Derivatives of L-pimaric acid in the synthesis of chiral organophosphorus ligands from decahydrophenanthrene series

Article abstract of DOI:10.1023/A:1013144431609

Starting with maleopimaric and fumaropimaric acids were prepared chiral organophosphorus ligands from decahydrophenanthrene series. Cationic complexes of Rh(I) prepared therefrom were tested for catalysts of asymmetric hydrogenation of unsaturated precursors of N-acethylphenylalanine and its derivatives.

Full text of DOI:10.1023/A:1013144431609

Russian Journal of Organic Chemistry, Vol. 37, No. 8, 2001, pp. 1134 1148. Translated from Zhurnal Organicheskoi Khimii, Vol. 37, No. 8, 2001,
pp. 1193 1207.
Original Russian Text Copyright
,
2001 by Tolstikov, Karpyshev, Tolstikova, Khlebnikova, Sal nikov, Mamatyuk, Gatilov, Bagryanskaya.
Derivatives of L-Pimaric Acid in the Synthesis of Chiral
Organophosphorus Ligands
from Decahydrophenanthrene Series*
A. G. Tolstikov1, N. N. Karpyshev1, O. V. Tolstikova1,
T. B. Khlebnikova, G. E. Sal,nikov1, V. I. Mamatyuk1,
Yu. V. Gatilov2, and I. Yu. Bagryanskaya2
1Boreskov Institute of Catalysis, Siberian Division, Russian Academy of Sciences, Novosibirsk, 630090 Russia
2Novosibirsk Institute of Organic Chemistry, Siberian Division,
Russian Academy of Sciences, Novosibirsk, 630090 Russia
Received November 10, 2000
Abstract Starting with maleopimaric and fumaropimaric acids were prepared chiral organophosphorus
ligands from decahydrophenanthrene series. Cationic complexes of Rh(I) prepared therefrom were tested
for catalysts of asymmetric hydrogenation of unsaturated precursors of N-acethylphenylalanine and its
derivatives.
An important part of the fundamental research in
asymmetric catalysis is the study of hydrogenation of
unsaturated compounds in the presence of transition
metal complexes with chiral organophosphorus
ligands [1 3]. To this end were prepared numerous
phosphines, aminophosphines, and phosphinites
proceeding from tartaric acids esters, biogenic amino-
acids, carbohydrates, terpenes etc. [4 11]. At the
same time no data were published on application of
higher terpenes in the synthesis of the organo-
elemental ligands. Pursuing the studies on the stereo-
selective metal-complex catalysis we turned our atten-
tion to tricyclic diterpene acids contained in the
galipot of coniferous trees [12 14]. In particular, we
took an interest in the L-pimaric acid and its adducts
with maleic anhydride and fumaric acid [15 20]. The
high optical purity and specific structural features of
these compounds are attractive for an attempt to
transform them into organoelemental ligands of novel
structural types.
triol II [15]. The necessary differentiation of its three
hydroxy groups was performed in three stages. First
we obtained benzylideneoxy derivative III that had
1
in the H NMR spectrum a characteristic singlet at
5.21 ppm from the methine proton of the benzylidene
group. For protection of the hydroxymethyl group
attached to C8 atom compound III was treated with
benzyl chloride in the presence of tetrabutyl-
ammonium hydrogen sulfate and 50% aqueous NaOH
in dichloromethane. This reaction gave benzyl ether
IV in 86% yield. The attempt to relieve the
benzylidene protection in compound IV with the use
of 5% HCl solution in methanol resulted in a mixture
of compounds that was subjected to chromatography
to afford the target diol V (40%) and pentacyclic
diterpene with a furan ring VI (50%). A fair yield
of diol V (80%) was obtained only when the hydro-
lysis of ether IV was carried out by a reagent (PyH+ )
(TsO ) in methanol. In the former reaction the furan
ring in compound VI arises in the strongly acidic
medium through an intramolecular cyclization in diol
V due to protonation of the ethylidene fragment in
keeping with the Markownikoff rule followed by
reaction between the intermediate carbocation with
the nearest hydroxymethyl group.The structure of
compounds V and VI was established from their
NMR spectra**.
Here we report on the synthesis of chiral bis-
phosphines of decahydrophenanthrene series with the
use of enantiospecific transformations of maleo-
pimaric and fumaropimaric acids. Starting with
maleopimaric acid (I) whose structure was proved by
X-ray diffraction analysis [17] we prepared a known
*
The study was carried out under financial support from the
**
The carbon atoms in all compounds synthesized are numbered
Russian
Foundation
for
Basic
Research
(grant
1
so as is convenient for assignment of the signals in the H
no. 98-03-32900), and Noncommercial Partnership ASGL:
Development of new biologically active compounds for
medical applications (grant no.1-5-3/SNT-99).
and 13C NMR spectra. The numbering not always is
consistent with the IUPAC rules.
1070-4280/01/3708-1134$25.00 2001 MAIK Nauka/Interperiodica

DERIVATIVES OF L-PIMARIC ACID IN THE SYNTHESIS
1135
For instance, in the 13C NMR spectrum of diol V
the significant signals from atoms C16 and C17 appear
at 65.51 and 61.07 ppm respectively. The com-
number of times we disclosed that the previous data
concerned a mixture of bisphosphine IX and its
oxidized form (up to 15%) [31P NMR spectrum,
,
ppm, J, Hz: 28.17, 30.05, P(O)R3]. The partiPal
oxidation of the labile ligand with air oxygen readily
occurs during the preparation of the samples for
measurements, e.g., at the use of insufficiently
degassed solvents, or at prolonged measurements.
1
parative analysis of the spectra H NMR and two-
dimensional COSY H H (45 ) of compound VI
revealed that a doublet of doublets at 3.48 ppm
belonged to the proton H16a that is coupled with the
proton H16b whose signal appeared as a doublet at
3.95 ppm. The proton H16a has also a cross-peak
with H2 proton possessing a signal as doublet of
triplets at 2.36 ppm (J16a,2 3.7, J2,1 = J2,3 9.5 Hz).
To the methylene protons at the C17 atom that have
distinct cross-peaks with each other belong a triplet
at 3.67 ppm (Jgem = J17a,1 10.3 Hz) and a doublet of
doublets at 3.84 ppm (J17b,1 3.8 Hz).
The synthesis of ligand XIII, a diastereomer of
bisphosphine IX characterized by a formal C2-sym-
metry of chiral centers C1 and C2, was performed
starting with adduct X prepared by heating to 180 C
diethyl fumarate with benzyl ether of L-pimaric
alcohol. The latter was used together with benzyl
ethers of related structures that were obtained by
treating with benzyl bromide of reduced with LiAlH4
rosin acids mixture which were isolated directly from
pine galipot [22]. The structure of compound X
isolated as individual substance by chromatography
was established mainly from the high resolution
After treating diol V with tosyl chloride in
pyridine at 20 C we isolated from the reaction mix-
ture key ditosylate VII (75%) and furan derivative
(VIII) as a side product (20%). Note that in reaction
carried out at room temperature the yield of com-
pound VIII amounted to 80%. The structure of com-
pounds VII and VIII was confirmed by 1H and
13C NMR spectra. The furan fragment of molecule
VIII is revealed in the proton spectrum by four
equivalent triplets ( 3.07 3.86 ppm) from diastereo-
topic protons 2H16 and 2H17 having geminal and
vicinal coupling constants equal to 8.5 Hz.
1
NMR spectra (500 mHz). In the H NMR spectrum
of adduct X the doublet at 2.75 ppm belongs to the
proton H1 coupled with the H2 atom with a coupling
constant equal to 5.9 Hz. This value is in agreement
with a vicinal coupling constant calculated along
Karplus formula for a dihedral angle 131 C; the
value is consistent with trans-arrangement of H1 and
H2 atoms. The signal in the shape of doublet of
doublets at 2.55 ppm corresponds to H2 atom
Chiral bisphosphine ligand IX was synthesized in
31% yield by treating ditosylate VII with sodium
diphenylphosphide prepared in situ in dioxane [11].
possessing a vicinal constant J2,3 2.7 Hz and a
w
long-range constant J2,4 1.9 Hz [23]. Note that for
1
In the H NMR spectrum of bisphosphine IX the
the similar ABX-protons of 1 ,2 -isomer of trimethyl
fumaropimarate are given the values J1,2 6.0, J2,3 3.0
Hz, and for trimethyl maleopimarate with 1 ,2 -
configuration of the substituents at C1 and C2 atoms
these values are J1,2 11.1, J2,3 1.7 Hz [17]. The
comparison of our spectral data with those published
revealed that the synthesized adduct X has 1 ,2 -
configuration of the ethoxycarbonyl groups at C1 and
C2 atoms.
signals of methylene protons attached to atoms C16
and C17 appear in the 1.90 2.35 ppm range. The
multiplets at
7.0 7.52 ppm correspond to 25
protons of the five aromatic rings. In the 13C NMR
spectrum the doublet at 41.50 ppm (J16,P(1) = J17,P(2)
9 Hz) corresponds to coinciding signals of C16 and
C17 atoms. A quartet at 48.09 ppm (J1,P(1) 12, J1,P(2)
8 Hz) belongs to C1 atom, and a quartet at 39.26 ppm
(J2,P(1) 6, J2,P(2) 14 Hz) originates from C2 atom. The
doublet at 37.71 ppm (J3,P(1) 12 Hz) belongs to C3,
and the doublet at 30.57 ppm (J10,P(2) 14 Hz) is a
signal of C10a atom. In the 31P NMR spectrum of
bisphosphine IX appear two signals in the regions
10.61 and 16.26 ppm. These values are character-
istic of P(III) atoms [21]. For compound IX we
obtained reliable and reproducible values of mp 132
134 C and [ ]2D0 55.4 (c 1.0, CHCl3). In this
connection we should inform that in the previous
publication [12] we have reported dissimilar values of
mp 102 104 C and [ ]2D0 20.3 (c 0.7, CHCl3).
When the experiments were repeated for quite a
Compound X was reduced by LiAlH4 into diol XI
with quantitative yield. Reaction of diol XI with TsCl
in pyridine afforded the corresponding tosylate XII in
71% yield. The treatment of the latter with sodium
diphenylphosphide in dioxane completed the synthesis
of chiral bisphosphine XIII. Its structure and com-
position were confirmed by spectral data and
elemental analysis. For instance, in the 31P NMR
spectrum of the compound are present two character-
istic signals at 17.59 and 21.79 ppm belonging to
two P(III) atoms in the two diphenylphosphanyl-
methyl fragments of the molecule.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 37 No. 8 2001

1136
TOLSTIKOV et al.
Scheme 1.
Optically active bisphosphine XIX was synthesized
compound XIV with PCl3 afforded acyl chloride XV
that without additional purification was converted into
amide XVI by morpholine action in quantitative
yield. The latter was reduced by LiAlH4 in ether to
from diethyl fumaropimarate XIV possessing 1 ,2 -
configuration of substituents at the C1 and C2 centers
1
(according to H NMR data} [17]. The reaction of
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 37 No. 8 2001

DERIVATIVES OF L-PIMARIC ACID IN THE SYNTHESIS
1137
Scheme 2.
furnish aminodiol XVII in 93% yield. In its
13C NMR spectrum appear the following signals: at
69.62 ppm from C20 atom of morpholinomethylene
fragment, and at 66.63 and 63.95 ppm from C16 and
C17 of hydroxymethylene groups. Tosylation of
aminodiol XVII resulted in crystalline ditosylate
XVIII whose structure was proved by X-ray diffrac-
tion analysis and NMR spectra. The target ligand
XIX was prepared in 32% yield by the method used
multiplicity with the chemical shifts close to the
proton shifts values in the H NMR spectra of free
1
ligands. We tested the new Rh(I) complexes as cata-
lysts of asymmetric hydrogenation of the unsaturated
precursors of N-acetylphenylalanine and its deriv-
atives. At hydrogenation of (Z)-N-acetylamino-
cinnamic acid (XXIII) in the presence of complex XX
in ethanol at molar ratio [substrate]/[catalyst] 100: 1
and hydrogen pressure 1.5 at we obtained in 100%
yield optically active N-acetylphenylalanine (XXV)
{optical purity 37%; [ ]2D0 17.0 (c 1, ethanol), cf.
[24]: 46.5 (c 1, ethanol)}. The hydrogenation under
similar conditions of 3-(3,4-dimethoxyphenyl)-2-
acetylamino-2-propenoic acid (XXIV) with complex
XX as catalyst gave with 91% conversion dimethoxy-
phenylpropanoic acid (XXVI) ([ ]2D0 15.5 ), that was
hydrolyzed into S-enantiomerically enriched 3-(3,4-
dihydroxyphenyl-1)-2-aminopropanoic acid (L-DOPA)
1
to obtain bisphosphines IX and XIII. In the H NMR
spectrum of compound XIX the protons linked to
atoms C16 and C17 undergo upfield shift to the region
2.08 2.41 ppm due to the influence of phosphorus(III)
atoms; the latter appear in the 31P NMR spectrum as
two characteristic signals at 18.91 and 21.96 ppm.
Reactions of bisphosphines IX, XIII, XIX with
di- -chlorobis(1,5-cyclooctadiene)dirhodium
and
NaBF4 in dichloromethane furnished complexes
XX XXII that were characterized by elemental
analyses and 31P NMR spectra. The proton spectra of
the complexes contain a set of signals with unclear
(XXVII) {optical purity 27% [ ]2D0 3.2 (c 5, 1 N
HCl), cf. [25]: [ ]2D0 11.7 (c 5.3, 1 N HCl)}. The
hydrogenation of aminoacids XXIII, XXIV catalyzed
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 37 No. 8 2001

1138
TOLSTIKOV et al.
Scheme 3.
Table 1. Principal parameters and hydrogenation results
of unsaturated precursors of N-acetylphenylalanine and its
derivatives [substrate]/[catalyst] 100: 1; pH 1.5 at,
hydrogenation temperature 25 C, process tim2e 3 5 min
with complexes XXI, XXII at molar ratio [substrate]/
[catalyst] 100: 1 and hydrogen pressure 1.5 at is very
fast (3 5 min) and afforded in 100% conversion
racemic acids XXV, XXVI (Table 1).
Thus we for the first time demonstrated the
promising aspects of application of the natural
diterpene acids as initial compounds for the synthesis
of chiral organoelemental ligands for metal complexes
suitable as catalysts in homogeneous asymmetric
hydrogenation.
Substrate Catalyst Conversion, Hydrogenation Optical
%
product
purity, %
XXIII
XXIII
XXIII
XXIV
XXIV
XXIV
XX
100
100
100
91
XXV
XXV
XXV
XXVI
XXVI
XXVI
37 (S)
XXI
XXII
XX
0
0
EXPERIMENTAL
27 (S)
XXI
XXII
100
100
0
0
NMR spectra of compounds I, II, X, XIV were
registered on spectrometer Bruker DRX 500 in
1
CDCl3 (operating frequencies 500.13 MHz for H,
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 37 No. 8 2001

DERIVATIVES OF L-PIMARIC ACID IN THE SYNTHESIS
1139
Scheme 4.
of diffractometer Syntex P21 (CuK -irradiation,
graphite monochromator). Crystals of compound I
rhombic, a 7.933(2), b 11.995(2), c 23.361(5)
,
3
V 2222.9(8)
,
space group P212121, Z 4,
1
3
C25H34O5,
0.682 mm , dcalc 1.239 g cm .
Intensities of 2430 independent reflections with
2 < 140 were measured, scanning to /2 . A cor-
rection for crystal faces was introduced (transmission
0.61 0.85). The structure was solved by the direct
method using SHELX-86 program. The final refine-
ment of parameters was carried out by least-squares
procedure in the full-matrix anisotropic approxima-
tion (the positions of hydrogen atoms were calculated
from geometrical considerations and were not
included into refinement) along SHELXL-93 program
till wR2 0.1085, S 1.039 for all F2 (R 0.0397 for
2141 F0 > 4 , 272 parameters). Parameter x of the
absolute structure is equal to 0.05(34). Atom co-
ordinates and equivalent thermal factors of nonhydro-
gen atoms are presented in Table 2. The structure of
the molecule and the absolute configuration of dione I
are shown in Fig. 1. The structure of the carbocyclic
skeleton is as usual, the bond lengths in the skeleton
are close to the average values [26]. The orientation
of the isopropyl group [torsion angle C15C16C17C19
16.0(4) ] is the same as in the molecule of 4,14b-di-
methyl-7,8-dioxo-6a,13-(15-isopropyl)etheno-4-carb-
oxy-1,2,3,4,4a,5,6,6a,6b,7,8,12b,13,14,14a,14b-
hexadecahydropicene [27]. Oxolan ring is planar
within 0.025(2) . The atoms O23 and O24 deviate
from this plane to different sides by 0.087(4) and
R = R = H (XXIII, XXV), OMe (XXIV, XXVI),
OH (XXVII).
125.77 MHz for 13C spectra). The spectra of the other
compounds were recorded on Bruker AC-200 instru-
1
ment in CDCl3 at 200.13 MHz for H, 50.32 MHz
0.021(5)
respectively. The bond lengths in the
for 13C, and 81.01 for 31P spectra. Chemical shifts
were measured from chloroform signals used as
oxolan-2,5-dione fragment are consistent within the
error of measurement with the average values [C O
internal reference ( 7.24 ppm,
77.10 ppm). The
H
C
1.387(9), C=O 1.189(6), OC C 1.502(10)
indicated in the Cambridge Structural Databank [28]
for 30 structures with (C C) 0.005
]
31P NMR spectra were recorded with heteronuclear
decoupling relative to external reference (H3PO4).
IR spectra were registered on spectrophotometer
Specord M-80 from samples as thin films. The optical
rotation was measured on polarimeter JASCO model
DIP-360. The column chromatography was perform-
ed on silica gel l100/160 . The reactions were
monitored by TLC on plates with fixed layer of silica
gel (F254, Merck). All operations with ligands IX,
XIV, XIX and complexes XX XXII were carried out
in a flow of dry argon. The solvents were dried and
degassed before use. The solvents were degassed in a
vacuum by repeated freeze thaw procedure. The
maleopimaric acid used in the study had the following
characteristics: [ ]20 28 (c 1.2, CHCl3), cf. [15]:
[ ]2D0 28.1 (c 3.4,DCHCl3).
.
5,9-Dimethyl-16-isopropyl-5,13 ,14 -trihydr-
oxymethyltetracyclo[10.2.2.01,10.04,9]hexadec-15-
ene (II) [15]. [ ]2D4 8.1 (c 1.5, C2H5OH). H NMR
1
spectrum, , ppm (J, Hz): 0.68 s (3H, C18H3), 0.79
s (3H, C19H3), 0.89 m (1H, H5), 1.08 d (3H, C14H3,
6.8), 1.09 d (3H, C15H3, 6.8), 1.20 m (1H, H4), 1.28
m (2H, H7, H8a), 1.4 m (6H, H4a, H5, H6, H7, H9,
H10), 1.58 m (2H, H6, H9), 1.69 d.d.d (1H, H4,
12.6, 9.8, 2.8), 1.82 d.t (1H, H1, J1,2 = J1,17B 10,
J1,17A 3), 2.08 m (1H, H10), 2.19 m (1H, H2),
2.27 d.sept. (1H, H13, J13,11 1.3), 2.52 m (1H, H3),
3.08 d (1H, H20, 11.3), 3.29 t (1H, H17, J17A,1
=
J17A,17B 10), 3.38 d (1H, H20), 3.39 m (1H, H16),
X-ray diffraction study of a single crystal of
methyl maleopimarate (I) was performed with the use
3.70 m (1H, H16), 3.71 d.d (1H, H17), 5.42 s (1H,
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 37 No. 8 2001

1140
TOLSTIKOV et al.
Table 2. Coordinates ( 104) and equivalent thermal
2
factors (
,
103) of nonhydrogen atoms of methyl
maleopimarate (I)
Atom
x/a
y/b
z/c
Ueq
C1
5459(3)
5243(4)
6901(4)
8359(3)
8476(3)
9869(3)
10276(3)
8728(3)
7176(3)
6798(3)
5643(3)
6150(3)
7545(3)
9063(3)
8224(3)
6915(3)
6138(4)
4440(4)
7248(5)
6114(4)
8187(4)
9936(4)
8200(4)
10506(4)
11535(4)
10864(3)
9926(3)
7476(3)
11953(3)
10177(3)
3922(2)
2811(3)
2173(2)
2826(2)
4012(2)
4732(2)
5694(2)
6397(2)
5654(2)
4674(2)
6411(2)
7649(2)
7835(2)
7098(2)
7227(2)
7870(2)
8747(2)
8331(3)
9094(3)
5102(2)
2821(3)
2193(2)
9005(2)
7906(3)
562(3)
3416(1)
3724(1)
3734(1)
4018(1)
3745(1)
3994(1)
3591(1)
3437(1)
3274(1)
3698(1)
3151(1)
3194(1)
2747(1)
2884(1)
3892(1)
3777(1)
4161(1)
4382(2)
4654(1)
4276(1)
4675(1)
3842(1)
2772(1)
2937(1)
4000(2)
3455(1)
2864(1)
2728(1)
3025(1)
4166(1)
51(1)
60(1)
57(1)
44(1)
38(1)
42(1)
42(1)
36(1)
37(1)
41(1)
47(1)
44(1)
45(1)
43(1)
39(1)
41(1)
55(1)
81(1)
78(1)
52(1)
58(1)
47(1)
53(1)
56(1)
73(1)
67(1)
62(1)
79(1)
90(1)
67(1)
C2
C3
C4
C5
C6
C7
C8
C9
C10
C11
C12
C13
C14
C15
C16
C17
C18
C19
C20
C21
C22
C23
C24
C25
O22
O23
O23
O24
O25
2417(2)
8992(2)
9866(2)
7761(2)
1281(2)
Fig. 1. Crystalline structure of compound I according to
X-ray diffraction analysis.
H11). 13C NMR spectrum, C, ppm: 16.7 (C18), 18.3
(C19), 18.4 (C6), 20.5 (C9), 20.9 (C15), 21.7 (C14),
31.3 (C4), 34.4 (C13), 36.4 (C7), 37.4 (C10), 38.2
(C8), 38.5 (C3), 39.1 (C4b), 40.1 (C5), 41.1 (C10a),
46.5 (C2), 48.9 (C8a), 55.5 (C1), 56.6 (C4a), 61.2
(C17), 65.2 (C16), 72.1 (C20), 126.2 (C11), 148.8
(C12).
%5 solution of NaHCO3 (2 50 ml), with water
(2 50 ml), the organic layer was separated, dried on
MgSO4, evaporated, and the residue was crystallized
from ethyl acetate. We obtained 1.2 g (70%) of com-
pound III, mp 168 170 C, [ ]2D0 11.8 (c 2.0,
1
CHCl3). H NMR spectrum, , ppm (J, Hz): 0.60 s
(3H, C18H3), 0.75 s (3H, C19H3), 0.85 m (1H, H5),
1.04 d (3H, C14H3, 6.8), 1.07 d (3H, C15H3, 6.8),
1.10 1.60 m (11H, H4, H4a, H5, C6H2, C7H2, H8a,
C9H2, H10), 1.64 d.d.d (1H, H4, 12.6, 9.8, 2.8),
1.94 d.d (1H, H10, 8.8, 2.5), 2.11 d.d.d (1H, H1,
J1,2 8.3, J1,17A 12.3, J1,17B 4), 2.23 d.sept. (1H, H13,
J13,11 1.3), 2.23 m (1H, H3), 2.46 d (1H, H2, J2,3
2.5), 3.11 d (1H, H20, 10.9), 3.49 d (1H, H20), 3.29 t
(2H, H16, H17, J17A,1 = J17A,17B = J16A,2 = J16A,16B
13 , 19 -5-Hydroxymethyl-5,9-dimethyl-21-
isopropyl-16-phenyl-15, 17-dioxapentacyclo-
[10.7.2.01,10.04,9.013,19]heneicos-20-ene (III). To a
solution of 1.4 g (3.7 mmol) of triol II in 40 ml of
dichloromethane was added 0.85 g (5.6 mmol) of
benzaldehyde dimethylacetal and 0.05 g (0.29 mmol
of p-toluenesulfonic acid. The reaction mixture was
stirred at room temperature for 1 h, washed with
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 37 No. 8 2001

DERIVATIVES OF L-PIMARIC ACID IN THE SYNTHESIS
1141
12.3), 3.98 d.d (1H, H17, J17B,1 4), 4.23 d.d (1H,
sulfonate, and the mixture was stirred at 40 C for
3 h. Then the reaction mixture was evaporated, and
the residue was subjected to chromatography (SiO2,
eluent hexane ethyl acetate, 1: 1). We obtained
0.38 g (80%) of compound V, [ ]2D0 5.0 (c 1.3,
11
H16, J16B,2 4), 5.21 s (1H, CHPh), 5.42 s (1H, H ),
_
7.26 7.45 m (5H, C6H5). 13C NMR spectrum
(
C, ppm): 16.13 (C18), 17.33 (C6), 17.78 (C19),
19.34 (C9), 20.49 (C15), 21.21 (C14), 29.67 (C4),
33.34 (C13), 35.30 (C7), 35.97 (C10), 36.92 (C3),
37.28 (C8), 38.04 (C4b), 38.68 (C5), 39.80 (C10a),
45.22 (C2), 48.13 (C8a), 53.19 (C1), 55.23 (C4a),
1
CHCl3). H NMR spectrum, , ppm (J, Hz): 0.55 s
(3H, C18H3), 0.73 s (3H, C19H3), 0.85 m (1H, H5),
0.97 d (3H, C14H3, 6.8), 0.98 d (3H, C15H3, 6.8),
1.07 m (1H, H4), 1.19 1.52 m (10H, H4a, H5,
C6H2, C7H2, H8a, C9H2, H10), 1.62 d.d.d (1H, H4,
12.6, 9.8, 2.8), 1.83 d.t (1H, H1, J1,2 = = J1,17B
10.5, J1,17A 2.2), 1.94 d.d (1H, H10, 9, 2), 2.14
2.20 m (2H, H2, H13), 2.31 m (1H, H3), 2.91 d (1H,
71.87 (C17), 72.28 (C16), 74.70 (C20), 107.40
11
_
(CHPh), 124.79 (C ), 126.00, 128.25, 128.46,
139.19 (C6H5), 147.55 (C12).
13 ,19 -5-Benzyloxymethyl-5,9-dimethyl-21-
isopropyl-16-phenyl-15, 17-dioxapentacyclo-
[10.7.2.01,10.04,9.013,19]heneicos-20-ene (IV). To a
solution of 4.6 g (10 mmol) of compound III in 5 ml
of dichloromethane was added 5 ml of 50% solution
of NaOH, 0.17 g (0.5 mmol) of tetrabutylammonium
hydrogen sulfate, and 7 ml (61 mmol) of benzyl
chloride. The reaction mixture was vigorously stirred
at 45 50 C for 5 h, then washed with water till
pH 7, the organic layer was separated, dried on
MgSO4, evaporated, and the residue was subjected to
chromatography (SiO2, eluent hexane ethyl acetate,
7: 3). We obtained 4.8 g (86%) of compound IV,
H20, 8.9), 3.18 d (1H, H20), 3.43 t (1H, H17, J17A,1
=
J17A,17B 10.5), 3.45 3.57 m (2H, C16H2), 3.75 d.d
17
_
(1H, H ), 4.45 d (1H, CH2Ph, 12.5), 4.54 d (1H,
11
_
CH2Ph), 5.31 s (1H, H ), 7.26 7.39 m (5H, C6H5).
13C NMR spectrum, C, ppm: 16.00 (C18), 17.37
(C6), 18.19 (C19), 19.51 (C9), 20.48 (C15), 21.16
(C14), 30.28 (C4), 33.16 (C13), 36.01 (C7), 36.30
(C10), 36.95 (C8), 37.96 (C4b), 38.17 (C3), 38.63
(C5), 39.91 (C10a), 45.59 (C2), 48.16 (C8a), 53.96
(C1), 54.91 (C4a), 61.07 (C17), 65.51 (C16), 73.12
20
11
[ ]2D0 77.9 (c 1.8, CHCl3). H NMR spectrum, ,
1
_
(C ), 79.65 (CH2Ph), 124.86 (C ), 127.39, 128.31,
138.99 (C6H5), 147.61 (C12).
ppm (J, Hz): 0.58 s (3H, C18H3), 0.74 s (3H, C19H3),
0.86 m (1H, H5), 1.03 d (3H, C14H3, 6.8), 1.07 d
(3H, C15H3, 6.8), 1.15 m (1H, H4), 1.27 1.42 m
(8H, H4a, H5, H6, C7H2, H8a, H9, H10), 1.54 m (2H,
H6, H9), 1.64 m (1H, H4), 1.91 m (1H, H10),
2.12 d.d.d (1H, H1, J1,2 8.3, J1,17A 12.3, J1,17B 4),
2.22 d.sept. (1H, H13, J13,11 1.3), 2.29 m (1H, H3),
2.46 d.d.d.d (1H, H2, J2,3 2.5), 2.90d (1H, H20, 8.9),
16 ,17 -5-Benzyloxymethyl-17-hydroxymethyl-
5, 9-dimethyl-13-isopropyl-14-oxapentacyclo
[11.4.1.01,10.04,9.012,17]octadecane (VI). To a solu-
tion of 0.26 g (0.47 mmol) of compound IV in 5 ml
of methanol at 0 C was added 0.5 ml of 5% solution
of HCl in methanol, and the mixture was stirred at
20 C for 1 h, evaporated, the residue was dissolved
in 5 ml of ethyl acetate, washed with saturated solu-
tion of NaHCO3 (2 5 ml), with water (5 ml), dried
on Na2SO4, evaporated, the residue was subjected to
chromatography (SiO2, eluent hexane ethyl acetate,
1: 1). We obtained 0.09 g (40%) of diol V and 0.11 g
3.19 d (1H, H20), 3.48 t (2H, H16, H17, J17A,1
=
J17A,17B = J16A,2 = J16A,16B 12.3), 3.98 d.d (1H,
H16, J16B,2 4), 4.25 d.d (1H, H17, J17B,1 4), 4.45 d
_
_
(1H, CH2Ph), 4.54 d (1H, CH2Ph, 12.5), 5.21 s
11
_
(CHPh), 5.41 s (1H, H ), 7.25 7.46 m (10H,
2C6H5). 13C NMR spectrum ( C, ppm): 16.15 (C18),
17.43 (C6), 18.26 (C19), 19.37 (C9), 20.52 (C15),
21.24 (C14), 29.70 (C4), 33.36 (C13), 36.08 (C7,
C10), 36.93 (C3), 37.01 (C8), 38.05 (C4b), 38.63
(C5), 39.82 (C10a), 45.24 (C2), 48.19 (C8a), 53.24
(C1), 55.13 (C4a), 71.89 (C17), 73.15 (C16), 74.74
1
(50%) of compound VI. H NMR spectrum, , ppm
(J, Hz): 0.74 s (3H, C18H3), 0.85 m (1H, H5), 0.91 s
(3H, C19H3), 0.92 d (3H, C14H3, 6.8), 0.97 d (3H,
C15H3, 6.8), 1.10 1.67 m (13H, H4, H4a, H5, C6H2,
C7H2, H8a, C9H2, H10, C11H2, H13), 1.76 m (2H,
H1, H4), 1.89 d.d (1H, H10, 11, 1.8), 2.07 m(1H,
H3), 2.36 d.t (1H, H2, J2,1 = J2,3 9.5, J2,16A 3.7,
J2,16B 0), 2.89 d (1H, H20, 8.9), 3.20 d (1H, H20),
3.48 d.d (1H, H16, J16A,16B 8.4), 3.67 t (1H, H17,
20
11
_
_
(C ), 79.59 (CH2Ph), 107.42 (CHPh), 124.91 (C ),
126.00, 127.47, 128.26, 128.34, 128.46, 139.09,
139.56 (2C6H5), 147.46 (C12).
5-Benzyloxymethyl-13 ,14 -dihydroxymethyl-
J17A,1 = J17A,17B 10.3), 3.84 d.d (1H, H17, J17B,1
5,9-dimethyl-16-isopropyltetracyclo[10.2.2.01,0.04,9]-
hexadec-15-ene (V). To a solution of 0.55 g
(1 mmol) of compound IV in 10 ml of methanol was
added 0.03 g (0.1 mmol) of pyridinium p-toluene-
16
_
3.8), 3.95 d (1H, H ), 4.45 d (1H, CH2Ph, 12.5),
_
4.54 d (1H, CH2Ph), 7.27 7.39 m (5H, C6H5).
13C NMR spectrum ( C, ppm): 15.79 (C18), 16.59
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 37 No. 8 2001

1142
TOLSTIKOV et al.
(C19), 16.88 (C15), 17.48 (C6), 18.09 (C14), 18.82
(C9), 32.63 (C13), 32.97 (C4), 35.94 (C7), 36.98
(C10), 37.41 (C8), 37.99 (C4b), 38.06 (C3), 39.17
(C5), 39.52 (C2), 41.46 (C10a), 48.96 (C8a), 51.86
(C1), 54.77 (C4a), 60.87 (C17), 67.88 (C16), 73.14
125.11 (C11), 127.44, 127.85, 128.05, 128.29,
129.90, 129.96, 132.62, 132.73, 138.94, 144.81,
12
_
_
144.96 (CH2C6H5, 2CH3C6H4), 147.00 (C ).
Compound (VIII). [ ]2D0 +10.2 (c 2.0, CHCl3).
1H NMR spectrum, , ppm (J, Hz): 0.59 s 3H,
C18H3), 0.74 s (3H, C19H3), 0.85 m (1H, H5), 1.01
d (3H, C14H3, 6.8), 1.04 d (3H, C15H3, 6.8), 1.11 m
(1H, H4), 1.24 1.42 m (8H, H4a, H5, H6, C7H2,
H8a, H9, H10), 1.47 1.65 m (3H, H4, H6, H9), 1.78
d.d (1H, H10, 8.8, 2.5), 2.05 d.t (1H, H1, J1,2 8.2,
J1,17B = J1,17A 8.5), 2.15 d. sept. (1H, H13, J13,11
1.3), 2.38 d.d.t (2H, H3, H2, J2,3 2.6, J2,16B = J2,16A
8.5), 2.86 d (1H, H20, 8.9), 3.07 t (1H, H17, J17A,17B
8.5), 3.19 d (1H, H20), 3.21 t (1H, H16, 8.5), 3.76 t
20
12
_
(C ), 79.41 (CH2Ph), 84.41 (C ), 127.47, 128.33,
139.03 (C6H5).
5-Benzyloxymethyl-5,9-dimethyl-13 ,14 -di-
to s y l o x y meth y l -1 6 -i s o p ropyltetracyclo-
[10.2.2.01,10.04,9]hexadec-15-ene (VII) and 5-benzyl-
oxymethyl-5,9-dimethyl-19-isopropyl-15-oxapenta-
cyclo[10.5.2.01,10.04,9.013,17]-
nonadec-18-ene (VIII). To a solution of 0.27 g
(0.8 mmol) of diol V in 2 ml of pyridine at 20 C
in a flow of argon was added by portions 0.22 g
(1.2 mmol) of tosyl chloride, and stirring at 20 C
continued for 24 h. Then was added 10 ml of ice
water and 2 ml of ether, the separated viscous oily
substance was ground with a glass stick till crystals
formed. The crystals were filtered off, washed with
ice water, with cold ether, and dried in a high vacuum
at 20 C, We obtained 0.34 g (75%) of ditosylate VII.
From the water-ether filtrate the organic products
were extracted into ethyl acetate (2 10 ml), the
combined extracts were dried on Na2SO4, evaporated,
the residue was subjected to chromatography (SiO2,
eluent hexane ethyl acetate, 7: 3). We obtained 0.11g
(20%) of compound VIII. The reaction at room
temperature in 3 h afforded 15% of compound VII
and 80% of compound VIII.
16
17
_
(1H, H ), 3.86 t (1H, H ), 4.44 d (1H, CH2Ph,
11
_
12.5), 4.53 d (1H, CH2Ph), 5.37 s (1H, H ), 7.25
7.39 m (5H, C6H5). 13C NMR spectrum, C, ppm:
15.30 (C18), 16.17 (C6), 17.42 (C19), 18.17 (C9),
18.97 (C15), 20.14 (C14), 28.66 (C4), 33.61 (C13),
36.01 (C7), 36.11 (C10), 37.04 (C3), 37.04 (C8),
37.73 (C4b), 38.78 (C5), 39.39 (C10a), 45.70 (C2),
48.54 (C8a), 54.90 (C1), 54.90 (C4a), 70.75 (C17),
16
20
_
72.45 (C ), 73.09 (C ), 79.61 (CH2Ph), 125.22
(C11), 127.33, 128.23, 139.03 (C6H5), 147.26 (C12).
5-Benzyloxymethyl-13 ,14 -bis(diphenylphos-
phanylmethyl)-5,9-dimethyl-16-isopropyltetracyclo-
[10.2.2.01,10.04,9]hexadec-15-ene (IX). A mixture of
9 ml of dioxane, 0.69 g (30 mmol) of sodium metal,
and 1.29 g (5.8 mmol) of diphenylchlorophosphine
were refluxed at vigorous stirring in an argon flow
for 5 h. The orange dispersion obtained was cooled
to room temperature, and 2 g (2.6 mmol) of
ditosylate VIII was added thereto. The reaction mix-
ture was stirred for 2 h, and a dispersion of 30 g of
Al2O3 in 70 ml of anhydrous benzene was added. The
mixture was filtered, the filtrate was evaporated, the
viscous residue containing ligand IX was ground in
anhydrous ethanol till crystals formation. The solvent
was decanted, and the precipitate was recrystallized
from methanol. We obtained 0.65 g (31%) of com-
pound IX, mp 132 134 C, Rf 0.70 (benzene ethyl
Compound (VII). mp 60 62 C, [ ]2D0 +14.3 (c
1
4.7, CHCl3). H NMR spectrum, , ppm (J, Hz):
0.45 s (3H, C18H3), 0.70 s (3H, C19H3), 0.80 m (1H,
H5), 0.82 d (3H, C14H3, 6.8), 0.85 d (3H, C15H3,
6.8), 1.00 1.55 m (12H, C4H2, H4a, H5, C6H2,
C7H2, H8a, C9H2, H10), 1.79 m (3H, H1, H2, H10),
13
_
2.13 m (1H, H ), 2.45 s (3H, CH3C6H4), 2.46 s
3
20
_
(3H, CH3C6H4), 2.58 m (1H, H ), 2.86 d (1H, H ,
8.9), 3.16 d (1H, H20), 3.43 t (1H, H17, J17A,1
=
J17A,17B 9.5), 3.58 t (1H, H16, J16A,2 = J16A,16B 8),
4.04 d.d (1H, H16, J16B,2 2.5), 4.12 d.d (1H, H17,
acetate, 9: 1), [ ]D20 55.4 (c 1.0, CHCl3). H NMR
1
_
J17B,1 4.4), 4.43 d (1H, CH2Ph, 12.5), 4.52 d (1H,
_
spectrum, , ppm (J, Hz): 0.58 s (3H, C18H3), 0.73 s
(3H, C19H3), 0.86 2.32 m (21H, H1, H2, H3, C4H2,
H4a, C5H2, C6H2, C7H2, H8a, C9H2, C10H2, C16H2,
C17H2), 1.11 d (3H, C14H3, 6.8), 1.12 d (3H, C15H3,
6.8), 2.49 d.sept. (1H, H13, J13,1 1.3), 2.87 d (1H,
11
CH2Ph), 5.28 s (1H, H ), 7.30 7.78 m (13H, C6H5,
2C6H4). 13C NMR spectrum, C, ppm: 15.92 (C18),
17.25 (C6), 18.15 (C19), 19.08 (C9), 19.77 (C15),
14
4
_
20.92 (C ), 21.74 (2CH3C6H4), 28.54 (C ), 32.94
(C13), 35.11 (C3), 35.27 (C7), 35.87 (C10), 36.88
(C8), 37.96 (C4b), 38.37 (C5), 39.75 (C10a), 41.08
(C2), 47.91 (C8a), 49.27 (C1), 55.06 (C4a), 68.34
20
20
_
H , 8.9), 3.18 d (1H, H ), 4.44 d (1H, CH2Ph,
11
_
12.5), 4.52 d (1H, CH2Ph), 5.46 s (1H, H ), 7.25
7.50 m (25H, 4C6H5). 13C NMR spectrum, C, ppm
17
16
20
_
(C ), 70.87 (C ), 73.06 (C ), 79.32 (CH2Ph),
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 37 No. 8 2001

DERIVATIVES OF L-PIMARIC ACID IN THE SYNTHESIS
1143
(J, Hz): 15.95 s (C18), 17.24 s (C6), 18.05 s (C19),
19.36 s (C9), 20.32 s (C15), 21.31 s (C14), 29.66 s
(C4), 30.57 d (C10a, J10A,P(2) 14), 33.49 s (C13),
35.81 s (C7), 36.35 s (C10), 36.81 s (C8), 37.71 d
(C3, J3,P(1) 12), 37.85 s (C4b), 38.31 s (C5), 39.26 q
(C2, J2,P(1) 6, J2,P(2) 14), 41.50 d (C16, C17,
J16,P(1) = J17,P(2) 9), 47.85 s (C8a), 48.09 q (C1,
(C4b), 38.07 (C5), 38.28 (C10a), 41.05 (C8), 48.72
2
8a
1
4a
_
(C , C ), 54.59 (C , C ), 59.79, 60.34 (2CH2CH3),
20
11
_
73.16 (C ), 79.93 (CH2Ph), 124.69 (C ), 127.13,
127.25, 128.07, 139.04 (C6H5), 147.85 (C12),
173.51, 173.98 (2CO).
5-Benzyloxymethyl-13 ,14 -dihydroxymethyl-
5 , 9 - d i m e t h y l - 1 6 - i s o p r o p y l t e t r a c y c l o -
J1,P(2) 8, J1,P(1) 12), 55.06 s (C4a), 72.90 s (C20),
[10.2.2.01,10.04,9]hexadec-15-ene (XI). To a suspen-
sion of 0.4 g (10.5 mmol) of LiAlH4 in 20 ml of
ether was added dropwise at 20 C a solution of 3.1 g
(5.6 mmol) of compound X in 20 ml of ether, The
reaction mixture was boiled for 4 h, 50 ml of ethyl
acetate was added, then 50 ml of 1 N HCl. The
organic layer was separated, washed with water,
dried with Na2SO4, evaporated, and the residue was
subjected to chromatography (SiO2, chloroform).
We obtained 2.5 g (95%) of compound XI, oily sub-
stance, [ ]2D9 2.2 (c 1.0, CHCl3). 1H NMR
spectrum, , ppm (J, Hz): 0.57 s (3H, C18H3), 0.72
s (3H, C19H3), 0.86 m (1H, H5), 0.97 d (6H, C14H3,
C15H3, 6.8), 1.10 1.90 m (14H, H2, C4H2, H4a, H5,
C6H2, C7H2, H8a, C9H2, C10H2), 2.00 m (1H, H1),
2.29 d.sept. (1H, H13, J13,11 1.3), 2.39 m (1H, H3),
2.90 m (1H, H16), 2.93 d (1H, H20, 9), 3.15 d (1H,
H20), 3.59 t (1H, H17, J17A,1 = J17A,17B 10), 3.60 m
11
_
79.29 s (CH2Ph), 124.83 s (C ), 127.14, 128.11,
_
139.00 3 s (CH2C6H5), 127.83, 128.73 2d [8Cortho
,
,
4(PC6H5), JC,P 9], 128.24, 128.38 2d [4Cpara
4(PC6H5), JC,P 7], 132.15, 133.70, 133.78,
133.82 4d [8Cmeta, 4(PC6H5), JC,P 19), 137.40,
138.22, 140.25, 140.51 4d [4Copso, 4(PC6H5), JC,P
14], 148.04 s (C12). 31P NMR spectrum, P, ppm:
10.61, 16.26. Found, %: C 82.18; H 7.92.
C45H64OP2. Calculated, %: C 82.26; H 8.03.
5-Benzyloxymethyl-5, 9-dimethyl-13 , 14 -
diethoxycarbonyl-16-isopropyltetracyclo-
[10.2.2.01,10.04,9]hexadec-15-ene (X). A mixture of
resin alcohols (20g), 10g of sodium hydride, and 18g
of benzyl bromide in 200 ml of THF were stirred for
5 days. Then 30 ml of methanol was added, the mix-
ture was evaporated, the residue was dissolved in
300 ml of ether, washed with 10% solution of HCl
(2 100 ml) and with water (2 50 ml). The organic
layer was dried with Na2SO4, evaporated, and the
residue was subjected to chromatography (SiO2,
hexane ethyl acetate, 7: 3). We obtained 22 g of a
mixture of benzyl ethers of resin alcohols. 7 g of this
mixture and 7 g of diethyl fumarate was heated for 4h
to 180 c, the excess diethyl fumarate was distilled off
in a vacuum, and the residue was subjected to
chromatography (SiO2, hexane). We obtained 3.2 g
(31%) of compound X, oily substance, [ ]2D9 27.0
16
17
_
(2H, H , H ), 4.41 d (1H, CH2Ph, 12.5), 4.52 d
11
_
(1H, CH2Ph), 5.28 s (1H, H ), 7.31 7.28 m (5H,
C6H5). 13C NMR spectrum, C, ppm: 15.96 (C18),
17.35 (C6), 18.06 (C19), 19.34 (C9), 20.62 (C14,
C15), 23.36 (C4), 32.63 (C13), 35.60 (C3), 35.65
(C10), 36.14 (C7), 37.05 (C4b), 37.96 (C5), 38.74
(C10a), 40.03 (C8), 44.90 (C2), 48.49 (C8a), 55.53
(C1), 55.82 (C4a), 64.35 (C17), 66.98 (C16), 73.24
20
11
_
(C ), 79.98 (CH2Ph), 124.41 (C ), 127.21, 127.30,
128.14, 139.10 (C6H5), 150.07 (C12).
1
(c 1.0, CHCl3). H NMR spectrum, , ppm (J, Hz):
5-Benzyloxymethyl-13 ,14 -ditosyloxymethyl-
5 , 9 - d i m e t h y l - 1 6 - i s o p r o p y l t e t r a c y c l o -
[10.2.2.01,10.04,9]hexadec-15-ene (XII). To a mix-
ture of 3.26 g (7 mmol) of diol XI and 20 ml of
pyridine cooled to 20 C was added by portions in an
argon flow 4 g (21 mmol) of tosyl chloride, and the
stirring at this temperature continued for 16 h. The
reaction mixtures was poured into 100 ml of water
cooled to 5 C, the separated oily substance was
extracted with ether (3 60 ml). The combined
extracts were dried on Na2SO4, evaporated, and the
residue was subjected to chromatography (SiO2,
hexane ethyl acetate, 7: 3). We obtained 4 g (74%)
of oily compound XII, [ ]2D9 11.8 (c 1.0, CHCl3).
1H NMR spectrum, , ppm (J, Hz): 0.50 s (3H,
C18H3), 0.67 s (3H, C19H3), 0.73 m (1H, H5), 0.82 d
0.57 s (3H, C18H3), 0.72 s (3H, C19H3), 0.83 m (1H,
H5), 1.06 d (6H, C14H3, C15H3, 6.8), 1.25 m (6H,
4
4a
5
_
2(OCH2CH3), 1.29 1.79 m (13H, C H2, H , H ,
C6H2, C7H2, H8a, C9H2, C10H2), 2.39 d.sept. (1H,
H13, J13,11 1.3), 2.55 d.d.d (1H, H2, J2,1 5.9, J2,3
2.7, J2,4 2.7), 2.75 d (1H, H1, J1,2 5.9), 2.85 q.d
(1H, H3, J3,2 2.7, J3,4 = J3,4 2.8, J3,11 1.5), 2.89 d
(1H, H20, 9), 3.17 d (1H, H20), 4.04 q (2H,
_
_
OCH2CH3, 7), 4.13 q (2H, OCH2CH3), 4.42 d (1H,
11
_
_
CH2Ph, 9), 4.52 d (1H, CH2Ph), 5.36 s (1H, H ),
7.24 7.33 m (5H, C6H5). 13C NMR spectrum,
,
C
ppm: 14.14 (C18), 16.07 (C19), 17.26 (C6), 17.96,
19.25 (C14, C15), 19.11 (C9), 20.54 (C4), 32.64
(C13), 34.79 (C10), 35.92 (C3), 36.06 (C7), 37.01
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 37 No. 8 2001

1144
TOLSTIKOV et al.
4a
20
(3H, C14H3, 6.8), 0.84 d (3H, C15H3, 6.8), 1.05
1.75 m (16H, H1, H2, H3, C4H2, H4a, H5, C6H2,
C7H2, H8a, C9H2, C10H2), 2.13 d.sept. (1H, H13,
10), 55.21 s (C ), 72.98 s (C ), 79.73 s (CH2Ph),
127.01 s (C11), 127.11, 127.99, 128.30, 138.90 4 s
_
_
(CH2C6H5), 127.62, 128.87 2 d (8Cortho, 4PC6H5,
JC,P 17), 128.24, 128.58 2d (4Cpara, 4PC6H5, JC,P 7),
131.83, 133.58, 133.84, 134.08 4d (8Cmeta, 4PC6H5,
_
J13,11 1.3), 2.40 s (3H, CH3C6H4), 2.41 s (3H,
_
20
20
CH3C6H4), 2.83 d (1H, H , 9), 3.13 d (1H, H ),
3.28 t (1H, H16, J16A,2 = = J16A,16B 10), 3.73 t (1H,
H17, J17A,1 = J17A,17B 10), 4.02 m (2H, H16, H17),
JC,P 19), 136.94, 137.57, 140.16, 140.45 4d (4Cipso
,
4PC6H5, JC,P 14), 148.50s (C12). 31P NMR spectrum,
, ppm: 17.59, 21.79. Found, %: C 82.35; H 8.11.
C45H64OP2. Calculated, %: C 82.26; H 8.03.
_
4.39 d (1H, CH2Ph, 12.5), 4.50 d (1H, CH2Ph),
5.16 s (1H, H11), 7.24 7.82 m (13H, C6H5, 2C6H4).
13C NMR spectrum, C, ppm: 15.71 (C18), 17.21
(C6), 17.99 (C19), 18.96 (C9), 20.36, 20.48 (C14,
5, 9-Dimethyl-13 ,14 -diethoxycarbonyl-16-
isopropyl-5-carboxytetracyclo[10.2.2.01,10.04,9]-
hexadec-15-ene (XIV). A mixture of 23.5 g of pine
galipot and 14.9 g of diethyl fumarate was heated to
180 C for 2 h, the excess diethyl fumarate was
distilled off in a vacuum, and the residue was sub-
jected to chromatography (SiO2, hexane ethyl
acetate, 7: 3), Rf 0.42. We obtained 9.5 g (25%) of
oily compound XIV. 1H NMR spectrum, , ppm
(J, Hz): 0.55 s (3H, C18H3), 1.04 d (6H, C14H3,
C15H3, 6.8), 1.10 s (3H, C19H3), 1.20 m (6H,
15
4
13
_
C ), 21.36 (2CH3C6H4), 21.82 (C ), 32.44 (C ),
33.18 (C3), 35.09 (C10), 35.95 (C7), 36.90 (C4b),
37.64 (C5), 38.51 (C10a), 39.75 (C8), 41.14 (C2),
48.23 (C8a), 49.85 (C1), 54.95 (C4a), 71.60 (C17),
16
20
_
72.65 (C ), 73.17 (C ), 79.67 (CH2Ph), 123.97
(C11), 127.24, 127.32, 127.61, 127.72, 128.13,
129.68, 129.75, 133.20, 133.38, 138.94, 144.54
(C6H5, 2C6H4), 149.96 (C12). Found, %: C 69.81; H
7.48. C45H58O7S2. Calculated, %: C 69.73; H 7.54.
4
4a
5
_
2OCH2CH3), 1.32 1.95 m (14H, C H2, H , C H2,
C6H2, C7H2, H8a, C9H2, C10H2), 2.48 d. sept. (1H,
H13, J13,11 1.3), 2.53 d.d.d (1H, H2, J2,1 5.9, J2,3 2.7,
J2,4 2.7), 2.72 d (1H, H1, J1,2 5.9), 2.82 q.d (1H,
5-Benzyloxymethyl-13 , 14 -bis(diphenyl-
phosphanylmethyl)-5,9-dimethyl-16-isopropyl-
tetracyclo[10.2.2.01,10.04,9]hexadec-15-ene (XIII).
A mixture of 9 ml of dioxane, 0.69 g (30 mmol) of
sodium metal, and 1.29 g (5.8 mmol) of diphenyl-
chlorophosphine were refluxed at vigorous stirring in
an argon flow for 5 h. The orange dispersion obtained
was cooled to room temperature, and 2 g (2.6 mmol)
of ditosylate XII was added thereto in one portion.
The reaction mixture was stirred for 2 h, and a
dispersion of 30 g of Al2O3 in 70 ml of anhydrous
benzene was added. The mixture was filtered, the
filtrate was evaporated, the residue was subjected to
chromatography (SiO2, benzene ethyl acetate, 9: 1).
We obtained 0.72 g (35%) of compound XIII, Rf
H3, J3,2 2.7, J3,4 = J
=2.8, J3,11 1.5), 4.01 q
3,4
_
_
(2H, OCH2CH3, 7), 4.12 q (2H, OCH2CH3), 5.35 s
(1H, H11). 13C NMR spectrum, C, ppm: 14.00 (C18),
14.15 (C19), 15.88, 20.35 (C14, C15), 16.86 (C6),
21.79 (C9), 23.41 (C4), 32.58 (C13), 34.41 (C10),
35.65 (C3), 36.75 (C7), 37.25 (C4b), 37.48 (C5),
41.12 (C10a), 46.80 (C8), 48.56 (C2), 48.99 (C8a),
54.16 (C ), 54.45 (C ), 60.06, 60.53 (2OCH2CH3),
124.17 (C11), 148.00 (C12), 173.56 (CO), 174.18
(CO), 185.23 (CO). Found, %: C 70.98; H 12.69.
C28H42O6. Calculated, %: C 70.85; H 12.59.
1
4a
_
0.70, [ ]2D0 1.8 (c 1.0, CHCl3). H NMR spectrum,
1
, ppm (J, Hz): 0.58 s (3H, C18H3), 0.73 s (3H,
C19H3), 0.87 d (6H, C14H3, C15H3, 6.8), 0.95 2.82
m (22H, H1, H2, H3, C4H2, H4a, C5H2, C6H2, C7H2,
H8a, C9H2, C10H2, H13, C16H2, C17H2), 2.89 d (1H,
5, 9-Dimethyl-13 ,14 -diethoxycarbonyl-16-
i s o p r o p y l - 5 - ch l o ro ca rb o n y l tetra cy cl o -
[10.2.2.01,10.04,9]hexadec-15-ene (XV). A mixture
of 2 g (4.2 mmol) of compound XIV and 1.64 g
(12 mmol) of PCl3 was kept at 20 C for 24 h, the
excess PCl3 was distilled off, the residue was diluted
with toluene and evaporated. We obtained 2.1 g of
20
20
_
H , 8.9), 3.19 d (1H, H ), 4.42 d (1H, CH2Ph,
11
_
12.5), 4.48 d (1H, CH2Ph), 5.29 s (1H, H ), 7.21
7.91 m (25H, 5C6H5). 13C NMR spectrum, C, ppm
(J, Hz): 15.75 s (C18), 17.25 s (C6), 17.94 (C19),
19.26 s (C9), 20.30, 20.87 2s (C14, (C15), 22.66 s
(C4), 32.19 s (C13), 32.77 d (C10a, J10a,P(2) 14),
35.91 s (C10), 36.00 s (C7), 36.90 s (C4b), 37.12 s
(C3, J3,P(1) 13), 37.82 s (C5), 38.59 s (C8), 42.81 q
1
crude oily acyl chloride XV. IR spectrum, cm :
1725, 1795.
5,9-Dimethyl-13 ,14 -diethoxycarbonyl-16-iso-
propyl-5-morpholinocarbonyltetracyclo-
[10.2.2.01,10.04,9]hexadec-15-ene (XVI). To a stirred
mixture of 7.4 g (15 mmol) of acyl chloride XV and
100 ml of toluene at 5 C was slowly (within 0.5 h)
added 5.31 g (61 mmol) of morpholine. The stirring at
(C2, J2,P(1) 6, J2,P(2) 14), 41.67 d (C16, C17, J16,P(1)
J17,P(2) 9), 48.39 s (C8a), 54.43 q (C1, J1,P(2) 8, J1,P(1)
=
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 37 No. 8 2001

DERIVATIVES OF L-PIMARIC ACID IN THE SYNTHESIS
1145
20 C was continued for 16 h. The separated pre-
cipitate was filtered off, the filtrate was diluted with
100 ml of ethyl acetate, washed with 50 ml of 10%
HCl, with water, the organic layer was separated,
dried on Na2SO4, evaporated, the residue was sub-
jected to chromatography (SiO2, hexane ethyl
acetate, 1: 1). We obtained 7.52 g (95%) of oily
16.01 (C18), 17.27 (C6), 18.97 (C19), 19.25 (C9),
20.82 (C14, C15), 23.29 (C4), 32.45 (C13), 35.40
(C3), 35.62 (C10), 36.53 (C7), 37.93 (C4b), 38.25
(C5), 38.34 (C10a), 39.76 (C8), 44.69 (C2), 48.53
(C8a), 55.47 (C1), 55.77 (C4a), 56.26 [(CH2)2N],
63.95 (C17), 66.63 (C16), 67.28 [(CH2)2O], 69.62
(C20), 124.05 (C11), 149.75 (C12). Found, %: C
75.58; H 10.71; N 3.02. C28H47NO5. Calculated, %:
C 75.46; H 10.63; N 3.14.
compound XVI, [ ]D20 4.8 (c 3.0, CHCl3). H NMR
1
spectrum, , ppm (J, Hz): 0.53 s (3H, C18H3), 0.99 d
(6H, C14H3, C15H3, 6.8), 1.13 s (3H, C19H3), 1.17 m
4
4a
5,9-Dimethyl-13 ,14 -ditosyloxymethyl-16-iso-
p r o p y l -5 -mo rp h o l i n o meth y l tetra cy cl o -
_
(6H, 2OCH2CH3), 0.68 1.90 m (14H, C H2, H ,
C5H2, C6H2, C7H2, H8a, C9H2, C10H2), 2.33 d.sept.
(1H, H3, J13,11 1.3), 2.48 d.d.d (1H, H2, J2,1 5.9,
J2,3 2.7, J2,4 2.7), 2.68 d (1H, H1, J1,2 5.9 ), 2.80
q.d. (1H, H3, J3,2 2.7, J3,4 = J3,4 2.8, J3,11 1.5),
[10.2.2.01,10.04,9]hexadec-15-ene (XVIII). To
a
mixture of 5.5 g (12 mmol) of diol XVII and 50 ml
of pyridine at 20 C in an argon flow was added by
small portions 9.34 g (49 mmol) of tosyl chloride.
The stirring at 20 C was continued for 16 h. Then
to the reaction mixture was added 40 ml of ice water,
10 ml of ether, and the separated thick oily substance
was ground till crystallization. The crystals were
filtered off, washed on filter with 20 ml of ice water,
10 ml of cold ether, and dried in a vacuum (1 mm Hg,
40 C). We obtained 4.52 g (50%) of compound
XVIII, mp 89 92 C, [ ]2D0 2.4 (c 4.0, CHCl3).
1H NMR spectrum, , ppm (J, Hz): 0.48 s (3H,
C18H3), 0.62 s (3H, C19H3), 0.79 d (3H, C14H3,
6.8), 0.81 d (3H, C15H3, 6.8), 0.85 2.22 m (20H,
H1, H2, H3, C4H2, H4a, C5H2, C6H2, C7H2, H8a,
_
3.58 br.s (8H, 4CH2), 3.96 q (2H, OCH2CH3, 7),
11
4.07 q (2H, OCH2CH3), 5.31 s (1H, H ). 13C NMR
_
18
_
spectrum, C, ppm: 13.95 (C , 2OCH2CH3), 16.09
(C19), 16.22 (C6), 18.63, 20.26 (C14, C15), 21.86
(C9), 23.27 (C4), 32.48 (C13), 34.56 (C10), 35.58
(C3), 37.10 (C7), 37.47 (C4b), 37.64 (C5), 41.10
(C10a), 45.90 [(CH2)2N], 46.40 (C10a), 48.92 (C2),
49.50 (C8a), 54.06 (C1), 54.86 (C4a), 59.89, 60.37
11
_
(2OCH2CH3), 66.70 [(CH2)2O], 124.34 (C ), 147.82
(C12) 173.51 (CO), 174.18 (CO), 177.33 (CO).
Found, %: C 72.74; H 9.41; N 2.52. C32H49NO5.
Calculated, %: C 72.83; H 9.36; N 2.52.
9
10
13
20
_
C H2, C H2, H , C H2), 2.39 s (3H, CH3C6H4),
5, 9-Dimethyl-13 , 14 -dihydroxymethyl-16-
isopropyl-5-morpholinomethyltetracyclo-
_
2.40 s (3H, CH3C6H4), 2.40 m [4H, (CH2)N], 3.24 t
(1H, H16, J16A,2
=
J16A,16B 10), 3.62 m [4H,
[10.2.2.01,10.04,9]hexadec-15-ene (XVII). To a sus-
pension of 1.1 g (28 mmol) of LiAlH4 in 20 ml of
ether at 20 C was added a solution of 7.4 g (14 mmol)
of compound XVI in 100 ml of ether. The reaction
mixture was stirred for 8 h and was left overnight at
room temperature, then was added 10 ml of ethyl
acetate and 5 ml of 50% NaOH solution. The
separated precipitate was filtered off, washed with
20 ml of hot dioxane, filtrate was evaporated, the
residue was subjected to chromatography (SiO2,
hexane ethyl acetate, 1: 2). We obtained 5.8 g (93%)
of oily compound XVII, [ ]2D0 7.0 (c 4.4, CHCl3).
1H NMR spectrum, , ppm (J, Hz): 0.56 s (3H,
C18H3), 0.59 s (3H, C19H3), 0.73 m (1H, H5), 0.97
d (6H, C14H3, C15H3, 6.8), 1.10 1.63 m (14H,
H2, C4H2, H4a, H5, C6H2, C7H2, H8a, C9H2, C10H2),
1.82 d (2H, C20H2, 7), 2.15 m (1H, H1), 2.26 d.sept.
(1H, H13, J13,11 1.3), 2.34 m (1H, H3), 2.43 m [4H,
(CH2)2N)], 2.83 t (1H, H16, J16A,2 = J16A,16B 10),
3.44 t (1H, H17, J17A,1 = = J17A,17B 10), 3.57 m
(1H, H16), 3.62 m [4H, (CH2)2O], 3.83 m (1H, H17),
5.25 s (1H, H11). 13C NMR spectrum, C, ppm:
(CH2)O], 3.76t (1H, H17, J17A,1 = J17A,17B 10), 4.04m
(2H, H16, H17), 5.13 s (1H, H11), 7.26 7.78 m
(8H, 2C6H4). 13C NMR spectrum, C, ppm: 15.79
(C18), 17.19 (C6), 18.90 (C19), 18.97 (C9), 20.14,
14
15
4
_
20.28 (C , C ), 21.42 (2CH3C6H4), 21.65 (C ),
32.32 (C13), 32.77 (C3), 35.17 (C10), 36.47 (C7),
37.81 (C4b), 38.20 (C5), 38.45 (C10a), 39.49 (C8),
40.82 (C2), 48.81 (C8a), 49.57 (C1), 54.95 (C4a),
56.29 [(CH2)N], 67.23 [(CH2)O], 69.59 (C20), 71.45
(C17), 71.64 (C16), 123.70 (C11), 127.65, 127.75,
129.65, 129.75, 132.65, 132.83, 144.64 (2C6H4),
149.79 (C12).
X-ray diffraction study of the single crystal of
compound XVIII was carried out by standard
procedure on a diffractometer Bruker P4 (MoK -ir-
radiation, graphite monochromator). Crystallographic
parameters of compound XVIII: monoclinic crystal,
a 11.544(2), b
11.192(2), c 15.857(3)
,
105.90(1) , V 1970.3(6) 3. C42H59N1O7S2. M
754.02, Z 2, d 1.271 g/cm3, 0.186 mm , crystal
1
size 0.70 0.17 0.12 mm. Intensities of 3646
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 37 No. 8 2001

1146
TOLSTIKOV et al.
Table3. Coordinates ( 104) and equivalent thermal factors
independent reflections with 2 <50 were measured,
scanning by /2 . A correction for crystal faces was
introduced by integration method (transmission 0.97
0.99). The structure was solved by the direct method
using SHELXS-97 program. The final refinement of
parameters was carried out by least-squares procedure
in the full-matrix anisotropic for nonhydrogen atoms
(isotropic for hydrogen atoms) approximation along
all F2. The positions of hydrogen atoms were
determined from geometrical considerations (rider
model). The final values of R-factors are as follows:
wR2 0.1192, S 0.976 for all reflections (R 0.0566 for
2254 I> 2 ). The absolute structure parameter (Fluk
parameter) equals to 0.08(14) indicating that the
structure is sufficiently reliably solved. The co-
ordinates of nonhydrogen atoms of the molecule of
compound XVIII are listed in Table 3,the structure
of the molecule is presented in Fig. 2.
2
(
,
103) of nonhydrogen atoms in molecule XVIII
Atom
x
y
z
Ueq
S1
3668(1)
573(2)
3024(2)
4952(2)
2032(6)
3756(5)
3640(5)
3987(6)
2002(6)
3770(5)
5875(5)
5019(7)
183(7)
2411(1)
4884(1)
2366(3)
3776(3)
2604(3)
2102(3)
1881(3)
4350(3)
4330(4)
5308(3)
590(4)
53(1)
57(1)
49(1)
68(2)
54(1)
76(2)
70(2)
57(1)
76(2)
84(2)
45(2)
55(2)
54(2)
47(2)
36(2)
43(2)
40(2)
35(2)
34(2)
37(2)
43(2)
40(2)
37(2)
38(2)
37(2)
40(2)
54(2)
67(2)
80(3)
46(2)
63(2)
52(2)
45(2)
50(2)
60(2)
67(2)
69(2)
61(2)
45(2)
61(2)
66(2)
56(2)
59(2)
52(2)
81(3)
47(2)
59(2)
62(2)
62(2)
62(2)
59(2)
96(3)
S2
N1
3855(4)
3572(5)
2529(4)
4252(4)
3289(4)
448(4)
O1
O2
O3
O4
O5
O6
24(5)
O7
1830(4)
1697(5)
2609(6)
3362(6)
4020(6)
3074(5)
3573(5)
2574(5)
1632(5)
1237(5)
2262(5)
310(5)
C1
C2
1080(7)
1598(6)
679(6)
54(4)
618(4)
C3
C4
1036(4)
1528(4)
2004(4)
2672(4)
2265(4)
1664(3)
997(4)
1264(4)
1597(4)
2600(3)
3001(4)
1761(4)
1406(4)
880(4)
13 ,14 -Bis(diphenylphosphanylmethyl)-5,9-di-
methyl-16-isopropyl-5-morpholinomethyltetracyclo-
[10.2.2.01,10.04,9]hexadec-15-ene (XIX). A mixture
of 9 ml of dioxane, 0.69 g (30 mmol) of sodium
metal, and 1.29 g (5.8 mmol) of diphenylchloro-
phosphine were refluxed at vigorous stirring in an
argon flow for 5 h. The orange dispersion obtained
was cooled to room temperature, and 1.96 g
(2.6 mmol) of ditosylate XVIII was added thereto in
one portion. The reaction mixture was stirred for 2 h,
and a dispersion of 30 g of Al2O3 in 70 ml of
anhydrous benzene was added. The mixture was
filtered, the filtrate was evaporated, the residue was
ground in 10 ml of methanol till crystallization. The
solvent was decanted, the precipitate was recrystal-
lized from ethanol benzene, 4: 1. We obtained 0.65 g
(32%) of compound XIX, mp 154 156 C, Rf 0.70
C5
255(5)
C6
1250(6)
1862(6)
2415(6)
1511(6)
827(6)
2127(6)
3422(6)
3415(6)
2747(6)
3538(6)
4084(6)
5206(7)
4961(9)
6157(8)
1659(6)
126(8)
1319(6)
2873(7)
3447(7)
1735(7)
2533(7)
4060(8)
3327(7)
2570(7)
3409(7)
3043(8)
1856(8)
1031(8)
1407(7)
1469(9)
4675(6)
3976(7)
3745(8)
4239(8)
4928(8)
5146(7)
4006(10)
C7
C8
C9
C10
C11
C12
C13
C14
C15
C16
C17
C18
C19
C20
C21
C22
C23
C24
C25
C26
C27
C28
C29
C30
C31
C32
C33
C34
C35
C36
C37
C38
C39
C40
C41
C42
64(5)
458(5)
446(5)
2033(5)
1251(5)
1467(6)
1524(6)
531(8)
2944(5)
5093(6)
4621(6)
1709(5)
706(6)
4016(7)
3301(7)
3352(7)
4111(7)
4548(5)
5149(6)
5845(6)
6001(6)
5417(6)
4692(6)
6783(7)
215(6)
80(4)
1270(6)
256(4)
318(4)
(benzene ethyl acetate, 9: 1), [ ]2D0 32.7 (c 1.0,
1661(5)
2919(4)
3741(4)
3225(4)
3942(5)
2963(5)
2222(5)
3435(4)
4044(5)
4843(5)
5066(4)
4455(5)
3642(4)
5956(5)
5663(4)
6375(5)
7001(4)
6934(5)
6217(5)
5576(5)
7657(5)
1
CHCl3), mp 154 156 C. H NMR spectrum, , ppm
(J, Hz): 0.63 s (3H, C18H3), 0.71 s (3H, C19H3),
0.90 d (6H, C14H3, C15H3, 6.8), 0.65 2.85 m (22H,
H1, H2, H3, C4H2, H4a, C5H2, C6H2, C7H2, H8a,
C9H2, C10H2, H13, C16H2, C17H2), 1.82 d (2H,
C20H2, 7), 2.45 m [4H, (CH2)N], 3.70 m [4H,
(CH2)O], 5.30 s (1H, H11), 7.22 7.76 m (20H,
4C6H5). 13CNMR spectrum, C, ppm (J, Hz): 15.87 s
(C18), 17.35 s (C6), 19.13 s (C19), 19.43 s (C9),
20.34, 20.57 2s (C14, C15), 22.12 s (C4), 32.55 s
(C13), 32.90 d (C10a, J10A,P(2) 13), 35.28 d (C3, J3,P(1)
12), 35.90 s (C10), 36.46 s (C7), 37.74 s (C4b),
39.25 s (C5), 39.71 s (C8), 41.69 d (C16, C17, J16,P(1)
325(6)
258(7)
1385(7)
1897(6)
1327(6)
2001(8)
=
J17,P(2) 9), 42.70 q (C2, J2,P(1) 8, J2,P(2) 12),
48.32 s (C8a), 54.38 q (C1, J1,P(2) = J1,P(1) 8), 55.32
4a
_
_
s (C ), 56.22 s [(CH2)N], 67.21 s [(CH2)O], 69.29 s
(C20), 126.73 (C11), 127.71, 128.61 2d (8Cortho
,
,
4PC6H5, JC,P 28), 127.99, 128.17 2d (4Cpara
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 37 No. 8 2001

DERIVATIVES OF L-PIMARIC ACID IN THE SYNTHESIS
1147
Fig. 2. Crystal structure of compound XVIII according to X-ray diffraction analysis.
4PC6H5, JC,P 7), 131.69, 132.20, 133.61, 134.08 4d
(8Cmeta, 4PC6H5, JC,P 19), 137.13, 137.57, 140.55,
140.96 4d (4Cipso, 4PC6H5, JC,P 15), 149.92 s (C12).
31P NMR spectrum, P, ppm: 18.91, 21.96.
Found, %: C 79.97; H 8.45; N 1.84. C52H65NOP2.
Calculated, %: C 79.86; H 8.38; N 1.79.
Complex XXI. Under the conditions used in
preparation of complex XX from 0.06 g (0.12 mmol)
of
di- -chlorobis(1,5-cyclooctadiene)dirhodium,
0.16 g (0.24 mmol) of bisphosphine XIII, and 1 g of
NaBF4 we obtained 0.16 g (64%) of compound XXI,
orange crystals, mp 218 C (decomp.). 31P NMR
spectrum, P, ppm (J, Hz): 14.26 d.d (1P, JRh,P 138,
JP,P 30), 19.05 d.d (1P, JRh,P 143). Found, %:
Rh 9.23. C63H76ßF4OP2Rh. Calculated, %: Rh 9.35.
Complex XX. A mixture of 0.06 g (0.12 mmol) of
di- -chlorobis(1,5-cyclooctadiene)dirhodium, 20
l
of 1,5-cyclooctadiene, and 15 ml of dichloromethane
was boiled for 1 h, cooled to room temperature, and
0.16 g (0.024 mmol) of bisphosphine IX was added.
The reaction mixture was stirred for 2 h, and a solu-
tion of 1 g of NaBF4 in 5 ml of water was added.
After stirring for 3 h the water layer was separated,
the organic phase was dried with Na2SO4 and
evaporated. To the residue was added 5 ml of
methanol, 10 ml of water, the mixture was stirred for
1 h at 20 C, the precipitate was filtered off, washed
with 5 ml of water, and dried in a vacuum (1 mm Hg,
40 C). We obtained 0.17 g of complex XX, orange
crystals, mp 200 C (decomp.). 31P NMR spectrum,
P, ppm (J, Hz): 35.57 d.d (1P, JRh,P 116, JP,P 28),
39.49 d.d (1P, JRh,P 121). Found, %: Rh 9.48.
C63H76ßF4OP2Rh. Calculated, %: Rh 9.35.
Complex XXII. Under the conditions used in
preparation of complex XX from 0.06 g (0.12 mmol)
of
di- -chlorobis(1,5-cyclooctadiene)dirhodium,
0.18 g (0.24 mmol) of bisphosphine XIX, and 1 g of
NaBF4 we obtained 0.15 g (56%) of compound XXII,
dark-yellow crystals, mp 220 C (decomp.). 31P NMR
spectrum, P, ppm (J, Hz): 19.88 d.d (1P, JRh,P 142,
JP,P 37), 24.29 d.d (1P, JRh,P 144). Found, %: Rh
9.45.C60H77ßF4NOP2Rh. Calculated, %: Rh 9.53.
Hydrogenation of (Z)-2-acetylaminocinnamic
acid XXIII. To a solution of 0.62 g (3 mmol) of acid
XXIII in 10 ml of anhydrous ethanol was added
under hydrogen flow 0.03 mmol of complex XX. The
mixture was shaken at p(H2) 1.5 at, then the solvent
was evaporated, and the residue was subjected to
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 37 No. 8 2001

1148
TOLSTIKOV et al.
chromatography (SiO2, chloroform methanol, 15: 1,
then 10: 1, 1: 1). Similarly was carried out the
hydrogenation in the presence of complexes XXI,
XXII. The hydrogenation results are given in Table 1.
and Spirikhin, L.V., Mendeleev Commun., 1996,
no. 6, pp. 215 217.
13. Tolstikov, A.G., Karpyshev, N.N., Amosov, Yu.I.,
Tolstikova, O.V., Khlebnikova, T.B., Tolsti-
kov, G.A., Mamatyuk, V.I., and Salnikov, G.E.,
Mendeleev Commun., 1998, no. 2, pp. 60 62.
14. De Maio, P., Terpenoidy, Moscow: Inostr. Lit.,
1963, p. 245.
15. Zalkov, L.U., Ford, R.A., and Cutney, J.P., J. Org.
Chem., 1962, vol. 27, no. 10, pp. 3535 3539.
16. Halbrook, N.J. and Lawrence, R.V., J. Am. Chem.
Soc., 1958, vol. 80, no. 2, pp. 368 370.
17. Ayer, W.A., McDonald, C.E., and Stothers, J.B.,
Canad. J. Chem., 1963, vol. 41, no. 5, pp. 1113 1126.
18. Haslinger, E. and Hofner, D., Monatsh. Chem.,
1998, vol. 129, pp. 297 308.
19. Hofner, D. and Haslinger, E., Monatsh. Chem., 1998,
vol. 129, pp. 393 407.
Hydrogenation
of
2-acetylamino-3-(3,4-di-
methoxy-1-phenyl)-2-propenoic acid (XXIV). To a
solution of 0.82 g (3 mmol) of acid XXIV in 10 ml of
anhydrous tetrahydrofuran was added under hydrogen
flow 0.03 mmol of one of the complexes XX XXII.
The mixture was shaken at p(H2) 1.5 at, then the
solvent was evaporated, and the residue was subjected
to chromatography (SiO2, chloroform methanol,
10: 1, then ethyl acetate). The hydrogenation results
are given in Table 1.
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