MAGNETIC RESONANCE IN CHEMISTRY

Magn. Reson. Chem. 2000; 38: 977980

Note
Two epimeric friedelane triterpenes isolated from
Maytenus truncata Reiss:
1
H and
13
C chemical shift
assignments
G. C. M. Salazar,
1,2
G. D. F. Silva,
1

L. P. Duarte,
1
S. A. Vieira Filho
1,3
and I. S. Lula
1
1
UFMG, Departamento de Qumica, Instituto de Ci encias Exatas, Av. Ant onio Carlos 6627, Pampulha, CP 702, 31270-901 Belo Horizonte,
Minas Gerais, Brazil
2
UESB, Departamento de Qumica e Exatas, Rua Jos e Moreira Sobrinho s/n, CEP 45200-000, Jequi e, Bahia, Brazil
3
UFOP, DEFAR, Escola de Farmacia, Rua Costa Sena 171, CEP 35400-000, Ouro Preto, Minas Gerais, Brazil
Received 18 February 2000; revised 20 May 2000; accepted 30 June 2000
ABSTRACT: An NMR study of 3- and 3-friedelinol is described. In addition to conventional 1D NMR methods,
2D shift-correlated NMR experiments HMQC [(
1
J(C,H)], HMBC [
n
J(C,H); n D 2 and 3] and 2D
1
H,
1
H-NOESY
were used for
1
H and
13
C chemical shift assignments of these triterpenes. Copyright 2000 John Wiley & Sons, Ltd.
KEYWORDS: NMR;
1
H NMR;
13
C NMR; triterpenes; 3-friedelinol; 3-friedelinol; Maytenus truncata; Celastraceae
INTRODUCTION
This paper reports the
1
H and
13
C chemical shift assign-
ments of the triterpenes 3-friedelinol (1) and 3-friede-
linol (2), which were isolated during a phytochemical
investigation of Maytenus truncata Reiss (Celastraceae).
The results of the application of 1D and 2D spectral
techniques were used to identify the compounds and to
establish the
1
H and
13
C resonance assignments of these
triterpenes, which were also utilized to conrm
13
C NMR
data already published for -friedelinol. The
13
C NMR
spectral data for -friedelinol are hitherto unreported.
These data can be utilized in further investigations of
natural products.
* Correspondence to: G. D. F. Silva, UFMG, Departamento de Qumica,
Instituto de Ci encias Exatas, Av. Ant onio Carlos 6627, Pampulha,
CP 702, 31270-901 Belo Horizonte, Minas Gerais, Brazil; e-mail:
gdfsqui@dedalus.lcc.ufmg.br
Contract/grant sponsor: CNPq.
Contract/grant sponsor: CAPES.
EXPERIMENTAL
Plant material and isolation of the constituents
Maytenus truncata Reiss was collected in February 1996
at the periphery of the neighborhood Jequiezinho at the
margin of the river Contas in Jequi e City, Jequi e dis-
trict, Bahia State, Brazil. It was identied by botanist
Jos e Luiz Pedersoli, Universidade Federal de Minas
Gerais (UFMG). After botanical identication, a voucher
specimen (No. 25306A) representing this collection was
deposited at the Herbarium of the Natural History Museum
of the Universidade Federal de Minas Gerais, Belo Hori-
zonte, Minas Gerais, Brazil.
The dried and powdered leaves (1.0 kg) from Maytenus
truncata Reiss were extracted using n-hexane. The residue
(12.74 g) of the extract, after removal of the solvent,
was chromatographed on a silica gel column with n-
hexaneCH
2
Cl
2
, CH
2
Cl
2
AcOEt, AcOEt MeOH and
MeOH as eluents. The fraction eluted with CH
2
Cl
2
yielded
a mixture of friedelin, -friedelinol and -friedelinol. This
mixture was puried by preparative chromatography and
identied by comparation with
1
H and
13
C NMR data and
with an authentic sample isolated from other work.
NMR spectra
1
H and
13
C NMR spectra were measured on a Bruker
DRX 400 Avance spectrometer operating at 400 and
100 MHz, respectively, using CDCl
3
as solvent (approx-
imately 510 mg of sample were dissolved in 0.5 ml of
CDCl
3
with a few drops of pyridine-d
5
and transferred
into a 5 mm NMR tube), with TMS as internal reference.
Copyright 2000 John Wiley & Sons, Ltd. Magn. Reson. Chem. 2000; 38: 977980
978 G. C. M. SALAZAR ET AL.
One-dimensional
1
H and
13
C NMR spectra were acquired
under standard conditions. Standard pulse sequences were
used for 2D
1
H,
1
H-NOESY with a 290 ms mixing time.
Two-dimensional inverse hydrogen detected heteronuclear
shift correlation spectra were obtained by the HMQC pulse
sequence [
1
J(C,H)]. Two-dimensional inverse hydrogen
detected heteronuclear long-range correlation experiments
were carried out with HMBC pulse sequence [
n
J(CH); n D
2 and 3]. Data processing was carried out on an SGI work-
station computer with Bruker (DRX 400) microprograms.
RESULTS AND DISCUSSION
Comparative analysis of the
13
C NMR and DEPT-135
13
C NMR spectra of 1 and 2 was used to identify the
Table 1.
1
H (400MHz) and
13
C (100MHz) NMR for 3-friedelinol (1), including results obtained by heteronuclear
2D shift-correlated HMQC [
1
J(C,H)] and HMBC [
n
J(C,H); n D 2 and 3)
a
HMQC
Atom
C

H
HMBC
1
H,
1
H-NOESY
C
14 39.69 H-18, H-26, H-27
13 38.38 H-8, H-15, H-26, H-27
5 38.09 H-1, H-3, H-6, H-24
9 37.18 H-8, H-25
17 30.02 H-15, H-18, H-19, H-28
20 28.17 H-19, H-21, H-29, H-30
CH
3 71.59 3.81 (q-like, 2 H
eq
) H-2eq, H-23 H2
ax
, H-4, H-23
10 61.65 0.93 (dd, 12, 2 H
ax
) H-1, H-2, H-6, H-24, H-25 H-4, H-8, H-2
ax
, H-11
ax
8 53.27 1.28 (
b
, H
ax
) H-6, H-7, H-10, H-11, H-15,H-25, H-26 H-10, H-15
ax
, H-27
4 49.62 1.25 (
b
, H
ax
) H-2, H-23, H-24 H-23, H-2
ax
, H-10
18 42.88 1.56 (dd, 11, 6, H
ax
) H-12, H-27, H-28 H-26, H-28, H-12
CH
2
6 41.99 1.76 (td, 12, 3, H
eq
) H-24 H-23, H-24
0.99 (
b
, H
ax
)
22 39.28 0.93 (dd, 12, 2, H
ax
) H-18, H-28
1.49 (
b
, H
eq
)
2 36.14 1.99 (qd, 13, 3, H
eq
) H-1
ax
1.56 (
b
, H
ax
)
16 35.90 1.46 (
b
, H-16) H-22, H-28
1.18 (
b
, H-16)
11 35.66 1.42 (
b
, H-11) H-25
1.24 (
b
, H-11)
19 35.36 1.37 (
b
, H-19) H-18, H-29, H-30
1.21 (
b
, H-19)
21 32.88 1.49 (
b
, H-21) H-22, H-29, H-30
1.28 (
b
, H-21)
15 32.34 1.53 (
b
, H-15
ax
) H-8, H-26
1.28 (
b
, H-15
eq
)
12 30.69 1.34 (
b
, H-12) H-27
1.31 (
b
, H-12)
7 17.69 1.41 (
b
, H-7) H-6, H-8
1.39 (
b
, H-7)
1 16.16 1.69 (dt, 13, 3, H
ax
) H-3, H-10
1.45 (
b
, H
eq
)
CH
3
29 35.02 0.97 (s) H-19, H-30 H-27
28 32.12 1.18 (s) H-18, H-22 H-30, H-18, H-19, H-22
eq
30 31.85 1.02 (s) H-19, H-21, H-21, H-29
26 20.13 0.99 (s) H-15 H-25
27 18.69 1.02 (s) H-18 H-8, H-11, H-12,
25 18.35 0.89 (s) H-8 H-26, H-24, H-1
ax
24 16.58 1.10 (s) H-4, H-10 H-25, H-23, H1
ax
, H-6
eq
23 12.09 1.02 (d, 7) H-4 H-24
a
In CDCl
3
, with a few drops of the pyridine-d
5
, TMS used as internal reference (
H
D
C
D 0.00, chemical shifts () and coupling
constants (J, Hz, in parentheses). Chemical shifts and coupling constants of hydrogen atoms obtained from 1D
1
H NMR spectrum.
b
Overlapping signals.
Copyright 2000 John Wiley & Sons, Ltd. Magn. Reson. Chem. 2000; 38: 977980
EPIMERIC FRIEDELANE TRITERPENES 979
signals corresponding to six quatenary, ve methine,
eleven methylene and eight methyl carbon atoms. Cou-
plings were used to distinguish axial from equatorial ori-
entation when possible.
1
H and
13
C NMR resonance assignments of the natural
triterpenes were carried out by 2D shift-correlated NMR
techniques,
1
H,
1
H-NOESY, HMQC [
1
H,
13
C
1
J(C,H),
1
H
detected, reverse method], HMBC [
1
H,
13
C
n
J(C,H), n D 2
and 3,
1
H detected, reverse method].
1,2
The analysis of
these spectra was facilitated by comparison with published
13
C NMR data for friedelin
3
and 3-friedelinol.
4,5
The
data on the chemical shifts of hydrogen and carbons atom,
including 2D heteronuclear
1
J(C,H),
2
J(C,H) and
3
J(C,H)
correlations are summarized in Tables 1 and 2. The results
of this study were also used to conrm and eliminate some
wrong assignments reported in the literature.
Table 2.
1
H (400MHz) and
13
C (100MHz) NMR for 3-friedelinol (2), including results obtained by heteronuclear 2D
shift-correlated HMQC [
1
J(C,H)] and HMBC [
n
J(C,H); n D 2 and 3]
a
HMQC
Atom
C

H
HMBC
1
H,
1
H-NOESY
C
14 39.70 H-16, H-18, H-26, H-27
13 38.31 H-18, H-26, H-27
5 38.12 H-6, H-23, H-24
9 37.05 H-8, H-12, H-25
17 30.01 H-15, H-16, H-18, H-19, H-21, H-28
20 28.16 H-21, H-22, H-29, H-30
CH
3 71.11 3.41 (dt,10, 4, H
ax
) H-2, H-23 H-24, H-23, H1
ax
, H-2
eq
10 60.25 1.00 (
b
, H
ax
) H-2, H-6, H-24, H-25 H-8, H-6
ax
, H-4, H-2
ax
, H-11
4 53.41 1.17 (m, H
ax
) H-2, H-3, H-6, H-23, H-24 H-2
ax
, H-10
8 53.00 1.28 (
b
, H
ax
) H-6, H-25, H-26 H-10, H-15
ax
, H-27
18 42.88 1.54 (
b
, H
ax
) H-27, H-28 H-28, H-26, H-19, H-16
ax
CH
2
6 41.53 1.75 (td, 13, 2, H
eq
) H-24 H-23, H-24, H-7
ax
, H-7
eq
1.19 (
b
, H
ax
)
22 39.27 1.45 (dd, 5, 2 H
ax
) H-28 H-27, H-29, H-15
ax
0.89 (
b
, H
eq
)
2 37.00 2.16 (qd, 13, 3, H
eq
) H-1
ax
, H-1
eq
, H-3
1.38 (
b
, H
ax
)
16 36.12 1.48 (
b
, H-16) H-15, H-28
1.26 (
b
, H-16)
11 35.57 1.38 (
b
, H-11) H-8, H-12, H-25
1.18 (
b
, H-11)
19 35.36 1.41 (
b
, H-19) H-18, H-21, H-29, H-30
1.24 (d, 6, H
ax
)
21 32.88 1.46 (
b
, Hax) H-19, H-29, H-30
1.25 (
b
, Heq)
15 32.38 1.52 (
b
, Hax) H-16, H-26
1.28 (
b
, Heq)
12 30.64 1.31 (
b
, H-12) H-27
1.26 (
b
, H-12)
1 19.76 1.58 (m, Hax) H-2ax, H-2eq
1.35 (
b
, Heq)
7 17.92 1.38 (
b
, H-7)
1.32 (
b
, H-7)
CH
3
29 35.02 0.97 (s) H-19, H-30 H-21
eq
28 32.13 1.18 (s) H-16ax, H-16eq, H-18, H-22 H-16
30 31.86 1.02 (s) H-19ax, H19eq, H-21, H-29 H-19
26 20.18 0.98 (s) H-25, H-18
27 18.68 1.01 (s) H-12, H-18 H-29
25 18.17 0.81 (s) H-8 H-7, H-26
24 14.63 0.78 (s) H-10 H-25, H-7
ax
23 10.22 1.01 (d, 6) H-3, H-4 H-24, H-6
eq
a
In CDCl
3
, with a few drops of the pyridine-d
5
, TMS used as internal reference (
H
D
C
D 0.00, chemical shifts and coupling constants (J, Hz,
in parentheses). Chemical shifts and coupling constants of hydrogen atoms obtained from 1D
1
H NMR spectrum.
b
Overlapping signals.
Copyright 2000 John Wiley & Sons, Ltd. Magn. Reson. Chem. 2000; 38: 977980
980 G. C. M. SALAZAR ET AL.
The attribution of the chemical shifts of the non-
protonated and several protonated carbons was made
mainly on the basis of HMBC spectra. Methyl groups
are strategically located in these triterpenes, providing a
network of the two- and three-bond connectivities which
tie the molecule together and allow the assignment of the
13
C signals.
The starting point for the assignments for 1 was the
hydrogen attached to C-3 ( 71.59 and 3.81). This hydro-
gen H-3 showed correlations with C-5 ( 38.09) and C-1
( 16.16). C-3 showed a correlation with H-23 ( 1.02 d,
J D 7 Hz). which, in the 1D
1
HNMR spectrum, split into a
doublet, which ts the characteristic of the methyl group
at position 4 coupled with hydrogen H-4 ( 1.25). The
correlation of hydrogen atoms attached to C-23 with C-
4 ( 49.62) and C-3 conrm the above assignment. C-4
showed a correlation with H-24 (
H
1.10;
c
16.58), and C-
24 showed correlations with H-4 and H-10 ( 61.65, 0.93).
Working along the molecule in this fashion, it was possible
to assign all methyl
1
H signals and, by HMQC, the cor-
responding methyl
13
C signals (Table 1). The HMBC and
NOESY spectra allowed the assignment of other carbons.
NOESY spectra can give the stereo character of chem-
ical compounds. From the correlation between the hydro-
gen atom attached to C-3 and those attached to C-4, C-23
and C-2, it can be derived that the hydroxy group is on
the -face (Fig. 1). The 2 Hz coupling between H-3 and
H-4 and H-2 also conrms the stereochemistry. The cor-
relation between the hydrogen atom attached to C-29 and
those attached to C-27 allowed assignment these carbons
(Fig. 1).
Using the same procedure, the HMBC, HMQC and
NOESY spectra furnished the
1
H and
13
C chemical shifts
of 2 (Table 2). In compound 2 an inversion of C-4
and C-8 was observed, and also of C-1 and C-7 when
compared with -friedelinol. The stereochemistry of the
chiral carbon C-3, sustaining hydrogen atom H-3 (
H
3.41)
in an axial orientation (H-3), was dened on the basis
of the coupling constant value (dt, J D 10 and 4 Hz)
observed in the
1
H NMR spectrum and the NOE with
H-1
ax
, H-2
eq
, H-23 and H-24 revealed by the NOESY
spectrum (Table 2, Fig. 1).
In conclusion, the complete
1
H and
13
C chemical shift
assignments of the triterpenes 1 (Table 1) and 2 (Table 2),
possessing an extended proton spin system, were achieved
on the basis on the combined use of one-dimensional (
1
H
Figure 1. Some NOE relationship observed for - and
-friedelinol.
and
13
C) and two-dimensional NMR techniques (HMBC,
HMQC and NOESY). The two-dimensional NOESY tech-
nique proved to be particularly useful in making congu-
rational assignments for hydrogen atoms.
Acknowledgements
The authors are grateful to the CNPq and CAPES for grants and
fellowships and to Professor Jos e Luiz Pedersoli (UFMG) for botanical
identication.
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Copyright 2000 John Wiley & Sons, Ltd. Magn. Reson. Chem. 2000; 38: 977980