz; CDCl3): d
[a]D ¼241 (c¼1.11; CHCl3); 1H NMR (500 MHz;
5.57 (dd, J2,OH¼6.2 Hz, J2,3¼6.6 Hz, 1H, H-2), 3.50 (dd,
CDCl3): d 7.50–7.38 (m, 5H, Ar), 5.85 (d, J2,3¼9.0 Hz,
1H, H-3), 5.49 (dd, J2,3¼9.0 Hz, J2,OH¼6.1 Hz, 1H, H-2),
J2 ,3 A¼4.6 Hz, J2 ,3 B¼7.8 Hz, 1H, H-20); 13C (125 MHz;
CDCl3): d 170.6 (C-1), 99.6 (C-4), 89.6 (C-3), 71.6 (C-2),
52.20 (C-100), 48.6 (C-10), 47.6 (C-70), 44.3 (C-40), 26.0
(C-5 ), 13.7 (C-6).
0
0
0
0
3.97 (dd, J2 ,3 A¼4.9 Hz, J2 ,3 B¼7.8 Hz, 1H, H-20), 3.57
,
0
0
0
0
(dAB
,
J10 A,10 B¼13.8 Hz, 1H, HA-100), 3.55 (dAB
0
0
J10 A,10 B¼13.8 Hz, 1H, HB-100), 3.51 (d, J2,OH¼6.5 Hz,
1H, OH), 2.23–2.18 (m, 1H, HA-30), 2.10–2.04 (m, 1H, HB-
30), 1.99–1.85 (m, 4H, H-40, H-60), 1.50–1.45 (m, 1H, HA-
50), 1.39–1.33 (m, 1H, HB-50), 1.12 (s, 3H, H-80), 0.98 (s,
3H, H-90); 13C NMR (125 MHz; CDCl3): d 168.2 (C-1),
131.5 (i-Ar),130.0 (Ar), 128.9 (Ar), 128.3 (Ar), 87.9 (C-3),
70.80 (C-2), 65.0 (C-20), 52.6 (C-100), 0 49.5 (C-10), 47.8
(C-70), 44.3 (C-400), 37.4 (C-30), 32.5 (C-6 ), 26.3 (C-50), 20.4
(C-8 ), 19.7 (C-9 ).
0
0
4.2.10. (20R)-N-[4,4-Diethoxy-(2j)-hydroxy-(3j)-nitro-
butanoyl]-bornane-100,02-sultam (8ab). Selected signals
1
from differential NMR spectra: H (500 MHz; CDCl3): d
5.44 (dd, J3,4¼8.4 Hz, J2,3¼6.0 Hz, 1H, H-2), 3.97 (d,
0
0
0
0
J2,3¼6.0 Hz, 1H, OH), 3.31 (dd, J2 ,3 A¼4.8 Hz, J2 ,3 B
44.3 (C-40), 26.1 (C-50).
¼
7.8 Hz, 1H, H-20); 13C (125 MHz; CDCl3): d 47.5 (C-70),
4.2.11. (20R)-N-[4,4-Diethoxy-(2j)-hydroxy-(3j)-nitro-
butanoyl]-bornane-100,02-sultam (9ab). Selected signals
4.2.15. (20R)-N-[(2S)-Hydroxy-(3R)-nitro-4-phenyl-
butanoyl]-bornane-100,20-sultam (6ad). Colourless oil,
HRMS-ESI: Calcd for C20H26N2O6SNa (MþNa)þ
445.1404, found 445.1415. Anal. Calcd C. 56.86, H. 6.20,
N. 6.63, S. 7.59, found C. 57.09, H. 6.31, N. 6.46, S. 7.71; IR
(film): 3470, 2961, 1694, 1555, 1335, 1294, 1167, 1138,
1
from differential NMR spectra: H (500 MHz; CDCl3): d
0
0
3.82 (d, J2,3¼7.8 Hz, 1H, OH), 3.48 (dd, J2 ,3 A¼4.6 Hz,
J2 ,3 B¼7.8 Hz, 1H, H-20); 13C (50 MHz; CDCl3): d 168.4
(C-1), 96.1 (C-4), 65.1 (C-20), 52.0 (C-100), 47.4 (C-70), 44.2
(C-40), 14.9 (C-6).
0
0
1061, 753, 700, 535 cm21; [a]D ¼260 (c¼1.10; CHCl3);
20
1
Rf¼0.4 (hexane/AcOEt 7:3); H NMR (500 MHz; CDCl3):
4.2.12. (20R)-N-[(2S)-Hydroxy-(3R)-nitro-3-phenyl-
propanoyl]-bornane-100,20-sultam (6ac). Colourless
crystals, mp¼169–170 8C (hexane/AcOEt); HRMS-EI:
Calcd for C19H25N2O6S (MþH)þ 409.1433, found
409.1432. Anal. Calcd for C19H24N2O6S: C. 55.87, H.
5.92, N. 6.86, S. 7.85, found C. 55.79, H. 6.08, N. 6.80, S.
d 7.34–7.25 (m, 5H, Ar), 5.34 (ddd, J2,3¼2.2 Hz, J3,4A¼
5.8 Hz, J3,4B¼9.1 Hz, 1H, H-3), 4.92 (dd, J2,3¼2.2 Hz,
0
0
0
0
J2,OH¼7.1 Hz, 1H, H-2), 3.96 (dd, J2 ,3 A¼4.8 Hz, J2 ,3 B
7.9 Hz, 1H, H-20), 3.58 (ddAB, J3,4B¼9.1 Hz, J4A,4B
14.5 Hz, 1H, HB-4), 3.27 (ddAB, J3,4A¼5.8 Hz, J4A,4B
¼
¼
¼
0
0
14.5 Hz, 1H, HA-4), 3.13 (dAB, J10 A,10 B¼13.7 Hz, 1H, HA-
100), 3.08 (dAB, J10 A,10 B¼13.7 Hz, 1H, HB-100), 2.01–1.81
(m, 3H, H-30, H-40), 1.49–1.29 (m, 2H, H-60), 1.20–1.08 (m,
1H, H-50), 1.19 (s, 3H, H-80), 0.97 (s, 3H, H-90); 13C NMR
(125 MHz; CDCl3): d 170.3 (C-1), 134.9 (i-Ar),129.3 (Ar),
128.6 (Ar),0127.3 (Ar), 90.2 (C-3), 710.3 (C-2), 65.3 (C-20),
52.80 (C-10 ), 49.2 (C-10), 47.9 (C-7 ),0 44.3 (C-40), 37.2
(C-30), 35.4 (C-4), 32.5 (C-60), 26.4 (C-5 ), 20.2 (C-80), 19.8
(C-9 ).
0
0
7.87; IR (KBr): 3496, 3291, 2999, 2944, 2909, 1682, 1561,
20
1367, 1320, 1214, 1137, 1072, 719, 532 cm–1; [a]D
¼
268 (c¼1.39; CHCl3); Rf¼0.4 (hexane/AcOEt 7:3); 1H
NMR (500 MHz; CDCl3): d 7.60–7.35 (m, 5H, Ar), 5.95 (d,
J2,3¼6.6 Hz, 1H, H-3), 5.55 (dd, J2,3¼6.6 Hz, J2,OH
¼
0
0
0
0
6.5 Hz, 1H, H-2), 3.97 (dd, J2 ,3 A¼4.7 Hz, J2 ,3 B¼7.8 Hz,
1H, H-20), 3.66 (d, J2,OH¼6.5 Hz, 1H, OH), 3.51 (dAB
,
J10 A,10 B¼13.8 Hz, 1H, HA-100), 3.46 (dAB, J10 A,10 B¼13.8
Hz, 1H, HB-100), 1.95–1.85 (m, 4H, H-40, H-60), 1.78–1.74
(m, 1H, HA-30), 1.67–1.60 (m, 1H, HB-30), 1.42–1.36 (m,
1H, HA-50), 1.33–1.23 (m, 1H, HB-50), 0.92 (s, 3H, H-80),
0.79 (s, 3H, H-90); 13C NMR (125 MHz; CDCl3): d 168.7
0
0
0
0
4.2.16. (20R)-N-[(2j)-Hydroxy-(3j)-nitro-4-phenyl-
butanoyl]-bornane-100,20-sultam (7ad). Selected signals
1
from differential NMR spectra: H (500 MHz; CDCl3): d

4814
I. Kudyba et al. / Tetrahedron 60 (2004) 4807–4820
5.32 (dd, J2,3¼4.9 Hz, J2,OH¼5.8 Hz, 1H, H-2), 5.21 (ddd,
J2,3¼4.9 Hz, J3,4A¼4.0 Hz, J3,4B¼8.8 Hz, 1H, H-3), 3.92
(C-1), 87.6 (C-3), 69.5 (C-2), 65.3 (C-20), 63.5 (C-5), 520.7
(C-100), 49.4 (C-10), 48.0 (C-70), 044.5 (C-40), 37.2 (C-3 ),
32.5 (C-60), 26.9 (C-50), 20.3 (C-8 ), 19.6 (C-90) 13.6 (C-6).
(dd, J2 ,3 A¼4.4 Hz, J2 ,3 B¼7.9 Hz, 1H, H-20), 3.55 (dAB
,
0
0
0
0
J10 A,10 B¼13.7 Hz, 1H, HA-100), 3.49 (dAB, J10 A,10 B¼13.7
0
0
0
0
Hz, 1H, HB-100), 3.43 (ddAB, J3,4B¼8.8 Hz, J4A,4B
¼
¼
4.2.21. (20R)-N-[(2j)-Hydroxy-3-carboxyethyl-(3j)-
nitropropanoyl]-bornane-100,20-sultam (8ae). Selected
signals from differential NMR spectra: 1H (500 MHz;
CDCl3): d 5.64 (d, J2,3¼8.3 Hz, 1H, H-3), 5.39 (d,
J2,3¼J2,OH¼8.3 Hz, 1H, H-2), 1.12 (s, 3H, H-80), 0.94 (s,
3H, H-90); 13C (125 MHz; CDCl3): d 167.4 (C-1), 161.8
(C-1), 87.8 (C-3), 70.0 (C-2), 65.0 (C-20), 63.5 (C-5), 520.7
(C-100), 49.4 (C-10), 47.8 (C-70), 044.3 (C-40), 37.5 (C-3 ),
32.4 (C-60), 26.6 (C-50), 20.3 (C-8 ), 19.6 (C-90) 13.6 (C-6).
15.0 Hz, 1H, HB-4), 3.14 (ddAB, J3,4A¼4.0 Hz, J4A,4B
15.0 Hz, 1H, HA-4), 1.06 (s, 3H, H-80), 0.95 (s, 3H, H-90);
13C (125 MHz; CDCl3): d 169.3 (C-1), 134.8 (i-Ar), 129.0
(Ar), 128.7 (Ar), 127.3 (Ar), 88.2 (C-3), 70.4 (C-2), 650.3
(C-20), 52.8 (C-100), 49.1 (C-10), 47.8 (C-70), 44.4 (C-40),
37.7 (C-300), 35.4 (C-4), 32.7 (C-60), 26.2 (C-50), 20.7 (C-8 ),
19.7 (C-9 ).
4.2.17. (20R)-N-[(2j)-Hydroxy-(3j)-nitro-4-phenyl-
butanoyl]-bornane-100,20-sultam
(8ad).
Colourless
4.2.22. (20R)-N-[(2j)-Hydroxy-3-carboxyethyl-(3j)-
nitropropanoyl]-bornane-100,20-sultam (9ae). Selected
signals from differential NMR spectra: 1H (500 MHz;
CDCl3): d 5.60 (d, J2,3¼7.1 Hz, 1H, H-3), 5.51 (d,
J2,3¼J2,OH¼7.1 Hz, 1H, H-2), 1.10 (s, 3H, H-80), 0.90 (s,
3H, H-90); 13C (125 MHz; CDCl3): d 167.2 (C-1), 162.5
(C-1), 85.5 (C-3), 69.8 (C-2), 65.3 (C-20), 63.3 (C-5), 520.9
(C-100), 49.4 (C-10), 47.6 (C-70), 044.6 (C-40), 37.6 (C-3 ),
32.6 (C-60), 26.7 (C-50), 20.4 (C-8 ), 19.8 (C-90) 13.6 (C-6).
crystals, mp¼176–178 8C; 1H (500 MHz; CDCl3): d
7.15–5.40 (m, 5H, Ar), 5.35 (dd, J2,3¼11.0 Hz, J2,OH
¼
6.0 Hz, 1H, H-2), 5.20–5.32 (m, 1H, H-3), 3.97 (dd,
0
J2 ,3 A¼4.5 Hz, J2 ,3 B¼7.8 Hz, 1H, H-20), 3.68 (d, J¼6.0 Hz,
0
0
0
1H, OH), 3.61 (dAB, J10 A,10 B¼13.7 Hz, 1H, HA-100), 3.52
0
0
0
0
(dAB
,
J10 A,10 B¼13.7 Hz, 1H, HB-100), 3.49 (ddAB
,
,
J3,4B¼8.5 Hz, J4A,4B¼15.0 Hz, 1H, HB-4), 3.19 (ddAB
J3,4A¼4.0 Hz, J4A,4B¼15.0 Hz, 1H, HA-4), 1.84–2.15 (m,
5H), 1.30–1.55 (m, 2H), 1.13 (s, 3H, H-80), 1.01 (s, 3H,
H-90); 13C (125 MHz; CDCl3): d 168.2 (C-1), 134.6 (i-Ar),
128.9 (Ar), 128.8 (Ar), 127.5 (Ar), 89.4 (C-3), 70.7 (C-2),
65.30 (C-20), 52.7 (C-100), 49.3 (C-10),0 47.8 (C-70), 44.6
(C-40), 37.6 (C-300), 35.9 (C-4), 32.6 (C-6 ), 26.7 (C-50), 20.4
(C-8 ), 20.3 (C-9 ).
4.2.23. O-[(2S)-Hydroxy-3-nitropropanoyl]-(10R,
20S,50R)-80-phenylmenthol (4b). Colourless oil, HRMS-
LSIMS(þ): Calcd for C19H27O5NNa (MþNa)þ: 372.1786,
found 372.1790. Anal Calcd C. 65.31, H. 7.79, N. 4.01,
found C. 65.28, H. 8.03, N. 3.94; IR (film): 3486, 2957,
2924, 1732, 1557, 1376, 1224, 1124, 978, 766, 702 cm21
;
4.2.18. (20R)-N-[(2j)-Hydroxy-(3j)-nitro-4-phenyl-
butanoyl]-bornane-100,20-sultam (9ad). Selected signals
[a]D ¼26.40 (c¼1.15; CHCl3); Rf¼0.4 (hexane/AcOEt
20
1
8:2); H NMR (200 MHz; CDCl3): d 7.32–7.08 (m, 5H,
1
0
0
0
0
0
0
from differential NMR spectra: H (500 MHz; CDCl3): d
Ar), 4.85 (dt, J1 ,6 A¼J1 ,2 ¼10.8 Hz, J1 ,6 B¼4.3 Hz, 1H,
H-10), 4.11 (ddAB, J3A,3B¼14.5 Hz, J2,3A¼3.4 Hz, 1H, HA-
3), 3.83 (ddAB, J3A,3B¼14.5 Hz, J2,3B¼4.3 Hz, 1H, HB-3),
3.42 (t, J2,3A¼3.8 Hz, 1H, H-2), 2.40 (bs, 1H, OH), 2.40–
2.08 (m, 1H, H-20), 2.06–1.88 (m, 2H, HA-60, HA-30), 1.82–
1.68 (m, 1H, HA-40), 1.62–1.38 (m, 1H, HA-50), 1.25–1.18
5.19–5.16 (m, 1H, H-3), 5.11–5.08 (m, 1H, H-2), 1.13 (s,
3H, H-80); 13C (125 MHz; CDCl3): d 171.0 (C-1), 135.0
(i-Ar), 89.5 (C-3), 70.2 (C-2), 64.9 (C-20), 52.4 (C-100), 49.2
(C-100), 47.2 (C-70), 44.6 (C-40), 37.5 (C-30), 35.0 (C-4), 31.1
(C-6 ).
(m, 1H, HB-30), 1.27 (s, 3H, H-90), 1.15 (s, 3H, H-100), 1.10–
4.2.19. (20R)-N-[(2j)-Hydroxy-3-carboxyethyl-(3j)-
nitro-propanoyl]-bornane-100,20-sultam (6ae). Colourless
oil, HRMS-LSIMS(þ): Calcd for C16H25N2O8S (MþH)þ
405.1331, found 405.1316. Anal Calcd C. 47.52, H. 5.98, N.
6.93, S. 7.93, found C. 47.82, H. 6.16, N. 6.62, S. 7.87; IR
(film): 3476, 2963, 1752, 1695, 1567, 1335, 1320, 1297,
1221, 1168, 1138, 1062, 1023, 857, 765, 536 cm21; Rf¼0.6
0.90 (m, 2H, HB-40, HB-60), 0.90 (d, J5 ,7 ¼6.5 Hz, 3H, H-7 );
13C NMR (50 MHz; CDCl3): d 169.8 (C-1), 152.4 (i-Ar),
127.9 (Ar), 125.0 (Ar), 124.9 (Ar), 77.2 (C-2), 76.1 (C-100),
75.8 (C-3), 66.6 (C-20), 40.5 (C-60), 39.0 (C-80), 34.2 (C-4 ),
31.0 (C-50), 30.8 (C-90), 25.8 (C-30), 21.5 (C-70), 20.9
(C-1000).
0
0
0
(hexane/AcOEt 7:3); H NMR (500 MHz; CDCl3): d 5.84
4.2.24. O-[(2R)-Hydroxy-3-nitropropanoyl]-(10R,
20S,50R)-80-phenylmenthol (5b). Selected signals from
1
(d, J2,3¼5.2 Hz, 1H, H-3), 5.40 (d, J2,3¼J2,OH¼5.2 Hz, 1H,
H-2), 4.36–4.25 (m, 2H, H-5), 4.00–3.93 (m, 1H, H-20),
4.39–3.62 (m, 2H, H-100), 2.19–1.84 (m, 5H, H-300, H-40,
H-60), 1.75–1.25 (m, 8H, H-50, H-6), 1.15 (s, 3H, H-8 ), 0.99
(s, 3H, H-90); 13C NMR (125 MHz; CDCl3): d 167.6 (C-1),
161.6 (C-1), 88.7 (C-3), 69.6 (C-2), 65.1 (C-20), 63.6 (C-5),
52.80 (C-100), 49.3 (C-10), 47.9 (C-70), 044.4 (C-40)0, 37.4
(C-3 ), 32.6 (C-60), 26.3 (C-50), 20.4 (C-8 ), 19.7 (C-9 ) 13.7
(C-6).
1
differential NMR spectra: H (200 MHz; CDCl3): d 4.93
(dt, J1 ,6 A¼J1 ,2 ¼10.9 Hz, J1 ,6 B¼4.5 Hz, 1H, H-10), 4.18
(ddAB, J3A,3B¼15.4 Hz, J2,3A¼5.3 Hz, 1H, HA-3), 4.06
(ddAB, J3A,3B¼15.4 Hz, J2,3B¼6.1 Hz, 1H, HB-3), 1.30 (s,
3H, H-90), 1.19 (s, 3H, H-100); 13C (50 MHz; CDCl3): d
169.1 (C-1), 152.3 (i-Ar), 128.0 (Ar), 127.5 (Ar), 125.0 (Ar),
77.3 (C-2), 67.9 (C-20), 40.8 (C-60), 39.1 (C-80), 31.1 (C-50),
26.0 (C-30), 21.4 (C-70).
0
0
0
0
0
0
4.2.20. (20R)-N-[(2j)-Hydroxy-3-carboxyethyl-(3j)-
nitropropanoyl]-bornane-100,20-sultam (7ae). Selected
signals from differential NMR spectra: 1H (500 MHz;
CDCl3): d 5.70 (d, J2,3¼3.4 Hz, 1H, H-3), 5.51 (d,
J2,3¼J2,OH¼3.4 Hz, 1H, H-2), 1.13 (s, 3H, H-80), 0.95 (s,
3H, H-90); 13C (125 MHz; CDCl3): d 167.8 (C-1), 161.8
4.2.25. O-[syn-(2j)-Hydroxy-(3j)-nitrooctanoyl]-(10R,
20S,50R)-80-phenylmenthol (6ba). Colourless oil, HRMS-
LSIMS(þ): Calcd for C24H38O5N (MþH)þ: 420.2750,
found 420.2745. Anal Calcd C. 68.71, H. 8.89, N. 3.34,
found C. 68.71, H. 9.10, N. 3.35; IR (film): 3497, 2957,
2927, 2870, 1732, 1555, 1458, 1258, 1130, 1094, 976,

I. Kudyba et al. / Tetrahedron 60 (2004) 4807–4820
4815
766 cm21; [a]D ¼26.4 (c¼1.42; CHCl3); Rf¼0.6 (hexane/
20
H-4), 4.93 (dt, J1 ,6 A¼J1 ,2 ¼10.8 Hz, J1 ,6 B¼4.5 Hz, 1H,
H-10), 4.28 (dd, J2,3¼2.5 Hz, J3,4¼8.0 Hz, 1H, H-3), 3.63
(dd, J5A,5B¼9.2 Hz, J5,6¼7.1 Hz, 2H,00 H-5), 3.56 (dd,
0
0
0
0
0
0
AcOEt 8:2); 1H NMR (500 MHz; CDCl3): d 7.33–7.23 (m,
0
0
0
0
4H, Ar), 7.21–7.09 (m, 1H, Ar), 4.90 (dt, J1 ,6 A¼J1 ,2 ¼10.8
Hz, J1 ,6 B¼4.4 Hz, 1H, H-10), 4.00 (ddd, J2,3¼3.0 Hz,
J5 A,5 B¼9.2 Hz, J5 ,6 ¼7.1 Hz, 2H, H-5 ), 3.40 (dd, J2,3
¼
0
0
00
00
00 00
J3,4A¼10.9 Hz, J3,4B¼6.8 Hz, 1H, H-3), 3.10 (dd, J2,3
¼
2.5 Hz, J2,OH¼7.3 Hz, 1H, H-2), 2.91 (d, J2,OH¼7.3 Hz, 1H,
0
0
0
0
0
0
3.0 Hz, J2,OH¼6.5 Hz, 1H, H-2), 2.88 (d, J2,OH¼6.5 Hz, 1H,
OH), 2.31–2.12 (m, 1H, H-20), 2.10–2.00 (m, 1H, HA-30),
1.99–1.84 (m, 3H, H-4, HA-60), 1.76–1.71 (m, 3H, H-5, HA-
40), 1.56–1.29 (m, 6H, H-6, H-7, H-30, HA-50), 1.28 (s, 3H,
H-90), 1.16 (s, 3H, H-100), 1.01–0.86 (m, 8H, HB-40, HB-60,
H-70, H-8); 13C NMR (125 MHz; CDCl3): d 168.2 (C-1),
152.5 (i-Ar), 127.9 (Ar), 125.2 (Ar), 125.0 (Ar), 87.6 (C-3),
76.9 (C-100), 71.7 (C-2), 50.1 (C-20), 40.6 (C-60), 39.2 (C-80),
34.3 (C-40 ), 31.0 (C-90), 30.5 (C-50), 30.4 (C-5), 28.3 (C-4),
26.0 (C-3 ), 25.6 (C-6), 22.3 (C-7), 21.8 (C-70), 21.7 (C-100),
13.8 (C-8).
OH), 2.12 (ddd, J1 ,2 ¼10.8 Hz, J2 ,3 A¼12.3 Hz, J2 ,3 B¼
3.7 Hz, 1H, H-20), 1.98–1.92 (m, 1H, HA-30), 1.89–1.84 (m,
1H, HA-60), 1.75–1.70 (m, 1H, HA-40), 1.52–1.40 (m, 1H,
HA-50), 1.30 (s, 3H, H-90), 1.29 (t, J5,6¼7.1 Hz, 3H, H-6),
1.20–1.14 (m, 1H, HB-30), 1.10–0.91 (m, 2H, HB-40,00HB-60),
1.18 (s, 3H, H-100), 1.15 (t, J5 ,6 ¼7.1 Hz, 3H, H-6 ), 0.90
00 00
0
(d, J5 ,7 ¼6.5 Hz, 3H, H-7 ); 13C NMR (125 MHz; CDCl3): d
170.1 (C-1), 151.7 (i-Ar), 127.9 (Ar), 125.3 (Ar), 125.2 (Ar),
99.5 (C-4), 88.5 (C-3), 76.9 (C-100), 68.4 (C-2), 64.8 (C-5),
64.5 (C-500), 50.3 (C-20), 040.8 (C-6 ), 39.2 (C-80), 34.4 (C-40),
31.3 (C-50), 30.4 (C-9 ), 260.01 (C-30), 21.8 (C-70), 21.7
(C-100), 15.3 (C-6), 15.0 (C-6 ).
0
0
40.2.206. O-[anti-(2j)-Hydroxy-(3j)-nitrooctanoyl]-(10R,
0
1
2 S,5 R)-8 -phenylmenthol (7ba). Colourless oil, H NMR
4.2.30. O-[4,4-Diethoxy-(2j)-hydroxy-(3j)-nitrobuta-
noyl]-(10R,20S,50R)-80-phenylmenthol (7bb). Selected sig-
nals from differential NMR spectra: 1H (500 MHz; CDCl3):
d 5.01 (d, J3,4¼8.1 Hz, 1H, H-4), 4.41 (dd, J2,3¼1.7 Hz,
0
0
0
0
(500 MHz; CDCl3): d 4.92 (dt, J1 ,6 A¼J1 ,2 ¼10.8 Hz,
J1 ,6 B¼4.4, 1H, H-10), 4.19 (dt, J2,3¼J3,4B¼3.2 Hz, J3,4A
¼
0
0
7.3 Hz, 1H, H-3), 3.72 (dd, J2,3¼3.2 Hz, J2,OH¼4.8 Hz, 1H,
H-2), 2.95 (d, J2,OH Hz¼4.8, 1H), OH, 1.24 (s, 3H, H-90),
1.15 (s, 3H, H-100); 13C NMR (125 MHz; CDCl3): d 170.3
(C-1), 152.4 (i-Ar), 127.9 (Ar), 125.2 (Ar), 125.0 (Ar), 87.5
(C-3), 76.8 (C-100), 69.6 (C-2), 50.0 (C-20), 40.6 (C-600), 39.1
(C-80), 34.3 (C-4 ), 31.1 (C-90), 30.9 (C-5), 30.8 (C-50), 28.2
(C-4), 26.0 (C-30), 25.5 (C-6), 22.1 (C-7), 21.7 (C-7 ), 21.6
(C-100), 13.7 (C-8).
J3,4¼8.1 Hz, 1H, H-3), 3.40 (dd, J2,3¼1.7 Hz, J2,OH
¼
3.9 Hz, 1H, H-2); 13C (125 MHz; CDCl3): d 169.5 (C-1),
151.3 (i-Ar), 128.0 (Ar), 125.5 (Ar), 125.0 (Ar), 99.3 (C-4),
88.9 (C-3), 77.0 (C-100), 68.9 (C-20), 65.3 (C-5), 64.6 (C-5000),
50.1 (C-20), 41.0 (C-6 ),039.4 (C-8 ), 304.4 (C-40), 31.3 (C-5 ),
30.2 (C-90), 26.1 (C-3 ), 22.6 (C-7 ), 21.7 (C-100), 15.1
(C-6), 15.0 (C-600).
4.2.27. O-[(2j)-Hydroxy-(3j)-nitrooctanoyl]-(10R,
20S,50R)-80-phenylmenthol (8ba). Selected signals from
differential NMR spectra: 1H (500 MHz; CDCl3): d 4.97 (dt,
4.2.31. O-[4,4-Diethoxy-(2j)-hydroxy-(3j)-nitrobuta-
noyl]-(10R,20S,50R)-80-phenylmenthol (8bb). Selected sig-
nals from differential NMR spectra: 1H (500 MHz; CDCl3):
d 5.01 (d, J3,4¼7.7 Hz, 1H, H-4), 4.59 (dd, J2,3¼2.2 Hz,
3.9 Hz, 1H, H-2), 3.05 (d, J2,OH¼3.9 Hz, 1H, OH); 13C
(125 MHz; CDCl3): d 168.8 (C-1), 152.1 (i-Ar), 127.9 (Ar),
99.2 (C-4), 87.6 (C-3), 77.0 (C-100), 69.6 (C-2), 64.7 (C-5),
64.4 (C-500), 49.8 (C-20),039.2 (C-8 ), 34.4 (C-40), 31.2 (C-50),
29.6 (C-90), 26.3 (C-3 ), 22.8 (C-70), 22.1 (C-100), 15.2
(C-6), 14.1 (C-600).
J1 ,6 A¼J1 ,2 ¼10.8 Hz, J1 ,6 B¼4.5 Hz, 1H, H-10), 4.22 (dt,
0
0
0
0
0
0
J2,3¼J3,4B¼3.8 Hz, J3,4A¼9.9 Hz, 1H, H-3), 3.37 (dd, J2,3
¼
J3,4¼7.7 Hz, 1H, H-3), 4.11 (dd, J2,3¼2.2 Hz, J2,OH¼
3.8 Hz, J2,OH¼4.0 Hz, 1H, H-2), 3.03 (d, J2,OH¼4.0 Hz, 1H,
OH), 1.24 (s, 3H, H-90), 1.15 (s, 3H, H-100); 13C (125 MHz;
CDCl3): d 170.3 (C-1), 151.7 (i-Ar), 128.0 (Ar), 125.1 (Ar),
125.0 (Ar), 89.2 (C-30), 77.0 (C-100), 70.2 (C-2), 50.2 (C-200),
41.2 (C-60), 39.2 (C-8 ), 34.2 (C-40), 31.1 (C-90), 30.9 (C-5 ),
30.3 (C-50), 28.2 (C-4),026.0 (C-3 ), 25.5 (C-6), 22.1 (C-7),
21.7 (C-7 ), 21.6 (C-10 ), 13.7 (C-8).
4.2.32. O-[4,4-Diethoxy-(2j)-hydroxy-(3j)-nitrobuta-
noyl]-(10R,20S,50R)-80-phenylmenthol (9bb). Selected sig-
nals from differential NMR spectra: 1H (500 MHz; CDCl3):
d 5.15 (d, J3,4¼8.1 Hz, 1H, H-4), 4.73 (dd, J2,3¼2.9 Hz,
2.3 Hz, 1H, H-2); 13C (125 MHz; CDCl3): d 167.9 (C-1),
152.9 (i-Ar), 128.0 (Ar), 89.2 (C-3), 77.2 (C-10), 70.2 (C-2),
66.7 (C-5), 64.1 (C-500), 49.8 (C-20), 39.4 (C-80), 34.4 (C-40),
30.9 (C-50), 29.8 (C-90), 26.3 (C-30), 22.5 (C-70), 22.2
(C-100).
4.2.28. O-[(2j)-Hydroxy-(3j)-nitrooctanoyl]-(10R,
20S,50R)-80-phenylmenthol (9ba). Selected signals from
differential NMR spectra: 1H (500 MHz; CDCl3): d 4.94 (dt,
J1 ,6 A¼J1 ,2 ¼10.8 Hz, J1 ,6 B¼4.5 Hz, 1H, H-10), 4.49 (dt,
J2,3¼J3,4B¼4.5 Hz, J3,4A¼9.0 Hz, 1H, H-3), 1.30 (s, 3H,
H-90), 1.17 (s, 3H, H-100); 13C (125 MHz; CDCl3): d 169.5
(C-1), 152.5 (i-Ar), 87.0 (C-3), 76.6 (C-10), 70.8 (C-2), 49.5
(C-200), 40.9 (C-60), 39.3 (C-80), 34.4 (C-400), 31.2 (C-90), 30.4
(C-5 ), 30.3 (C-5), 28.8 (C-4), 26.2 (C-3 ), 25.4 (C-6), 22.1
(C-7), 21.7 (C-70), 21.5 (C-100), 13.8 (C-8).
J3,4¼8.1 Hz, 1H, H-3), 4.01 (dd, J2,3¼2.9 Hz, J2,OH
¼
0
0
0
0
0
0
4.2.33. O-[(2S)-Hydroxy-(3R)-nitro-3-phenylpropanoyl]-
(10R,20S,50R)-80-phenylmenthol (6bc). Colourless crystals,
mp¼179–180 8C (hexane/AcOEt); HRMS-LSIMS (þ):
Calcd for C25H31O5NNa (MþNa)þ 448.2099, found
448.2087. Anal. Calcd C. 70.57, H. 7.34, N. 3.29, found
C. 70.10, H. 7.55, N. 3.32; IR (KBr): 3479 2958, 2924,
1730, 1556, 1496, 1456, 1366, 1258, 1121, 957, 766,
4.2.29. O-[4,4-Diethoxy-syn-(2j)-hydroxy-(3j)-nitro-
butanoyl]-(10R,20S,50R)-80-phenylmenthol (6bb). Colour-
less oil, HRMS-LSIMS(þ): Calcd for C24H38O7N
(MþH)þ: 452.2648, found 452.2643. Anal. Calcd C.
63.87, H. 8.26, N. 3.10, found C. 63.62, H. 8.45, N. 3.10;
IR (film): 3492, 2961, 2926, 1737, 1556, 1445, 1327, 1278,
1120, 1066, 766, 702 cm21; [a]D ¼213.5 (c¼0.98;
701 cm–1; [a]D ¼7.2 (c¼0.93; CHCl3); Rf¼0.5 (hexane/
20
20
1
CHCl3); Rf¼0.5 (hexane/AcOEt 8:2); H NMR (500 MHz;
AcOEt 8:2)1H NMR (500 MHz; CDCl3): d 7.50–7.06 (m,
10H, 2xAr), 5.14 (d, J2,3¼5.1 Hz, 1H, H-3), 4.87 (dt,
CDCl3): d 7.29–7.10 (m, 5H, Ar), 4.97 (d, J3,4¼8.0 Hz, 1H,

4816
I. Kudyba et al. / Tetrahedron 60 (2004) 4807–4820
0
J1 ,6 A¼J1 ,2 ¼10.8 Hz, J1 ,6 B¼4.5 Hz, 1H, H-10), 3.63 (dd,
HB-60), 0.89 (d, J5 ,7 ¼6.5 Hz, 3H, H-7 ); 13C NMR
(125 MHz; CDCl3): d 170.3 (C-1), 151.8 (i-Ar), 135.0
(i-Ar), 129.3 (Ar), 128.8 (Ar), 127.6 (Ar0), 127.4 (Ar), 125.1
(Ar), 125.0 (Ar), 88.5 (C-3), 76.9 (C-1 ), 68.7 (C-2), 50.1
(C-200), 40.7 (C-600), 39.1 (C-800), 35.4 (C-4)0, 34.4 (C-40), 31.2
(C-5 ), 30.6 (C-9 ), 26.0 (C-3 ), 21.6 (C-7 ), 21.3 (C-100).
0
0
0
0
0
0
0
0
J2,3¼5.1 Hz, J2,OH¼6.1 Hz, 1H, H-2), 3.05 (d, J2,OH
¼
0
0
0
0
6.1 Hz, 1H, OH), 2.07 (ddd, J1 ,2 ¼10.8 Hz, J2 ,3 A¼3.6 Hz,
J2 ,3 B¼12.1 Hz, 1H, H-20), 1.99 (dd, J2 ,3 A¼J4 A,3 A¼3.6
0
0
0
0
0
0
Hz, J3 A,3 B¼13.5 Hz, 1H, HA-30), 1.78–1.71 (m, 1H, HA-
60), 1.67–1.62 (m, 1H, HA-40), 1.52–1.41 (m, 1H, HA-50),
1.30 (s, 3H, H-90), 1.26–1.19 (m, 1H, HB-30), 1.15 (s, 3H,
0
0
H-100), 1.00–0.89 (m, 2H, HB-40, HB-60), 0.87 (d,
4.2.37. O-[(2S)-Hydroxy-(3S)-nitro-4-phenylbutanoyl]-
(10R,20S,50R)-80-phenylmenthol (7bd). Colourless crystals,
0
J5 ,7 ¼6.5 Hz, 3H, H-7 ); 13C NMR (125 MHz; CDCl3): d
169.9 (C-1), 152.3 (i-Ar), 131.0 (i-Ar), 129.9 (Ar), 129.1
(Ar), 128.6 (Ar), 127.9 (Ar), 125.4 (Ar), 124.2 (Ar), 91.1
(C-3)0 , 76.9 (C-100), 71.1 (C-2), 50.1 (C-200), 40.5 (C-600), 39.1
(C-80), 34.2 (C-4 ), 31.1 (C-50), 30.8 (C-9 ), 25.9 (C-3 ), 21.6
(C-7 ), 21.3 (C-100).
0
0
20
mp¼91–93 8C (hexane/AcOEt); [a]D ¼221 (c¼1.27;
CHCl3); 1H NMR (500 MHz; CDCl3): d 7.31–7.21 (m,
7H, Ar), 7.16–7.12 (m, 1H, Ar), 7.08–7.025 (m, 2H, Ar),
4.94 (dt, J1 ,6 A¼J1 ,2 ¼10.8 Hz, J1 ,6 B¼4.4 Hz, 1H, H-10),
4.46 (ddd, J2,3¼3.9 Hz, J3,4A¼9.7 Hz, J3,4B¼4.5 Hz, 1H,
H-3), 3.47 (dd, J2,3¼3.9 Hz, J2,OH¼4.6 Hz, 1H, H-2), 3.19
(ddAB, J4A,4B¼14.9 Hz, J3,4A¼9.7 Hz, 1H, HA-4), 3.01 (d,
J2,OH¼4.6 Hz, 1H, OH), 2.73 (ddAB, J4A,4B¼14.9 Hz,
0
0
0
0
0
0
4.2.34. O-[anti-(2j)-Hydroxy-(3j)-nitro-3-phenylpropa-
noyl]-(10R,20S,50R)-80-phenylmenthol (7bc). Selected sig-
nals from differential NMR spectra: 1H (500 MHz; CDCl3):
0
0
J3,4B¼4.5 Hz, 1H, HB-4), 2.16 (ddd, J1 ,2 ¼10.8 Hz,
J2 ,3 A¼12.2 Hz, J2 ,3 B¼3.6 Hz, 1H, H-20), 1.96 (d0q,
0
0
0
0
0
0
0
0
d 5.25 (d, J2,3¼4.5 Hz, 1H, H-3), 4.94 (dt, J1 ,6 A¼J1 ,2
¼
10.8 Hz, J1 ,6 B¼4.2 Hz, 1H, H-10), 4.21 (dd, J2,3¼4.5 Hz,
J3 A,3 B¼13.5 Hz, J2 ,3 B¼J3 ,4 A¼3.6 Hz, 1H, HA-3 ),
1.80–1.71 (m, 1H, HA-60, HA-40), 1.53–1.41 (m, 1H, HA-
50), 1.23–1.16 (m, 1H, HB-30), 1.29 (s, 3H, H-90), 1.18 (s,
0
0
0
0
0
0
0
0
J2,OH¼4.8 Hz, 1H, H-2), 3.05 (d, J2,OH¼4.8 Hz, 1H, OH),
1.34 (s, 3H, H-90), 1.20 (s, 3H, H-100), 0.86 (d, J5 ,7 ¼6.5 Hz,
3H, H-70); 13C (125 MHz; CDCl3): d 169.7 (C-1), 152.0
(i-Ar), 131.3 (i-Ar), 129.9 (Ar), 129.8 (Ar), 128.3 (Ar),
128.2 (Ar), 125.3 (Ar), 125.0 (Ar), 89.6 (C-3), 77.5 (C-100),
70.5 (C-2), 50.3 (C-20), 40.9 (C-60), 39.3 (C-80), 34.4 (C-4 ),
31.2 (C-50), 30.4 (C-90), 26.0 (C-30), 21.6 (C-70), 21.5
(C-100).
0
0
3H, H-100), 1.10–0.91 (m, 2H, HB-40, HB-60), 0.90 (d,
0
J5 ,7 ¼6.5 Hz, 3H, H-7 ); 13C NMR (125 MHz; CDCl3): d
170.0 (C-1), 151.7 (i-Ar), 135.4 (i-Ar), 128.9 (Ar), 128.7
(Ar), 128.1 (Ar), 127.4 (Ar), 125.4 (Ar), 125.1 (Ar), 90.2
(C-3), 77.4 (C-10), 70.2 (C-2), 50.2 (C-200), 41.2 (C-600), 39.3
(C-800), 34.3 (C-4), 34.2 (C-40),031.3 (C-5 ), 30.4 (C-9 ), 26.1
(C-3 ), 21.8 (C-70), 21.6 (C-10 ).
0
0
4.2.35. O-[(2j)-Hydroxy-(3j)-nitro-3-phenylpropanoyl]-
(10R,20S,50R)-80-phenylmenthol (8bc). Selected signals
4.2.38. O-[(2j)-Hydroxy-(3j)-nitro-4-phenylbutanoyl]-
(10R,20S,50R)-80-phenylmenthol (8bd). Colourless crystals,
mp¼126–127 8C; [a]D ¼13 (c¼0.92; CHCl3); H NMR
(500 MHz; CDCl3): d 7.39–7.35 (m, 2H, Ar), 7.33–7.29
(m, 1H, Ar), 7.26–7.24 (m, 3H, Ar), 7.20–7.13 (m, 4H, Ar),
1
from differential NMR spectra: H (500 MHz; CDCl3): d
0
20
1
0
0
0
5.39 (d, J2,3¼5.2 Hz, 1H, H-3), 4.73 (dt, J1 ,6 A¼J1 ,2 ¼10.8
Hz, J1 ,6 B¼4.4 Hz, 1H, H-10), 4.60 (dd, J2,3¼5.1 Hz,
0
0
J2,OH¼3.8 Hz, 1H, H-2), 2.95 (d, J2,OH¼3.8 Hz, 1H, OH),
1.25 (s, 3H, H-90), 1.15 (s, 3H, H-100), 0.78 (d, J5 ,7 ¼6.5 Hz,
3H, H-70); 13C (125 MHz; CDCl3): d 168.7 (C-1), 152.5
(i-Ar), 129.8 (Ar), 129.2(Ar), 128.0 (Ar), 125.4 (Ar), 125.0
(Ar), 89.5 (C-3), 77.4 (C-10), 72.3 (C-2), 49.8 (C-200), 40.8
(C-600), 39.2 (C-800), 34.2 (C-40),031.1 (C-50), 30.2 (C-9 ), 26.3
(C-3 ), 22.3 (C-7 ), 21.0 (C-10 ).
4.90 (dt, J1 ,6 A¼J1 ,2 ¼10.8 Hz, J1 ,6 B¼4.4 Hz, 1H, H-10),
4.52 (ddd, J2,3¼2.33 Hz, J3,4A¼5.8 Hz, J3,4B¼10.3 Hz, 1H,
H-3), 3.45 (dd, J2,3¼2.3 Hz, J2,OH¼4.4 Hz, 1H, H-2), 3.43
(ddAB, J4A,4B¼13.6 Hz, J3,4A¼5.8 Hz, 1H, HA-4), 3.12
(ddAB, J4A,4B¼13.6 Hz, J3,4B¼10.3 Hz, 1H, HB-4), 2.21
0
0
0
0
0
0
0
0
0
0
0
0
0
0
(ddd, J1 ,2 ¼10.7 Hz, J2 ,3 A¼12.2 Hz, J2 ,3 B¼3.6 Hz, 1H,
H-20), 1.96 (dq, J3 A,3 B¼13.5 Hz, J2 ,3 B¼J3 ,4 A¼3.6 Hz,
1H, H-30), 1.94–1.90 (m, 1H, HA-60), 1.75–1.71 (m, 1H,
HA-40), 1.53–1.44 (m, 1H, HA-50), 1.25–1.16 (m, 1H, HB-
0
0
0
0
0
0
4.2.36. O-[(2S)-Hydroxy-(3R)-nitro-4-phenylbutanoyl]-
(10R,20S,50R)-80-phenylmenthol (6bd). Colourless crystals,
mp¼85 8C (hexane/Et2O); HRMS-ESI: Calcd for
C26H33O5NNa (MþNa)þ 462.2251, found 462.2251.
Anal. Calcd C. 71.05, H. 7.57, N. 3.19, found C. 70.90, H.
7.61, N. 3.03; IR (KBr): 3567, 2960, 2920, 1718, 1546,
30), 1.26 (s, 3H, H-90), 1.14 (s, 3H, H-100), 1.05–0.90 (m,
0
2H, HB-40, HB-60), 0.89 (d, J5 ,7 ¼6.5 Hz, 3H, H-7 ); 13C
NMR (125 MHz; CDCl3): d 169.6 (C-1), 152.5 (i-Ar), 135.5
(i-Ar), 129.3 (Ar), 128.9 (Ar), 127.9 (Ar0), 127.4 (Ar), 125.2
(Ar), 125.2 (Ar), 87.2 (C-3), 76.8 (C-1 ), 69.2 (C-2), 49.7
(C-200), 40.8 (C-600), 39.3 (C-800), 34.6 (C-4)0, 34.4 (C-40), 31.3
(C-5 ), 30.7 (C-9 ), 26.2 (C-3 ), 21.6 (C-7 ), 21.5 (C-100).
0
0
1367, 1282, 1126, 986, 758, 695, 491 cm–1; [a]D ¼26
20
1
(c¼1.11; CHCl3); Rf¼0.5 (hexane/AcOEt 8:2); H NMR
(500 MHz; CDCl3): d 7.40–7.30 (m, 3H, Ar), 7.22–7.19
(m, 4H, Ar), 7.07–7.02 (m, 2H, Ar), 6.75–6.71 (m, 1H, Ar),
4.92 (dt, J1 ,6 A¼J1 ,2 ¼10.8 Hz, J1 ,6 B¼4.5 Hz, 1H, H-10),
4.35 (ddd, J2,3¼2.7 Hz, J3,4A¼6.9 Hz, J3,4B¼8.5 Hz, 1H,
H-3), 4.31 (ddAB, J4A,4B¼13.9 Hz, J3,4A¼6.9 Hz, 1H, HA-
4), 3.07 (ddAB, J4A,4B¼13.9 Hz, J3,4B¼6.9 Hz, 1H, HB-4),
3.01 (dd, J2,3¼2.7 Hz, J2,OH¼6.9 Hz, 1H, H-2), 2.95 (d,
4.2.39. O-[(2j)-Hydroxy-3-carboxyethyl-(3j)-nitro-
propanoyl]-(10R,20S,50R)-80-phenylmenthol (6be). Colour-
less oil, HRMS-ESI: Calcd for C22H31O7NNa (MþNa)þ:
444.1993, found 444.1960. Anal. Calcd C. 62.69, H. 7.41, N.
3.32, foundC. 62.77,H. 7.41, N. 3.37;3493, 2961, 2927, 2871,
1754, 1567, 1496, IR (film): 1444, 1368, 1257, 1199, 1129,
0
0
0
0
0
0
0
0
J2,OH¼6.9 Hz, 1H, OH), 2.10 (ddd, J1 ,2 ¼10.6 Hz,
J2 ,3 A¼12.1 Hz, J2 ,3 B¼3.7 Hz, 1H, H-20), 1.96 (d0q,
1029, 767, 703, 532 cm21; Rf¼0.5 (hexane/AcOEt 8:2); H
1
0
0
0
0
0
0
0
0
0
0
J3 A,3 B¼13.5 Hz, J2 ,3 B¼J3 ,4 A¼3.7 Hz, 1H, HA-3 ),
1.87–1.84 (m, 1H, HA-60), 1.75–1.70 (m, 1H, HA-40),
1.52–1.41 (m, 1H, HA-50), 1.23–1.16 (m, 1H, HB-30), 1.24
(s, 3H, H-90), 1.12 (s, 3H, H-100), 1.00–0.90 (m, 2H, HB-40,
NMR (500 MHz; CDCl3): d 7.35–7.25 (m, 4H, Ar), 7.17–
0
0
0
0
7.08 (m, 1H, Ar), 0 4.94 (dt, J1 ,6 A¼J1 ,2 ¼10.7 Hz,
0
0
J1 ,6 B¼4.5 Hz, 1H, H-1 ), 4.84 (d, J2,3¼2.6 Hz, 1H, H-3),
4.35–4.16(m, 2H, H-5), 3.79(dd,J2,3¼2.6 Hz, J2,OH¼5.0 Hz,

I. Kudyba et al. / Tetrahedron 60 (2004) 4807–4820
4817
1H, H-2), 3.19 (d, J2,OH¼5.2 Hz, 1H, OH), 2.20–2.07 (m, 1H,
H-20), 2.02–1.94 (m, 1H, HA-30), 1.86–1.77 (m, 1H, HA-60),
1.77–1.71 (m, 1H, HA-40), 1.56–1.44 (m, 1H, HA-50), 1.37–
1.18 (m, 1H, HB-30), 1.19 (s, 3H, H-90), 1.18 (s, 3H, H-100),
H-5, H-6, H-7), 0.88–082 (m, 3H, H-8); 13C NMR
(50 MHz; CDCl3): d 90.3 (C-3), 72.5 (C-2), 62.9 (C-1),
30.9 (C-4), 29.9 (C-5), 25.2 (C-6), 22.2 (C-7), 13.8 (C-8).
1.00–0.89 (m, 3H, HB-40, HB-60, H-6), 0.88 (d, J5 ,7 ¼6.6 Hz,
3H, H-70); 13C NMR (125 MHz; CDCl3): d 168.4 (C-1), 161.6
(C-4),151.8(i-Ar),128.0(Ar),125.5(Ar), 125.4(Ar), 88.2(C-
3), 77.5 (C-10), 68.4 (C-2), 63.2 (C-5), 50.3 (C-20), 40.8 (C-600),
39.1 (C-800), 34.3 (C-40), 31.1 (C-50), 30.3 (C-90), 25.9 (C-3 ),
21.5 (C-7 ), 21.5 (C-100), 13.7 (C-6).
4.3.3. anti-(3j)-Nitrooctane-(1,2j)-diol (11b). The title
compound was obtained with 85% yield; colourless oil,
HRMS-ESI: Calcd for C8H17NO4Na (MþNa)þ: 214.1050,
found 214.1052. Anal. Calcd C. 50.25, H. 8.96, N. 7.32,
found C. 50.10, H. 8.89, N. 7.19; IR (film): 3370, 2958,
0
0
2932, 2865, 1552, 1464, 1378, 1098, 1038, 834 cm21
;
[a]D ¼221.0 (c¼1.70; MeOH); 1H NMR (200 MHz;
20
4.2.40. O-[(2j)-Hydroxy-3-carboxyethyl-(3j)-nitropro-
panoyl]-(10R,20S,50R)-80-phenylmenthol (7be). Selected
signals from differential NMR spectra: 1H (500 MHz;
CDCl3): d 4.63 (ddd, J2,3¼5.8 Hz, J3,4A¼3.5 Hz, J3,4B
10.3 Hz, 1H, H-3), 4.09 (dd, J2,3¼J2,1A¼5.8 Hz, J2,1B
3.8 Hz, 1H, H-2), 3.76 (ddAB, J2,1B¼3.8 Hz, J1A,1B
11.7 Hz, 1H, HB-1), 3.66 (ddAB, J2,1A¼5.8 Hz, J1A,1B
¼
¼
¼
¼
0
0
0
0
0
0
CDCl3): d 4.88 (dt, J1 ,6 A¼J1 ,2 ¼10.8 Hz, J1 ,6 B¼4.3 Hz,
1H, H-10), 4.45 (d, J2,3¼3.4 Hz, 1H, H-3), 3.70 (dd, J2,3
¼
11.7 Hz, 1H, HA-1), 2.30–1.80 (m, 21H, H-4), 1.60–1.30
(m, 6H, H-5, H-6, H-7), 0.99–082 (m, 3H, H-8); 13C NMR
(50 MHz; CDCl3): d 89.4 (C-3), 72.2 (C-2), 62.7 (C-1), 31.0
(C-4), 29.0 (C-5), 25.4 (C-6), 22.2 (C-7), 13.8 (C-8).
3.4 Hz, J2,OH¼7.8 Hz, 1H, H-2), 3.11 (d, J2,OH¼7.8 Hz, 1H,
OH), 1.18 (s, 3H, H-90), 1.15 (s, 3H, H-100), 0.90 (d,
0
J5 ,7 ¼6.6, 3H, H-7 ); 13C (125 MHz; CDCl3): d 168.2 (C-1),
161.8 (C-4), 152.6 (i-Ar), 128.0 (Ar), 125.4 (Ar), 125.2 (Ar),
87.7 (C-3), 77.4 (C-100), 68.6 (C-2), 63.2 (C-5), 50.0 (C-200),
40.2 (C-600), 39.0 (C-8 ), 34.3 (C-40),031.0 (C-50), 30.4 (C-9 ),
25.8 (C-3 ), 21.6 (C-70), 21.6 (C-10 ), 13.8 (C-6).
0
0
4.3.4. (3R)-Nitro-3-phenylpropane-(1,2S)-diol (12a). The
title compound was obtained with 90% yield. Colourless
crystals, mp¼83 8C (hexane/AcOEt); HRMS-ESI: Calcd for
C9H11NO4 (MþNa)þ 220.0580; found 220.0572. Anal.
Calcd C. 54.82, H. 5.62, N. 7.10, found C. 55.00, H. 5.78, N.
7.21; IR (KBr): 3541, 3400, 2928, 1649, 1539, 1370, 1320,
4.3. General procedure for the synthesis of nitrodiols
20
To a precooled solution (0 8C) of nitroalcohol (1 mmol) in
THF (1 mL), NaBH4 (1.1 mmol) was portionwise added.
Progress of the reaction was monitored by TLC, and when
finished, it was quenched by addition of saturated aqueous
NaCl and extracted with AcOEt. The combined organic
extracts were dried over MgSO4 and evaporated. All
products were purified by column chromatography
(hexane/AcOEt 8:2–4:6).
1100, 1049, 903, 732, 692, 632, 497 cm21; [a]D ¼211.1
i
1
(c¼0.51; PrOH); Rf¼0.2 (hexane/AcOEt 1:1); H NMR
(400 MHz; CDCl3): d 7.60–7.35 (m, 5H, Ar), 5.60 (d,
J2,3¼9.9 Hz, 1H, H-3), 4.64 (ddd, J2,3¼9.9 Hz, J2,1A
¼
2.9 Hz, J2,1B¼4.6 Hz, 1H, H-2), 3.73 (bs, 1H, OH-2), 3.56
(ddAB, J2,1A¼2.9 Hz, J1A,1B¼11.7 Hz, 1H, HA-1), 3.29
(ddAB, J2,1B¼4.6 Hz, J1A,1B¼11.7 Hz, 1H, HB-1), 2.79 (bs,
1H, OH-1); 13C NMR (125 MHz; CDCl3): d 131.2
(i-Ar),130.4 (Ar), 129.3 (Ar), 128.0 (Ar), 93.3 (C-3), 72.9
(C-2), 62.1 (C-1).
4.3.1. 3-Nitropropane-(1,2S)-diol (10). The title compound
was obtained in 85% yield from 4a, and 87% from 4b:
colourless oil, HRMS-ESI: Calcd for C3H8NO4 (MþH)þ
122.1005; found 122.1008. Anal. Calcd C. 29.75, H. 5.82,
N. 11.56, found C. 29.60, H. 5.92, N. 11.31; IR (film): 3366,
4.3.5. anti-(3j)-Nitro-3-phenylpropane-(1,2j)-diol (12b).
The title compound was obtained with 87% yield. Colour-
20
i
less oil, [a]D ¼28.8 (c¼0.70; PrOH); Rf¼0.2 (hexane/
AcOEt 1:1); 1H NMR (400 MHz; CDCl3): d 7.55–7.40 (m,
5H, Ar), 5.61 (d, J2,3¼7.1 Hz, 1H, H-3), 4.65 (m, 1H, H-2),
3.77 (ddAB, J2,1A¼3.8 Hz, J1A,1B¼11.5 Hz, 1H, HA-1), 3.68
(ddAB, J2,1B¼4.9 Hz, J1A,1B¼11.5 Hz, 1H, HB-1); 13C NMR
(125 MHz; CDCl3): d 131.2 (i-Ar),130.4 (Ar), 129.3 (Ar),
128.0 (Ar), 93.3 (C-3), 72.9 (C-2), 62.1 (C-1).
1552, 1384, 1111, 1048, 875 cm21; [a]D ¼26.7 (c¼0.99;
20
1
CHCl3); Rf¼0.1 (hexane/AcOEt 1:1); H NMR (500 MHz;
D2O): d 4.75 (ddAB, J2,3A¼3.2 Hz, J3A,3B¼13.0 Hz, 1H,
HA-3), 4.59 (ddAB, J2,3B¼9.0 Hz, J3A,3B¼13.0 Hz, 1H, HB-
3), 4.43 (dddd, J2,3A¼3.2 Hz, J2,3B¼9.0 Hz, J2,1A¼5.0 Hz,
J2,1B¼5.6 Hz, 1H, H-2), 3.69 (ddAB
,
J2,1A¼5.0 Hz,
J1A,1B¼11.9 Hz, 1H, HA-1), 3.65 (ddAB, J2,1B¼5.6 Hz,
J1A,1B¼11.9 Hz, 1H, HB-1); 13C NMR (125 MHz;
CDCl3): d 77.7 (C-3), 68.8 (C-2), 63.4 (C-1).
4.3.6. (3S)-Nitro-3-phenylpropane-(1,2R)-diol (12c). The
title compound was obtained in 86% yield. Colourless
crystals, mp¼82–84 8C (hexane/AcOEt); Rf¼0.2 (hexane/
20
i
4.3.2. (3R)-Nitrooctane-(1,2S)-diol (11a). The title com-
pound was obtained with 88% yield; colourless oil, HRMS-
ESI: Calcd for C8H17NO4Na (MþNa)þ: 214.1050, found
214.1054. Anal. Calcd C. 50.25, H. 8.96, N. 7.32, found C.
50.03, H. 8.83, N. 7.20; IR (film): 3371, 2958, 2931, 2863,
1554, 1464, 1377, 1099, 1039, 833 cm21; Rf¼0.2 (hexane/
AcOEt 1:1); [a]D ¼12.0 (c¼0.63; PrOH).
4.3.7. O-[(2S)-t-Butyldimethylsilyloxy-3-nitropropa-
noyl]-(10R,20S,50R)-80-phenylmenthol (4c). To a solution
of nitroalcohol 4b (797 mg, 2.27 mmol) in DMF (3 mL)
TBDMSCl (375 mg, 2.49 mmol) and imidazole were added
(617 mg, 9.08 mmol). The progress of reaction was
monitored by TLC. After stirring at rt for 17 h, solvents
were evaporated and purification was achieved on silica-gel
column using hexane/AcOEt to give compound 4c (970 mg,
92%), (Rf¼0.8 hexane/AcOEt 8:2). Colourless oil, HRMS-
LSIMS(þ): Calcd for C25H45O5SiNNa (MþNa)þ
486.2651, found 486.2677. Anal. Calcd C. 64.62, H. 9.11,
20
AcOEt 1:1); [a]D ¼10.5 (c¼1.74; MeOH); 1H NMR
(200 MHz; CDCl3): d 4.64 (ddd, J2,3¼8.3 Hz, J3,4A
¼
3.9 Hz, J3,4B¼10.4 Hz, 1H, H-3), 4.15 (dd, J2,3¼8.3 Hz,
J2,1A¼3.0 Hz, J2,1B¼5.5 Hz, 1H, H-2), 3.79 (ddAB
,
,
J2,1A¼3.0 Hz, J1A,1B¼11.9 Hz, 1H, HA-1), 3.61 (ddAB
J2,1B¼5.5 Hz, J1A,1B¼11.9 Hz, 1H, HB-1), 2.10–1.87 (m,
1H, HA-4), 1.83–1.63 (m, 1H, HB-4), 1.50–1.10 (m, 6H,

4818
I. Kudyba et al. / Tetrahedron 60 (2004) 4807–4820
N. 3.01, found C. 64.76, H. 9.17, N. 2.88; IR (film): 2956,
2929, 2857, 1752, 1562, 1472, 1379, 1254, 1207, 1154, 969,
3), 3.14 (ddAB, J3A,3B¼12.6 Hz, J2,3B¼5.1 Hz, 1H, HB-3);
13C NMR (50 MHz; CDCl3): d 177.3 (C-1), 68.7 (C-2), 42.8
(C-3).
838, 766, 782, 701 cm21; [a]D ¼23.0 (c¼1.11; CHCl3);
20
1H NMR (200 MHz; CDCl3): d 7.40–7.05 (m, 5H, Ar), 4.92
(dt, J1,6A¼J1,2¼10.8 Hz, J1,6B¼4.5 Hz, 1H, H-10), 4.18
(ddAB, J3A,3B¼14.5 Hz, J2,3A¼10.8 Hz, 1H, HA-3), 3.42
4.3.10. General procedure for the synthesis of N-Boc-
aminoalcohols. Through a solution of a nitroalcohol
(0.39 mmol) in MeOH (5 mL) H2 was bubbled in the
presence of catalytic amounts of Raney Ni. Progress of the
reaction was monitored by TLC, and when finished,
the catalyst was filtered off, solvents were evaporated and
the residue was redissolved in a mixture of AcOEt and
saturated aq. NaHCO3 (10 mL, 1:1), followed by addition of
(Boc)2O (0.43 mmol). After 2h stirring the layers were
separated, and water phase was extracted with CH2Cl2.
After drying of combined organic layers (MgSO4), solvents
were removed under reduced pressure. Purification was
achieved on silica gel using hexane/AcOEt (9:1–7:3).
(dd, J2,3A¼10.8 Hz, J2,3B¼7.2 Hz, 1H, H-2), 4.15 (ddAB
,
J3A,3B¼14.5 Hz, J2,3B¼7.2 Hz, 1H, HB-3), 2.12–2.05 (m,
1H, H-20), 2.02–1.80 (m, 2H, HA-60, HA-30), 1.74–1.59 (m,
2H, HA-40, HA-50), 1.35–1.22 (m, 1H, HB-30), 1.32 (s, 3H,
H-90), 1.24 (s, 3H, H-100), 1.15–1.07 (m, 2H, HB-40, HB-60),
0
0
0
0.89 (s, 9H, (CH3)3), 0.86 (d, J5 ,7 ¼6.5 Hz, 3H, H-7 ), 0.08
(s, 6H, 2xCH3); 13C NMR (50 MHz; CDCl3): d 156.8 (C-1),
150.5 (i-Ar), 128.4 (Ar), 127.9 (Ar), 125.7 (Ar), 77.5 (C-100),
72.9 (C-2)0, 62.9 (C-3), 50.2 (C-20), 40.9 (C-60), 39.7 (C-8 ),
34.2 (C-4 ), 31.3 (C-50), 27.4 (0C-90), 26.5 (C-30), 25.6
(3xCH3), 21.9 (C-70), 21.6 (C-10 ), 17.9 (C(CH3)3), 23.6
(2xCH3).
4.3.11. O-[syn-(3j)-t-Butoxycarbonylamino-(2j)-
hydroxyoctanoyl]-(10R,20S,50R)-80-phenylmenthol (15a).
The title compound was obtained in 90% yield: colourless
oil, HRMS-ESI: Calcd for C29H48O5N (MþH)þ: 490.3527,
found 490.3542; IR (film): 3449, 2957, 2928, 2870, 1718,
1498, 1456, 1366, 1243, 1172, 764, 700 cm21; Rf¼0.55
4.3.8. O-[3-Amino-(2S)-t-butyldimethylsilyloxy-propa-
noyl]-(10R,20S,50R)-80-phenylmenthol (13). Through
a
solution of 2-nitroalcohol 4c (227 mg, 0.49 mmol) in
MeOH (5 mL) in the presence of catalytic amounts of
Raney Ni, hydrogen was bubled. Progress of the reaction
was monitored by TLC. After stirring at rt for 24 h, catalyst
was separated, solvents evaporated and purification was
achieved on silica-gel column using hexane/AcOEt to give
compound 13 (206 mg, 91%). Colourless oil, (Rf¼0.1
hexane/AcOEt 8:2). Colourless oil, HRMS-ESI: Calcd for
C25H44O5SiN (MþH)þ 434.3085, found 434.3093. Anal.
Calcd C. 69.07, H. 10.20, N. 3.22, found C. 69.06, H. 10.09,
N. 3.24; IR (film): 3392, 2954, 2928, 2857, 1745, 1600,
1496, 1471, 1389, 1363, 1252, 1172, 1134, 1082, 985, 915,
20
1
(hexane/AcOEt 7:3); [a]D ¼213.0 (c¼0.48; CHCl3); H
NMR (200 MHz; CDCl3): d 7.33–7.20 (m, 5H, Ar), 4.85
(dt, J1 ,6 A¼J1 ,2 ¼10.6 Hz, J1 ,6 B¼4.2 Hz, 1H, H-10), 4.78
(d, J2,3¼10.4 Hz, 1H, H-2), 3.62–3.44 (m, 1H, H-3), 3.02
(d, J3,NH¼2.8 Hz, 1H, NH), 2.30–2.23 (m, 1H, H-20), 2.15–
2.06 (m, 1H, HA-30), 2.03–1.85 (m, 3H, H-4, HA-60), 1.78–
1.71 (m, 3H, H-5, HA-40), 1.56–1.25 (m, 6H, H-6, H-7, H-30,
HA-50), 1.38 (s, 9H, 3xCH3), 1.30 (s, 3H, H-90), 1.18 (s, 3H,
H-100), 1.01–0.92 (m, 5H, HB-40, HB-60, H-8), 0.91 (d,
0
0
0
0
0
0
837, 779, 700 cm21; [a]D ¼228.0 (c¼1.31; CHCl3); H
J5 ,7 ¼7.3 Hz); 13C NMR (50 MHz; CDCl3): d 155.4 (CvO
Boc), 152.4 (i-Ar), 128.3 (Ar), 125.7 (Ar), 96.6 (C(CH3)3),
79.7 (C-100), 72.0 (C-2), 52.6 (C-3), 50.3 (C-200), 41.2 (C-60),
39.8 (C-80), 34.9 (C-40), 33.4 (C-4), 32.1 0(C-5 ), 31.9 (C-5),
30.7 (C-9 ), 28.9 (3xCH3 Boc), 26.7 (C-3 ), 26.3 (C-6), 23.2
(C-70), 22.8 (C-100), 22.3 (C-7), 14.6 (C-8).
20
1
0
0
NMR (400 MHz; CDCl3): d 7.25–7.20 (m, 4H, Ar), 7.16–
7.11 (m, 4H, Ar), 4.76 (dt, J1,6A¼J1,2¼10.7 Hz, J1,6B
¼
4.3 Hz, 1H, H-10), 3.44 (dd, J2,3B¼5.1 Hz, J2,3A¼3.9 Hz,
1H, H-2), 2.58 (ddAB, J3A,3B¼13.4 Hz, J2,3A¼3.9 Hz, 1H,
HA-3), 2.53 (ddAB, J3A,3B¼13.4 Hz, J2,3B¼5.1 Hz, 1H, HB-
3), 2.11–2.04 (m, 1H, H-20), 2.00–1.91 (m, 1H, HA-30),
1.75–1.60 (m, 3H, HB-30, HA-40, HA-60,), 1.56–1.41 (m, 1H,
HA-50), 1.29 (s, 3H, H-90), 1.19 (s, 3H, H-100), 1.16–1.07
(m, 2H, HB-40, HB-600), 0.92 (s, 9H, (CH3)3), 0.86 (d,
4.3.12. O-[anti-(3j)-t-Butoxycarbonylamino-(2j)-
hydroxyoctanoyl]-(10R,20S,50R)-80-phenylmenthol (15b).
The title compound was obtained as a colourless oil, in
20
0
0
J5 ,7 ¼6.5 Hz, 3H, H-7 ), 0.12 (s, 3H, CH3), 0.05 (s, 3H,
CH3); 13C NMR (50 MHz; CDCl3): d 171.5 (C-1), 151.9
(i-Ar), 127.8 (A0r), 125.1 (Ar), 124.8 (Ar), 75.3 (C-100), 73.6
(C-20), 50.0 (C-2 ), 46.6 (C-3),041.4 (C-60), 39.4 (C-10 ), 34.4
(C-4 ), 31.1 (C-50), 28.9 (C-9 ), 26.4 (C-30), 25.6 (3xCH3),
24.5 (C-70), 21.6 (C-100), 18.2 (C(CH3)3), 24.6 (CH3), 25.3
(CH3).
92% yield: (Rf¼0.50 hexane/AcOEt 7:3); [a]D ¼210.0
(c¼0.1; CHCl3); 1H NMR (200 MHz; CDCl3): d 7.35–7.22
0
0
0
0
0
0
(m, 5H, Ar), 4.92 (dt, J1 ,6 A¼J1 ,2 ¼10.7, J1 ,6 B¼4.3, 1H,
H-10), 4.60 (d, J2,3¼9.5 Hz, 1H, H-2), 3.75–3.50 (m, 1H,
H-3), 3.21 (d, J3,NH¼2.8 Hz, 1H, NH), 2.30–2.25 (m, 1H,
H-20), 2.18–2.08 (m, 1H, HA-30), 2.03–1.84 (m, 3H, H-4,
HA-60), 1.79–1.73 (m, 3H, H-5, HA-40), 1.54–1.23 (m, 6H,
H-6, H-7, H-30, HA-50), 1.45 (s, 9H, 3xCH3), 1.30 (s, 3H,
4.3.9. 3-Amino-(2S)-hydroxypropionic acid ((2)-iso-
serin) (14). The solution of ester 13 (150 mg, 0.35 mmol)
in 6N HCl aq. (5 mL) was heated at 80 8C. Progress of the
reaction was monitored by TLC, and when finished (24 h)
acid was removed under reduced pressure. To the residue,
dry EtOH (2 mL) and epoxypropane (49 mL, 0.7 mmol)
were added. The compound 14 spontaneously precipitated
from the reaction mixture (49 mg, 89%). Colourless
crystals, mp¼187–189 8C (MeOH/H2O); LRMS-ESI:
H-90), 1.25 (s, 3H, H-100), 1.11–0.98 (m, 5H, HB-40, HB-60,
0
H-8), 0.90 (d, J5 ,7 ¼7.2 Hz, 3H, H-7 ), 13C NMR (50 MHz;
CDCl3): d 172.7 (C-1), 155.9 (CvO Boc), 151.7 (i-Ar),
128.8 (Ar), 125.7 (Ar), 79.7 (C(CH3)3), 76.2 (C-10), 73.3
(C-2), 53.3 (C-3), 50.8 (C-200), 42.1 (C-60), 41.1 (C-800), 34.9
(C-40), 32.0 (C-4), 31.8 (C-5 ), 29.9 (C-5), 29.6 (C-9 ), 28.9
(3xCH3 Boc), 26.8 (C-30), 25.8 (C-6), 24.2 (C-70), 23.0
(C-100), 22.3 (C-7), 14.5 (C-8).
0
0
found for (MþNa)þ 128.0; [a]D ¼232.0 (c¼0.52;
4.3.13. O-[syn-(3j)-t-Butoxycarbonylamino-4,4-
diethoxy-(2j)-hydroxybutanoyl]-(10R,20S,50R)-80-phenyl-
menthol (16a). The compound 16a was obtained as a
20
1
H2O); H NMR (400 MHz; H2O): d 4.27–4.21 (m, 1H,
H-2), 3.36 (ddAB, J3A,3B¼12.6 Hz, J2,3A¼2.8 Hz, 1H, HA-

I. Kudyba et al. / Tetrahedron 60 (2004) 4807–4820
4819
colourless oil in 92% yield, (Rf¼0.50 hexane/AcOEt 7:3).
4.4. General procedure of isopropylidene formation
solution of N-Boc-aminoalcohols (0.19 mmol),
dimethoxy-propane (0.21 mmol) and catalytic amounts of
TsOH in toluene (2 mL) was heated at 50 8C. Progress of the
reaction was monitored by TLC. After 5 h the mixture was
cooled, solvents were evaporated and the residue was
purified on silica gel using hexane/AcOEt (9:1–7:3).
HRMS-LSIMS(þ): Calcd for C29H47O7NNa (MþNa)þ:
544.3250, found 544.3234; IR (film): 3450, 3386, 2973,
2927, 1723, 1501, 1367, 1247, 1171, 1124, 1063, 764,
A
701 cm21; [a]D ¼24.4 (c¼1.61; CHCl3); 1H NMR
20
(200 MHz; CDCl3): d 7.40–7.10 (m, 5H, Ar), 5.05–4.75
(m, 1H, H-10), 4.41 (d, J3,4¼6.5 Hz, 1H, H-4), 3.80–3.50
(m, 4H, H-5, H-500, H-3), 3.11–3.05 (m, 1H, H-2), 2.14–
2.02 (m, 1H, H-20), 1.98–1.84 (m, 2H, HA-30, HA-60), 1.75–
1.70 (m, 1H, HA-40), 1.52–1.41 (m, 1H, HA-50), 1.40 (s, 9H,
3xCH3), 1.31 (s, 3H, H-90), 1.28 (t, J5,6¼7.1 Hz, 3H, H-6),
4.4.1. O-[anti-(3j)-t-Butoxycarbonylamino-(2j)-
hydroxy-2,3-isopropylideneoctanoyl]-(10R,20S,50R)-80-
phenyl-menthol (18a). The compound was obtained as a
colourless oil in 86%. HRMS-ESI: Calcd for C32H51O5NNa
(MþNa)þ: 552.3659, found: 552.3666; IR (film): 2955,
1.22–1.15 (m, 1H, HB-30), 1.10–0.91 (m, 2H, HB-40, 0HB-60),
00
00 00
1.17 (t, J5 ,6 ¼7.1 Hz, 3H, H-6 ), 1.16 (s, 3H, H-10 ), 0.90
0
(d, J5 ,7 ¼6.5 Hz, 3H, H-7 ); 13C NMR (50 MHz; CDCl3): d
172.7 (C-1), 155.4 (CvO Boc), 151.9 (i-Ar), 128.5 (Ar),
126.0 (Ar), 125.7 (Ar), 101.9 (C-4), 79.7 (C(CH3)3), 76.7
(C-100), 70.0 (C-2), 64.2 (C-5), 61.6 (C-5000), 53.5 (C-3), 50.6
(C-20), 41.4 (C-60), 40.1 (C-80), 34.9 (C-4 ), 310.9 (C-50), 29.4
(C-9 ), 28.9 (3xCH3), 27.0 (C-80), 24.4 (C-3 ), 22.3 (C-70,
C-100), 15.8 (C-6), 15.6 (C-600).
0
0
2923, 2860, 1747, 1699, 1456, 1381, 1213, 1104, 1061, 769,
701 cm21
;
Rf¼0.5 (hexane/AcOEt 8:2); [a]D ¼8.6
20
1
(c¼1.70; CHCl3); H NMR (500 MHz; CDCl3): d 7.30–
0
0
7.24 (m, 4H, Ar), 7.15–7.09 (m, 1H, Ar), 4.90 (dt, J1 ,6 A
¼
J1 ,2 ¼10.7 Hz, J1 ,6 B¼4.4 Hz, 1H, H-10), 3.77–3.74 (m, 1H,
H-3), 3.29 (d, J2,3¼2.7 Hz, 1H, H-2), 2.05–1.98 (m, 1H,
H-20), 2.13–2.04 (m, 1H, HA-30), 2.01–1.80 (m, 3H, H-4,
HA-60), 1.78–1.72 (m, 3H, H-5, HA-40), 1.55–1.25 (m, 6H,
H-6, H-7, H-30, HA-50), 1.47 (s, 6H, 2xCH3), 1.42 (s, 9H,
3xCH3), 1.29 (s, 3H, H-90), 1.18 (s, 3H, H-100), 1.02–0.91
0
0
0
0
4.3.14. O-[anti-(3j)-t-Butoxycarbonylamino-4,4-
diethoxy-(2j)-hydroxybutanoyl]-(10R,20S,50R)-80-phenyl-
menthol (16b). The title compound was obtained as a
colourless oil in 88% yield, (Rf¼0.6 hexane/AcOEt 6:4). 1H
NMR (200 MHz; CDCl3): d 7.50–7.00 (m, 5H, Ar),
5.00–4.80 (m, 1H, H-10), 4.41 (d, J3,4¼5.5 Hz, 1H, H-4),
3.90–3.75 (m, 1H, 1, H-3), 3.70–3.36 (m, 4H, 2H-5, H-500),
3.20–3.02 (m, 1H, H-2), 2.13–2.01 (m, 1H, H-20), 1.96–
1.80 (m, 2H, HA-30, HA-60), 1.77–1.71 (m, 1H, HA-40),
1.54–1.42 (m, 1H, HA-50), 1.45 (s, 9H, 3xCH3), 1.30 (s, 3H,
H-90), 1.29 (t, J5,6¼7.1 Hz, 3H, H-6), 1.23–1.15 (m, 1H,
HB-30), 1.11–0.90 (m, 2H, HB-40, HB-60), 1.19 (t,
(m, 2H, HB-40, HB-60), 0.91 (t, J7,8¼7.5 Hz, 3H, H-8), 0.87
0
(d, J5 ,7 ¼7.3 Hz, 3H, H-7 ); 13C NMR (125 MHz; CDCl3): d
170.7 (C-1), 151.7 (CvO Boc), 128.0 (Ar), 125.3 (Ar),
124.9 (Ar), 95.6 (C(CH3)2), 80.0 (C(CH3)2), 74.6 (C-10),
60.6 (C-2), 50.5 (C-20), 41.6 (C-60), 39.4 (C-80), 34.4 (C-40),
31.4 (C-5), 31.2 (C-50), 28.8 (C-90), 28.3 (5xCH3), 26.3
(C-30), 24.8 (C-6), 23.5 (C-70), 22.6 (C-7), 21.6 (C-100), 14.0
(C-8).
0
0
00
0
00 00
J5 ,6 ¼7.1 Hz, 3H, H-6 ), 1.17 (s, 3H, H-10 ), 0.89 (d,
4.4.2. O-[syn-(3j)-t-Butoxycarbonylamino-(2j)-hydroxy-
2,3-isopropylideneoctanoyl]-(10R,20S,50R)-80-phenyl-
menthol (18b). The title compound was obtained in 84%
0
J5 ,7 ¼6.5 Hz, 3H, H-7 ); 13C NMR (50 MHz; CDCl3): d
172.1 (C-1), 155.5 (CvO Boc), 151.9 (i-Ar), 128.5 (Ar),
125.7 (Ar), 125.5 (Ar), 101.5 (C-4), 79.9 (C(CH3)3), 76.0
(C-100), 71.8 (C-2), 64.6 (C-5), 62.0 (C-5000), 53.8 (C-3), 50.7
(C-20), 41.8 (C-60), 40.9 (C-90), 35.0 (C-4 ), 310.8 (C-50), 29.7
(C-9 ), 28.9 (3xCH3), 26.9 (C-80), 24.0 (C-3 ), 22.4 (C-70,
C-100), 15.8 (C-6), 15.6 (C-600).
0
0
20
yield. Rf¼0.45 (hexane/AcOEt; colourless oil, [a]D
¼
1
210.8 (c¼0.77; CHCl3); H NMR (500 MHz; CDCl3): d
7.31–7.24 (m, 4H, Ar), 7.15–7.08 (m, 1H, Ar), 4.97–4.94
(m, 1H, H-10), 3.54–3.50 (m,01H, H-3), 3.23–3.20 (m, 1H,
H-2), 2.05–1.99 (m, 1H, H-2 ), 2.12–2.04 (m, 1H, HA-30),
2.04–1.83 (m, 3H, H-4, HA-60), 1.79–1.71 (m, 3H, H-5, HA-
40), 1.58–1.26 (m, 6H, H-6, H-7, H-30, HA-50), 1.48 (s, 6H,
2xCH3), 1.43 (s, 9H, 3xCH3), 1.31 (s, 3H, H-90), 1.19 (s, 3H,
4.3.15. O-[anti-(3j)-t-Butoxycarbonylamino-(2j)-
hydroxy-3-phenylpropanoyl]-(10R,20S,50R)-80-phenyl-
menthol (17b). The title compound was obtained as a
colourless oil in 88% yield (Rf¼0.5 hexane/AcOEt 8:2).
HRMS-ESI: Calcd for C30H41O5NNa (MþNa)þ 518.2882,
found 518.2899; IR (KBr): 3445 2967, 1722, 1496, 1456,
H-100), 1.02–0.90 (m, 5H, HB-40, HB-60, H-8), 0.89 (d,
0
J5 ,7 ¼7.6 Hz, 3H, H-7 ); 13C NMR (125 MHz; CDCl3): d
167.0 (C-1), 152.0 (CvO Boc), 151.6 (i-Ar), 127.9 (Ar),
125.2 (Ar), 124.8 (Ar), 93.8 (C(CH3)2), 79.6 (C(CH3)2),
74.9 (C-10), 50.1 (C-20)0, 41.4 (C-60), 40.2 (C-80), 34.4 (C-40),
31.9 (C-5), 31.0 (C-5 ), 30.3 (C-90), 28.4 (5xCH3), 26.4
(C-30), 24.9 (C-6), 23.5 (C-70), 22.4 (C-7), 21.7 (C-100), 13.9
(C-8).
0
0
1
1367, 1256, 1169, 700; H NMR (400 MHz; CDCl3): d
7.35–7.20 (m, 7H, Ar), 7.15–7.04 (m, 3H, Ar), 5.50 (d,
J2,3¼9.1 Hz, 1H, H-2), 5.00 (d, J2,3¼9.1 Hz, 1H, H-3), 4.93
(dt, J1 ,6 A¼J1 ,2 ¼10.8 Hz, J1 ,6 B¼4.4 Hz, 1H, H-10), 3.91
(bs, 1H, NH), 2.19–2.10 (m, 1H, H-20), 1.94–1.85 (m, 1H,
HA-30), 1.80–1.73 (m, 1H, HA-60), 1.71–1.66 (m, 1H, HA-
40), 1.52 (s, 9H, 3xCH3), 1.50–1.40 (m, 1H, HA-50), 1.31 (s,
3H, H-90), 1.28–1.21 (m, 1H, HB-30), 1.19 (s, 3H, H-100),
0
0
0
0
0
0
4.4.3. O-[anti-(3j)-Amino-4,4-diethoxy-(2j)-hydroxy-
2,3-isopropylidenebutanoyl]-(10R,20S,50R)-80-phenyl-
menthol (19a). The title compound was obtained as a
colourless oil in 85% yield, (Rf¼0.5 hexane/AcOEt 8:2).
HRMS-LSIMS(þ): Calcd for C24H43O5NNa (MþNa)þ:
484.6302, found 484.6308; IR (film): 3455, 2957, 2926,
1705, 1496, 1456, 1391, 1366, 1257, 1173, 1150, 1119, 765,
1.01–0.89 (m, 2H, HB-40, HB-60), 0.86 (d, J5 ,7 ¼6.6 Hz, 3H,
H-70); 13C NMR (50 MHz; CDCl3): d 170.5 (C-1), 154.7
(CvO Boc), 152.2 (i-Ar), 139.4 (i-Ar), 128.2 (Ar), 127.9
(Ar), 127.3 (Ar), 126.6 (Ar), 125.3 (Ar), 79.3 (C(CH3)3
Boc), 76.1 (C-10), 74.3 (C-2), 55.7 (C-3), 49.9 (C-200), 41.1
(C-60), 39.4 (C-80), 34.2 (C-40), 31.2 (C-50), 28.3 (C-9 ), 27.3
(3xCH3 Boc), 26.1 (C-30), 22.5 (C-70), 21.6 (C-100).
0
0
701 cm21; [a]D ¼24.4 (c¼1.61; CHCl3); 1H NMR
20
(500 MHz; C6D6): d 7.20–6.90 (m, 5H, Ar), 5.00 (dt,
0
J1 ,6 A¼J1 ,2 ¼10.8 Hz, J1 ,6 B¼4.4 Hz, 1H, H-10), 4.74 (d,
0
0
0
0
0

4820
I. Kudyba et al. / Tetrahedron 60 (2004) 4807–4820
J3,4¼1.5 Hz, 1H, H-4), 3.85 (dd, J3,4¼1.5 Hz, J3,2¼8.6 Hz,
62.9 (C-3), 50.6 (C-20), 41.9 (C-60), 40.2 (C-80), 34.9 (C-40),
31.9 (C-50), 28.3 (C-90), 27.1 (C-30), 25.3 (C-70), 22.3
(C-100).
1H, H-3), 3.75 (ddd, J5A,5B¼9.6 Hz, J5A,6¼7.1 Hz, J5B,6
¼
00
00 00
00 00
7.0 Hz, 2H, H-5), 3.42 (dd, J5 A,5 B¼9.6 Hz, J5A ,6
¼
00 00
7.1 Hz, J5B ,6 ¼7.0 Hz, 2H, H-5 ), 3.37 (d, J3,2¼8.6 Hz,
1H, H-2), 2.00–1.90 (m, 3H, H-20, HA-30, HA-60), 1.75–1.68
(m, 1H, HA-40), 1.55–1.45 (m, 1H, HA-50), 1.24 (s, 6H,
3xCH3), 1.23–1.17 (m, 1H, HB-30), 1.15–0.92 (m, 2H, HB-
40, HB-60), 1.12 (s, 3H, H-90), 1.00–0.92 (m, 6H, H-6,0H-600),
Acknowledgements
1.12 (s, 3H, H-100), 0.69 (d, J5 ,7 ¼6.5 Hz, 3H, H-7 ); 13C
NMR (50 MHz; CDCl3): d 168.0 (C-1), 152.9 (i-Ar), 128.7
(Ar), 125.8 (Ar), 125.6 (Ar), 99.9 (C-4), 97.8 (C(CH3)2),
75.7 (C-10), 74.9 (C-2), 66.2 (C-50), 62.9 (C-5000), 51.2 (C-3),
42.3 (C-20), 39.8 (C-60), 39.1 (C-8 ), 35.0 (C-4 ), 31.7 (C-50),
31.2 (C-90), 29.2 (2xCH3), 27.0 (C-80), 26.5 (C-30), 23.9
(C-70), 22.3 (C-100), 15.8 (C-6), 15.6 (C-600).
0
0
This work was supported by the State Committee for
Scientific Research (Project PBZ 605/T09/1999).
References and notes
1. Henry, L. Compt. Rend. 1895, 120, 1265.
4.4.4. O-[3-O-[syn-(3j)-Amino-4,4-diethoxy-(2j)-hydro-
xy-2,3-isopropylidenebutanoyl]-(10R,20S,50R)-80-phenyl-
menthol (19b). The title compound was obtained as a
colourless oil in 84% yield (Rf¼0.50 hexane/AcOEt 8:2):
1H NMR (500 MHz; C6D6): d 7.20–6.90 (m, 5H, Ar), 5.22
2. (a) Rosini, G.; Ballini, R. Synthesis 1988, 833. (b) Rosini, G. In
Comprehensive Organic Synthesis; Trost, B. M., Ed.;
Pergamon: Oxford, 1991; pp 321–340. (c) Luzzio, F. A.
Tetrahedron 2001, 57, 915.
3. (a) Wade, P. A.; Giuliano, R. M. In Nitro Compounds: Recent
Advances in Synthesis and Chemistry; Feuer, H., Nielsen,
A. T., Eds.; VCH, 1990; pp 137–265. (b) Ono, N. The Nitro
Group in Organic Synthesis; Wiley: New York, 2001; pp 30–
69.
0
0
0
0
(d, J3,4¼1.8 Hz, 1H, H-4), 4.92 (dt, J1 ,6 A¼J1 ,2 ¼10.4 Hz,
J1 ,6 B¼4.4 Hz, 1H, H-10), 3.87 (dd, J3,4¼1.8 Hz,
J3,2¼7.8 Hz, 1H, H-3), 3.70–3.65 (m, 2H, H-5), 3.49–
3.41 (m, 2H, H-500), 3.44 (d, J3,2¼7.8 Hz, 1H, H-2), 2.01–
1.92 (m, 3H, H-20, HA-30, HA-60), 1.78–1.69 (m, 1H, HA-40),
1.56–1.47 (m, 1H, HA-50), 1.25 (s, 6H, 3xCH3), 1.23–1.16
(m, 1H, HB-30), 1.15–0.90 (m, 2H, HB-40, HB-60), 1.13 (s,
0
0
4. (a) Hanessian, S.; Devasthale, P. V. Tetrahedron Lett. 1996,
¨
¨
37, 987. (b) Jager, V.; Ohrlein, R.; Wehner, V.; Poggendorf,
P.; Steuer, B.; Raczko, J.; Griesser, H.; Kiess, F-M.; Menzel,
A. Enantiomer 1999, 4, 205, and references cited therein.
5. (a) Shibasaki, M.; Sasai, H.; Arai, T. Angew. Chem. Int. Ed.
1997, 36, 1237. (b) Shibasaki, M. Enantiomer 1999, 4, 513. (c)
Corey, E. J.; Zheng, F.-Y. Angew. Chem. Int. Ed. 1999, 38,
1931.
3H, H-90), 1.00–0.91 (m, 6H, H-6, H-600), 1.15 (s, 3H,
0
H-100), 0.70 (d, J5 ,7 ¼6.5 Hz, 3H, H-7 ).
0
0
4.4.5. O-[syn-(3j)-t-Butoxycarbonylamino-(2j)-hydroxy-
2,3-isopropylidene-3-phenyl-propanoyl]-(10R,20S,50R)-80-
phenylmenthol (20b). The title compound was obtained as
a colourless oil in 90% yield, (Rf¼0.6 hexane/AcOEt 8:2).
HRMS-ESI: Calcd for C33H45O5N (MþH)þ 558.3190,
found 558.3182; IR (KBr): 2959, 2927, 1730, 1703, 1456,
´
6. (a) Solladie-Cavallo, A.; Khiar, N. Tetrahedron Lett. 1988, 29,
´
2189. (b) Solladie-Cavallo, A.; Khiar, N. J. Org. Chem. 1990,
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7. Bauer, T.; Jezewski, A.; Chapuis, C.; Jurczak, J. Tetrahedron:
Asymmetry 1996, 7, 1385.
1378, 1366, 1255, 1177, 1099, 764, 700 cm21
;
20
[a]D ¼21.75 (c¼1.17; CHCl3); 1H NMR (500 MHz;
8. Achmatowicz, M.; Jurczak, J. Polish J. Chem. 1999, 73, 1079,
and references cited therein.
CDCl3): d 7.20–6.80 (m, 10H, Ar), 5.48 (bs, 1H, H-2), 5.01
(dt, J1 ,6 A¼J1 ,2 ¼10.6 Hz, J1 ,6 B¼4.4 Hz, 1H, H-10), 3.89
(bs, 1H, H-3), 2.17–2.10 (m, 1H, H-20), 1.95–1.88 (m, 1H,
HA-30), 1.81–1.75 (m, 1H, HA-60), 1.72–1.69 (m, 1H, HA-
40), 1.48–1.40 (m, 1H, HA-50), 1.21 (s, 3H, H-90), 1.17 (bs,
9H, H-100, 2xCH3), 1.22–1.19 (m, 1H, HB-30), 1.06 (s, 9H,
9. Handbook of Reagents for Organic Synthesis; Reagents,
Auxiliaries and Catalysts for C–C Bonds; Coates, R. M.,
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2894.
0
0
0
0
0
0
3xCH3), 1.01–0.90 (m, 2H, HB-40, HB-60), 0.67 (d,
11. Kudyba, I.; Raczko, J.; Jurczak, J. Tetrahedron Lett. 2003, 44,
8685.
0
J5 ,7 ¼6.3 Hz, 3H, H-7 ); 13C NMR (125 MHz; CDCl3): d
169.9 (C-1), 152.1 (CvO Boc), 151.4 (i-Ar), 128.7 (Ar),
128.4 (Ar), 127.9 (Ar), 125.8 (Ar), 125.5 (Ar), 960.6
(C(CH3)2), 81.3 (C-2), 80.6 (C(CH3)3 Boc), 76.2 (C-1 ),
0
0
12. Sheldrick, G. H. Acta Crystallogr., Sect. A 1990, 46, 467.
13. Sheldrick, G. M. SHELXL97, Program for the Refinemenof
¨
Crystal Structures, University of Gottingen: Germany, 1997.