SUPPLEMENTARY MATERIAL
A New Rosane type Diterpenoid from Stachys parviflora and its
Density Functional Theory Studies
Umar Farooqa,*, Khurshid Ayuba,b, Muhammad Ali Hashmia, Rizwana
Sarwara, Afsar Khana,**, Mumtaz Alic, Manzoor Ahmadc, Ajmal Khand
a
) Department of Chemistry, COMSATS Institute of Information Technology,
Abbottabad-22060, Pakistan
b
) Department of Chemistry, College of Science, King Faisal University, Al-Hafouf,
31982, Saudi Arabia
c
) Department of Chemistry, University of Malakand, Chakdara, Dir (L), Pakistan
d
) H. E. J. Research Institute of Chemistry, International Center for Chemical and
Biological Sciences, University of Karachi, Karachi-75270, Pakistan
*Corresponding Author Address: Department of Chemistry, COMSATS Institute of
Information Technology, Abbottabad-22060, Pakistan
Ph. +92-992-383591–5; E-mail: umarf@ciit.net.pk (U. Farooq)
**Co-corresponding Author Address: Department of Chemistry, COMSATS Institute
of Information Technology, Abbottabad-22060, Pakistan
Ph. +92-992-383591–5; E-mail: afsarhej@gmail.com (A. Khan)
A New Rosane type Diterpenoid from Stachys parviflora and its
Density Functional Theory Studies
A New rosane type diterpenoid (1) has been isolated from the chloroform
fraction of Stachys parviflora. Structure of 1 was confirmed by one-(1D) and
two-dimensional (2D)-NMR techniques including correlation spectroscopy
(COSY), heteronuclear multiple quantum coherence (HMQC), heteronuclear
multiple bond correlation (HMBC), and nuclear Overhauser effect
spectroscopy (NOESY). A theoretical model for the electronic and
spectroscopic properties of compound 1 is also developed. The geometries and
electronic properties were modeled at B3LYP/6-31G* and the theoretical data
correlates nicely with the experimental ones.
Keywords: density functional theory; B3LYP; DFT; GIAO; Stachys parviflora;
diterpenoid
Fig S1. Linear regression analysis for 13C chemical shifts of compound 1
Fig S2. Linear regression analysis for 1H chemical shifts of compound 1
Fig. S3: (a). 1H▬1H COSY and important HMBC (H→C) correlations of compound
1; (b). NOESY correlations of compound 1
Table S1: 1H-NMR data (in CDCl3) and 13C-NMR of compound 1 in ppm and J in
Hz. Chemical shifts in ppm
(δ) 1H-NMR
(δ) 13C-NMR
13C1H-NMR (δ) and
Positio
calculated at
calculated at
NMR
B3LPY/6n
multiplicity
B3LPY/6(δ)
311+(2d,p)
311+(2d,p)
1
5.60, m
5.58
117.3
122
2
1.90, m
1.94,
24.1
24.3
1.27, m
1.89
3
1.82-1.87, m
1.27-0.91
30.2
31.4
4
43.1
48.2
5
2.60, d, J = 6 Hz
2.08
52.6
47.2
6
3.60, dd, J = 10, 6 Hz
4.23
81.9
77.9
7
1.60-1.69, m
1.39,1.22
30.4
32.3
8
1.80, m
1.36
33.3
40.41
9
40.4
41.0
10
146.9
149.56
11
1.52, m
1.52
39.6
36.3
1.45, m
1.36
12
1.30-1.35, m
1.51, 1.04
31.8
33.6
13
36.1
40.1
14
1.15, m
1.38, 0.84
42.4
39.0
1.22, m
15
16
17
18
19
20
5.87, dd, J = 16.8, 10.6 Hz
5.02, dd, J = 16.8, 1.4 Hz
4.92, dd, J = 10.6, 1.4 Hz
0.98, s
1.30, s
4.10, d, J = 10 Hz
3.45, d, J = 10 Hz
1.08, s
5.56
4.66, 4.22
154.6
105.6
149.9
1.02
1.02
3.30, 2.95
24.1
23.4
68.7
17.4
24.3
1.06
19.3
18.3
103.5
75.6
Table S2. 1H-NMR data (in CDCl3) and its comparison with the theoretical values
calculated at different levels of theories
3
4
5
6
7
8
9
10
11
1.41-1.01
(δ) 1H-NMR
calculated at
B3LPY/6311+(2d,p)
Sclaed
5.58
1.94,
1.89
1.27-0.91
2.32
4.71
1.55, 1.35
1.51
2.08
4.23
1.39,1.22
1.36
1.69, 1.51
12
13
14
1.68, 1.15
1.52
1.36
1.51, 1.04
1.53, 0.93
1.38, 0.84
15
16
17
18
19
20
6.18
5.18, 5.14
1.18
1.18
3.66, 3.27
1.27
5.56
4.66, 4.62
1.02
1.02
3.30, 2.95
1.06
Position
1
2
(δ)
calculated at
B3LPY/6311+(2d,p)
Unscaled
6.2
2.16, 2.14
1H-NMR
(δ)
calculated at
B3LPY/6311+(2d,p)
Unscaled
132.69
13C-NMR
27.63
35.37
52.28
53.34
85.33
36.23
43.88
45.64
162.41
40.54
37.64
44.66
43.44
162.75
112.86
20.27
27.56
82.86
21.14
(δ) 13C-NMR
calculated at
B3LPY/6311+(2d,p)
Scaled
122
24.3
31.4
48.2
47.2
77.9
32.3
40.41
41.0
149.56
36.3
33.6
40.1
39.0
149.9
103.5
17.4
24.3
75.6
18.3
Cartesian coordinates
Compound 1 optimized in gas phase
C
-2.37630200 -1.02032300
C
-0.91144100 -0.74204800
C
-0.46099600 0.70204200
C
-1.42145400 1.67362100
C
-2.90472400 1.42693400
C
-3.38830500 -0.03349100
H
-0.84901800 -0.81251500
H
-2.49585500 -0.98880200
H
-2.63741100 -2.04446500
H
-1.25442400 1.57662100
H
-1.17382200 2.71220100
H
-3.53031600 2.11125800
H
-3.08462800 1.68854700
C
0.08062100 -1.77232100
H
0.29629000 -1.58754600
H
-0.32655600 -2.78905700
C
3.85131000 1.15016500
C
3.04005400 2.30365800
C
1.58511800 2.11861900
C
1.82322700 -0.24879900
C
3.34885700 -0.22851100
H
3.75945500 1.22564500
H
3.18967200 2.32147700
H
1.02734300 2.99130500
C
1.00039000 0.91187500
H
1.76740500 -0.15875500
H
3.40654000 3.26735200
C
-4.72466900 -0.20558300
H
-4.68697500 -0.01336000
C
-5.89645200 -0.55517700
H
-6.02419800 -0.76525700
H
-6.78678400 -0.64562500
C
-3.50770500 -0.30952900
H
-4.23503300 0.36700100
H
-3.83594600 -1.33823000
H
-2.55485700 -0.16808400
C
-0.52893200 0.97049300
H
-0.29470500 2.02128500
H
0.20104600 0.37058700
H
-1.51624700 0.76413200
C
3.34922300 -1.28802800
C
1.37698400 -1.69929100
O
2.47500800 -2.31565300
H
1.23407400 -2.28141700
H
4.91724000 1.25907700
H
2.99342300 -0.84458000
H
4.33074600 -1.73962500
-0.40543700
-0.03285600
-0.39871900
0.34041600
0.00922000
0.25349200
1.06509700
-1.49676800
-0.10729400
1.42120200
0.08902300
0.59698300
-1.04168300
-0.58505600
-1.64368900
-0.52482600
-0.26733100
0.34902900
0.00497500
0.60736800
0.21055000
-1.35840200
1.44066100
-0.32958000
0.04613700
1.70132900
-0.02320300
-0.44505900
-1.51992200
0.08785400
1.14583100
-0.52895200
1.76297600
2.22581900
1.95096000
2.28087100
-1.92634500
-2.12592000
-2.47789800
-2.34957600
-0.90503100
0.22806000
-0.46293800
1.14733000
-0.03133700
-1.85127200
-1.08618000
C
H
H
H
4.18902500
5.24296400
4.13898000
3.83855300
-0.72486800 1.40243400
-0.83021300 1.11720900
-0.02008000 2.24143200
-1.70029200 1.75617500
Compound 1 optimized in CHCl3
C
-2.37626100 -1.02050200
C
-0.91165100 -0.74194400
C
-0.46164300 0.70242400
C
-1.42106500 1.67189300
C
-2.90447800 1.42659000
C
-3.38814300 -0.03469900
H
-0.84871200 -0.81466500
H
-2.49607700 -0.98688100
H
-2.63600200 -2.04511100
H
-1.25442500 1.56985700
H
-1.17352600 2.71105500
H
-3.52898800 2.10924500
H
-3.08423200 1.69121200
C
0.08043900 -1.77108600
H
0.29603600 -1.58164200
H
-0.32812300 -2.78753400
C
3.85207200 1.14861300
C
3.04150000 2.30300800
C
1.58597500 2.11830000
C
1.82314700 -0.24957900
C
3.34922500 -0.22925000
H
3.76048400 1.22256800
H
3.19232900 2.32162600
H
1.02830400 2.99104400
C
1.00055600 0.91158800
H
1.76666200 -0.16084600
H
3.40778200 3.26588000
C
-4.72364000 -0.20449500
H
-4.68339200 -0.01258200
C
-5.89778900 -0.55153000
H
-6.02737600 -0.76091100
H
-6.78738900 -0.64009300
C
-3.50864200 -0.31463300
H
-4.23475800 0.36194000
H
-3.83860600 -1.34334200
H
-2.55536900 -0.17621300
C
-0.53260700 0.97413200
H
-0.30106600 2.02610800
H
0.19748100 0.37620400
H
-1.52034700 0.76704900
C
3.35315600 -1.28816800
C
1.37496100 -1.69870900
O
2.47592600 -2.31849600
H
1.23064300 -2.28007800
-0.40669000
-0.03333600
-0.39770800
0.34546400
0.01373000
0.25448400
1.06410700
-1.49782100
-0.10866000
1.42587000
0.09675900
0.60477000
-1.03633700
-0.58802800
-1.64599000
-0.52944900
-0.26920600
0.34633000
0.00351000
0.60613100
0.21080400
-1.36037400
1.43769900
-0.33133900
0.04529900
1.69985000
-0.02782000
-0.44673300
-1.52159200
0.08457500
1.14267700
-0.53406200
1.76321800
2.22803900
1.94840500
2.28103600
-1.92473100
-2.12151500
-2.47857000
-2.34651900
-0.90411900
0.22738400
-0.46355200
1.14636600
H
H
H
C
H
H
H
4.91789200
2.99750700
4.33565200
4.18876300
5.24157500
4.14208600
3.83330400
1.25684500
-0.84711200
-1.73858400
-0.72098800
-0.83328900
-0.00872400
-1.69085300
-0.03316900
-1.85072600
-1.08261800
1.40515700
1.11872200
2.23779500
1.76967700
Compound 1 optimized in methanol
C
-2.37633600 -1.02047100
C
-0.91182600 -0.74191400
C
-0.46199300 0.70250600
C
-1.42065200 1.67127000
C
-2.90432500 1.42650600
C
-3.38796000 -0.03521900
H
-0.84877300 -0.81543200
H
-2.49632400 -0.98564500
H
-2.63545300 -2.04531700
H
-1.25357300 1.56740500
H
-1.17337900 2.71059200
H
-3.52790100 2.10819900
H
-3.08481200 1.69282900
C
0.08020400 -1.77086600
H
0.29565500 -1.58011800
H
-0.32923800 -2.78705700
C
3.85290000 1.14815200
C
3.04185800 2.30279400
C
1.58635400 2.11809200
C
1.82292300 -0.24990600
C
3.34940200 -0.22953400
H
3.76275000 1.22152900
H
3.19226900 2.32178900
H
1.02875800 2.99088100
C
1.00061600 0.91135500
H
1.76545000 -0.16159300
H
3.40824600 3.26536300
C
-4.72337200 -0.20353400
H
-4.68262800 -0.01049300
C
-5.89822700 -0.55008700
H
-6.02808700 -0.76029900
H
-6.78783400 -0.63723800
C
-3.50836700 -0.31731000
H
-4.23406000 0.35888200
H
-3.83873000 -1.34615500
H
-2.55481400 -0.18011900
C
-0.53488400 0.97545900
H
-0.30234600 2.02737900
H
0.19331700 0.37644800
H
-1.52364900 0.77022600
C
3.35557700 -1.28773400
-0.40763500
-0.03385900
-0.39790700
0.34719300
0.01609200
0.25504000
1.06330200
-1.49867100
-0.10964000
1.42736500
0.09901800
0.60936500
-1.03334700
-0.58922000
-1.64707600
-0.53048600
-0.26871900
0.34566100
0.00225600
0.60526200
0.21138100
-1.36004900
1.43703900
-0.33276800
0.04411400
1.69879200
-0.02901500
-0.44691900
-1.52155300
0.08401000
1.14200600
-0.53501700
1.76341700
2.22952300
1.94731000
2.28096900
-1.92461500
-2.12064700
-2.47992300
-2.34478400
-0.90371900
C
O
H
H
H
H
C
H
H
H
1.37427900
2.47625200
1.23016400
4.91839200
3.00145200
4.33855600
4.18787100
5.24034700
4.14220100
3.82976500
-1.69845200
-2.31908100
-2.27984100
1.25609800
-0.84723200
-1.73792000
-0.71993400
-0.83517600
-0.00494800
-1.68742800
0.22664900
-0.46525400
1.14550100
-0.03150100
-1.85082200
-1.08017500
1.40711000
1.12074000
2.23733200
1.77570400