Dattatraya H. Dethe*, Vijay Kumar B. and Rakesh Maiti ...
Transcript of Dattatraya H. Dethe*, Vijay Kumar B. and Rakesh Maiti ...
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Supporting InformationBiomimetic Total Syntheses of Chromane Meroterpenoids, Guadials B-C, Guapsidial A
and Psiguajadial D
Dattatraya H. Dethe*, Vijay Kumar B. and Rakesh Maiti
Department of Chemistry, Indian Institute of Technology-Kanpur, Kanpur - 208016, India.
Tel: + 91-512-2596537, Fax: + 91-512-2597436.
Email: [email protected]
Electronic Supplementary Material (ESI) for Organic & Biomolecular Chemistry.This journal is © The Royal Society of Chemistry 2018
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Table of Contents
General Information…………………………………..……………………………………….3
General procedures for the Substrates……………..………………………………..…………4
Preparation of substrates………..……………………………………..………………………5
General procedure for the products……………………………………..…………..…………7
Preparation of compounds……………………………………………...………...……………8
1H and 13C NMR Spectra of substrates…………………………………..…………………20
1H and 13C NMR Spectra of Compounds…………………………….……….…………….25
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1. General Information
All reactions were carried out under nitrogen atmosphere with dry solvents under anhydrous
conditions unless otherwise mentioned. All the chemicals used were purchased commercially,
and used without further purification. Anhydrous DMF was prepared by distilling from KOH.
Yields refer to chromatographically pure material, unless otherwise stated. Reactions were
monitored by thin layer chromatography (TLC) carried out on 0.25 mm Merck silica gel
plates (60F-254) using UV light as a visualizing agent and p-anisaldehyde stain as coloring
agent, and heat as development agents. Merck silica gel (particle size 100-200 and 230-400
mesh) was used for flash column chromatography.
Reagents were purchased at the highest commercial quality and used without further
purification, unless otherwise stated. NMR spectra were recorded on JEOL ECX 500 (1H:
500/400 MHz, 13C: 125/100 MHz) in Acetonitrile-D3 or CDCl3 having TMS 0.03% as
internal standard. Mass spectrometric data were obtained using WATERS-Q-T of Premier-
ESI-MS.
The following abbreviations were used to explain the multiplicities: s = singlet, d = doublet, t
= triplet, q = quartet, dd = doublet of doublet, ddd = doublet of a doublet of a doublet, dt =
doublet of a triplet, td = triplet of a doublet, m = multiplet, br = broad.
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Experimental Procedures:
Guadial B (1):
OH
HO OH
H
O OH
HO OH
H
O
Ph
O
Ph H
O+
H O
i) TMEDA (20 mol%)Et3N, MeOH, 25 °C
18 h, 40%ii) SiO2, MeOH
(+)--Pinene (9)
neat, 90 °C, 46%
OMe
CHOHO
OHCOH
Guadial B (1)
OH
H
6 8
Compound 6 was synthesized from commercially available phloroglucinol following the
procedure reported by Liu and co-workers.1
To a mixture of dialdehyde 6 (64 mg, 0.35 mmol, 1 equiv.), triethylamine (146 μL, 1.05
mmol, 3 equiv.) and benzaldehyde (0.36 mL, 3.50 mmol, 10 equiv.) in MeOH (0.500 mL)
was added, at 25°C, N,N,N′,N′-tetramethylethane-1,2-diamine (TMEDA) (10.5 μl, 0.07
mmol, 0.2 equiv.). And the reaction mixture was stirred for 18 h at the same temperature. The
reaction mixture was directly subjected to chromatography on silica gel (DCM/MeOH 20:1)
to give a yellow solid which was passed through a bed of silica gel (DCM) to give crude 8
(40.0 mg, 40 % yield) as colourless oil. Compound 8 was readily undergoing decomposition
hence the next reaction was performed immediately without proper purification.
A mixture of ether 8 (40.0 mg, 0.13 mmol, 1 equiv.) and (+)-α-pinene 9 (63.06 μL, 0.39
mmol, 3 equiv.) was stirred for 24 hrs. at 90 °C without adding any solvent. The mixture was
purified using column chromatography with 1-2% EtOAc-Hexane to separate excess α-
pinene. Then crude fraction obtained was further purified by preparative TLC to isolate
desired natural product (1) in pure state as a colorless oil; yield = 22.6 mg, 42%. Rf = 0.5 in
90:10 hexane-EtOAc; = +126.0° (c 0.025, CHCl3); IR (neat): vmax/cm-1 2921, 1635, [𝛼]28𝐷
1493, 1444, 1388, 1308, 1250, 1224, 1150, 1112, 1082, 1010, 945, 911, 885, 844, 782, 758,
734, 645, 607, 575, 547, 518; 1H NMR (400 MHz, CDCl3) δ 13.53 (s, 1H), 13.21 (s, 1H),
10.19 (s, 1H), 10.03 (s, 1H), 7.30 (br s, 1H), 7.28 (br s, 1H), 7.20 (t, J = 7.3 Hz, 1H), 7.10 (br
s, 1H), 7.08 (br s, 1H), 4.24 (s, 1H), 3.00 (br t, J = 8.6 Hz, 1H), 2.53 – 2.41 (m, 1H), 2.15 –
2.06 (m, 2H), 1.93 (dd, J = 9.3, 3.9 Hz, 1H), 1.57 – 1.49 (m, 1H), 1.28 (s, 3H), 1.06 (s, 3H),
1.01 (s, 3H); 13C NMR (100 MHz, CDCl3) δ 192.23, 191.68, 169.45, 168.90, 166.46, 142.61,
128.73, 127.47, 126.77, 104.10, 103.78, 101.59, 89.01, 56.37, 41.24, 40.69, 40.29, 39.19,
36.61, 29.78, 29.25, 27.97, 27.63, 22.94. HRMS (ESI) m/z calcd. for C25H27O5 [M+H]+
407.1853, found 407.1856.
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Guadial C (2):
OH
HO OH
H
O
Ph
O
H O8
(-)- -Pinene (10)neat, 90 °C, 42%
OCHO
HO
OHCOH
Guadial C (2)
A mixture of ether 8 (40.0 mg, 0.13 mmol, 1 equiv.) and (-)-β-pinene 10 (62.02 μL, 0.39
mmol, 3 equiv.) was stirred for 24 hrs. at 90 °C without adding any solvent. The mixture was
purified using column chromatography with 1-2% EtOAc-Hexane to separate excess β-
pinene. Then crude fraction obtained was further purified by preparative TLC to isolate
desired natural product (2) in pure state as a colorless oil; yield = 23 mg, 42%. Rf = 0.5 in
90:10 hexane-EtOAc; = -75.2° (c 0.029, CHCl3); IR (neat): vmax/cm-1 3433, 2923, 1634, [𝛼]28𝐷
1442, 1385, 1302, 1185, 1161, 1146, 1090, 1014, 978, 855, 766, 701, 609, 533; 1H NMR
(400 MHz, CDCl3) δ 13.51 (s, 1H), 13.13 (s, 1H), 10.11 (s, 2H), 7.28 (t, J = 7.2 Hz, 3H), 7.24
– 7.18 (m, 1H), 7.13 (d, J = 7.0 Hz, 2H), 3.99 (dd, J = 10.2, 6.9 Hz, 1H), 2.43 (dd, J = 14.4,
6.9 Hz, 1H), 2.32 – 2.27 (m, 1H), 2.25 – 2.16 (m, 1H), 2.15 – 2.10 (m, 1H), 2.07 (dd, J =
14.4, 3.0 Hz, 1H), 2.03 – 1.97 (m, 2H), 1.78 (ddd, J = 13.8, 11.4, 2.6 Hz, 2H), 1.50 (d, J =
10.2 Hz, 1H), 1.30 (s, 3H), 1.00 (s, 3H); 13C NMR (100 MHz, CDCl3) δ 192.28, 191.66,
169.56, 168.70, 164.73, 144.46, 128.64, 126.85, 126.38, 104.53, 104.17, 103.05, 86.27,
47.63, 43.74, 40.62, 38.39, 35.15, 30.01, 29.78, 27.60, 26.42, 24.65, 23.20; HRMS (ESI) m/z
calcd. for C25H27O5 [M+H]+ 407.1853, found 407.1858.
Compound 7:OH
HO OH
H
O
OPh7
OH
HO OH
OPh7a
POCl3, DMF
EtOAc, rt, 1h, 91%
Compound 7a was synthesized from commercially available phloroglucinol following the
procedure reported by Jonathan and co-workers.2
According the procedure reported by Bharate and co-workers3, To the solution of benzoyl-
phloroglucinol 7a (400 mg, 1.74 mmol, 1 equiv.) in ethyl acetate (12 mL) were added DMF
(0.15 mL, 1.91 mmol, 1.1 equiv.) and phosphoryl chloride (0.18 mL, 1.91 mmol, 1.1 equiv.)
at room temperature. The reaction mixture was further stirred for 30 min at the same
temperature. Water was added to the reaction mixture and extracted with ethyl acetate (2 x 50
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mL). The combined ethyl acetate layers were washed with brine and dried over Na2SO4 and
concentrated to afford the crude product. Column chromatography over silica gel using
hexane/EtOAc (70:30) as eluent provided 7 as a pale yellow solid. Yield = 408 mg, 91 %. Rf
= 0.3 in 70:30 hexane-EtOAc; MP = 170 °C ; IR (neat): vmax/cm-1 3242, 2925, 2854, 1627,
1599, 1523, 1489, 1434, 1380, 1307, 1274, 1228, 1192, 1130, 1100, 973, 927, 896, 875, 817,
802, 761, 730, 691, 607, 577, 432; 1H NMR (400 MHz, CD3CN) δ 13.46 (s, 1H), 10.02 (s,
1H), 7.59 – 7.54 (m, 2H), 7.51 (t, J = 7.4 Hz, 1H), 7.39 (t, J = 7.7 Hz, 2H), 5.90 (s, 1H); 13C
NMR (100 MHz, CD3CN) δ 198.96, 192.23, 140.55, 131.79, 128.16, 127.91, 117.41, 104.52,
103.83, 94.69; HRMS (ESI) m/z calcd. for C14H11O5 [M+H]+ 259.0606, found 259.0609.
Compound 11:OH
HO OH
H
O
OPh
KOH, MeI, MeOH
rt to reflux, 2 h, 50%
OH
HO OH
H
O
OPh
CH3
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According the procedure reported by Bharate and co-workers3, to the solution of formylated
benzoyl phloroglucinol 7 (258 mg, 1 mmol, 1 equiv.) in methanol (10 mL), was added
potassium hydroxide (112 mg, 2 mmol, 2 equiv.) was added, at room temperature, methyl
iodide (0.3 mL, 5 mmol, 5 equiv.). The reaction mixture was refluxed for 2 h. Solvent was
evaporated and the crude product was purified by silica gel column chromatography using
hexane/EtOAc (80:20) as eluent to afford 11 (136 mg, 50%) as pale yellow solid. Rf = 0.5 in
70:30 hexane-EtOAc. MP =140 °C; IR (neat): vmax/cm-1 2955, 2925, 2853, 1626, 1492, 1448,
1429, 1377, 1321, 1276, 1226, 1157, 1097, 976, 948, 836, 734, 697, 624, 607, 541, 476, 440; 1H NMR (400 MHz, CDCl3) δ 13.13 (s, 1H), 10.78 (s, 1H), 10.16 (s, 1H), 8.56 (s, 1H), 7.60
(t, J = 19.6 Hz, 5H), 2.00 (s, 3H); 13C NMR (100 MHz, CDCl3) δ 192.33, 166.22, 132.90,
129.75, 127.91, 29.78, 6.58; HRMS (ESI) m/z calcd. for C15H13O5 [M+H]+ 273.0757, found
273.0762.
Guapsidial A (3) and Psiguajadial D (4):
OH
HO OH
H
O
OPh
CH3
DDQ, CH3NO2, 50 °C, 2 hO
H H
Me
OH
OH
Psiguajadial D (4), 28%
CHO
O
O
OH H
Me
OH
OHCHO
Guapsidial A (3), 32%
-Caryophyllene (5)
H
+
11
To a solution of 11 (50 mg, 0.184 mmol, 1 equiv.) and DDQ (41.7 mg, 0.184 mmol, 1 equiv.)
in nitromethane (5 mL) was added β-caryophyllene (37.6 mg, 0.184 mmol) and the reaction
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mixture was stirred at 50 °C for 2 h. The solvent was then evaporated under vacuum and the
crude product was purified by silica gel column chromatography (hexane/ EtOAc = 95:5) to
get a viscous liquid as a mixture of two isomers. They could not be separated through silica
gel column chromatography. However, they were separated by careful preparative thin layer
chromatography (hexane/ EtOAc = 98:2) to afford 3 and 4 as colorless oils in 1:1 ratio in
60% combined yield (52 mg); Rf = 0.5 in 95:5 hexane-EtOAc.
Guapsidial A (3): Yield = 28mg (32%); = -25.4° (c 0.032, CHCl3); IR (neat): vmax/cm-1 [𝛼]28𝐷
2924, 2853, 1628, 1447, 1432, 1367, 1294, 1227, 1206, 1170, 1147, 1116, 1057, 1005, 888,
868, 773, 754, 695, 662, 606, 459; 1H NMR (400 MHz, CDCl3) δ 13.69 (s, 1H), 13.60 (s,
1H), 10.00 (d, J = 3.7 Hz, 1H), 7.61 (br d, J = 7.0 Hz, 2H), 7.51 (br t, J = 7.4 Hz, 1H), 6.4 Hz,
1H), 7.41 (br t, J = 7.6 Hz, 2H), 4.92 (br s, 1H), 4.89 (br s, 1H), 2.71 (dd, J = 11.2, 10.6 Hz,
1H), 2.53 – 2.39 (m, 2H), 2.20 (m, 2H), 2.12 (br d, 2H), 2.01 – 1.88 (m, 2H), 1.78 (m, 1H),
1.74 (m, 2H), 1.6 (m, 2H), 1.47 (m, 1H), 1.24 (s, 3H), 1.00 (s, 6H); 13C NMR (100 MHz,
CDCl3) δ 199.73, 191.80, 169.53, 166.88, 162.08, 152.04, 140.84, 131.58, 128.15, 127.87,
110.61, 104.20, 102.89, 101.36, 84.42, 53.39, 41.90, 38.00, 36.48, 35.36, 33.93, 33.88, 33.68,
30.33, 24.80, 22.59, 22.29, 21.31; HRMS (ESI) m/z calcd. for C30H35O5 [M+H]+ 475.2479,
found 475.2484.
Psiguajadial D (4): Yield = 24.3mg (32%); = -122.4° (c 0.046, CHCl3); IR (neat): [𝛼]28𝐷
vmax/cm-1 2924, 2853, 1628, 1447, 1431, 1367, 1226, 1206, 1169, 1147, 1057, 1005, 888,
868, 773, 754, 695, 662, 606, 459; 1H NMR (400 MHz, CDCl3) δ 13.70 (s, 1H), 13.23 (s,
1H), 10.23 (s, 1H), 7.46 (dd, J = 9.0, 4.7 Hz, 1H), 7.39 (m, 4H), 4.82 (d, J = 10.9 Hz, 2H),
2.61 (dd, J = 16.6, 5.4 Hz, 1H), 2.41 – 2.20 (m, 2H), 2.08 – 1.97 (m, 2H), 1.86 – 1.77 (m,
1H), 1.72 – 1.41 (m, 9H), 1.00 (s, 3H), 0.93 (s, 3H), 0.87 (s, 3H); 13C NMR (101 MHz,
CDCl3) δ 200.25, 192.04, 168.76, 167.16, 162.09, 151.90, 142.35, 130.12, 127.63, 126.62,
110.21, 104.08, 103.55, 100.63, 84.49, 53.06, 41.36, 37.36, 36.21, 34.88, 33.54, 33.43, 33.02,
30.09, 24.18, 21.98, 20.32; HRMS (ESI) m/z calcd. for C30H35O5 [M+H]+ 475.2479, found
475.2482.
REFERENCES:
1) Gao, Y.; Wang, G. Q.; Wei, K.; Hai, P.; Wang, F.; Liu, J. K. Org. Lett. 2012, 14, 5936–5939.
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2) Pepper, H. P.; Tulip, S. J.; Nakano, Y.; George, J. H. J. Org. Chem. 2014, 79, 2564−2573.
3) Bharate, S. B.; Bhutani, K. K.; Khan, S. I.; Tekwani, B. I.; Jacob, M. R.; Khan, I. A.; Singh, I. P. Bioorganic Med. Chem., 2006, 14, 1750–1760.
Specific rotation comparison of reported and synthesized natural products:
Natural product Specific rotation ( ) of the [𝛼]28𝐷
natural products isolated
Specific rotation ( ) of the [𝛼]28𝐷
synthesized natural products
(Current manuscript)
Guadial B (1)
(Chem. Eur. J., 2015, 21,
9022-9027)
+ 122.5° (c 0.56, CHCl3) +126.0° (c 0.025, CHCl3)
Guadial C (2)
(Chem. Eur. J., 2015, 21,
9022-9027)
- 75.1° (c 0.64, CHCl3) -75.2° (c 0.029, CHCl3)
Guapsidial A (3)
(Chem. Eur. J., 2015, 21,
9022-9027)
- 32.7° (c 0.95, CHCl3) -25.4° (c 0.032, CHCl3)
Psiguajadial D (4)
(Sci. Rep., 2017, 7, 1-15.)−149.0° (c 0.2, CHCl3) -122.4° (c 0.046, CHCl3)
1H and 13C NMR comparison of reported and synthesized Guadial B (1):
S.N.
1H-NMR data of 1(500 MHz, CDCl3)from natural source
(Chem. Eur. J. 2015, 21, 9022 – 9027)
1H-NMR data of 1(400 MHz, CDCl3)synthesized by us
(current manuscript)
13C-NMR data of 1(125 MHz, CDCl3)from natural source
(Chem. Eur. J. 2015, 21, 9022 – 9027)
13C-NMR data of 1(100 MHz, CDCl3)synthesized by us
(current manuscript)
1 13.52 (s, 1H) 13.53 (s, 1H) 192.3 192.23
2 13.21 (s, 1H) 13.21 (s, 1H) 191.7 191.68
3 10.19 (s, 1H) 10.19 (s, 1H) 169.5 169.45
4 10.03 (s, 1H) 10.03 (s, 1H) 169.0 168.90
5 7.28 (t, 7.4, 1H) 7.28 (br s, 1H) 166.5 166.46
6 7.28 (t, 7.4, 1H) 7.30 (br s, 1H) 142.7 142.61
7 7.20 (t, 7.4, 1H) 7.20 (t, J = 7.3 Hz, 1H) 128.8 128.73
8 7.09 (d, 7.4, 1H) 7.10 (br s, 1H) 126.8 126.77
9 7.09 (d, 7.4, 1H) 7.08 (br s, 1H) 127.5 127.47
10 4.24 (br s, 1H) 4.24 (s, 1H) 104.2 104.10
11 3.00 (ddd, 9.5, 9.0, 1.0, 1H) 3.00 (br t, J = 8.6 Hz, 1H) 103.9 103.78
9
12 2.47 (ddd, 13.5, 9.5, 3.5, 1H) 2.53 – 2.41 (m, 1H) 101.7 101.59
13 2.11, 2.13 (2H) 2.15 – 2.06 (m, 2H) 89.1 89.01
14 1.93 (m, 1H) 1.93 (dd, J = 9.3, 3.9 Hz, 1H) 56.5 56.37
15 1.53 (ddd, 13.5, 9.0, 1.6, 1H) 1.57 – 1.49 (m, 1H) 41.3 41.24
16 1.28 (s, 3H) 1.28 (s, 3H) 40.8 40.69
17 1.06 (s, 3H) 1.06 (s, 3H) 40.4 40.29
18 1.01 (s, 3H) 1.01 (s, 3H) 39.3 39.19
19 -- -- 36.7 36.61
20 -- -- 29.3 29.25
21 -- -- 28.1 27.97
22 -- -- 27.7 27.63
23 -- -- 23.0 22.94
1H and 13C comparison of reported and synthesized Guadial C (2):
S.N.
1H-NMR data of 2(500 MHz, CDCl3)from natural source
(Chem. Eur. J. 2015, 21, 9022 – 9027)
1H-NMR data of 2(400 MHz, CDCl3)synthesized by us
(current manuscript)
13C-NMR data of 2(125 MHz, CDCl3)from natural source
(Chem. Eur. J. 2015, 21, 9022 – 9027)
13C-NMR data of 2(100 MHz, CDCl3)synthesized by us
(current manuscript)
1 13.51 13.51 (s, 1H) 192.3 192.28
2 13.13 13.13 (s, 1H) 191.7 191.66
3 10.12 10.11 (s, 2H) 169.6 169.56
4 7.28 (t, 7.4, 1H) 7.28 (t, J = 7.2 Hz, 3H) 168.8 168.70
5 7.28 (t, 7.4, 1H) 7.24 – 7.18 (m, 1H) 164.8 164.73
6 7.13 (d, 7.4, 1H) 7.13 (d, J = 7.0 Hz, 2H) 144.5 144.46
7 3.99 (dd, 10.2, 7.0 Hz, 1H) 3.99 (dd, J = 10.2, 6.9 Hz, 1H) 128.7 128.64
8 2.43 (dd, 14.5, 7.0 Hz, 1H) 2.43 (dd, J = 14.4, 6.9 Hz, 1H) 126.9 126.85
9 2.30 (dd, 5.0, 4.8 Hz, 1H) 2.32 – 2.27 (m, 1H) 126.4 126.38
10 2.20 (m, 1H) 2.25 – 2.16 (m, 1H) 104.6 104.53
11 2.12 (dd, 14.5, 10.2, 1H) 2.15 – 2.10 (m, 1H) 104.2 104.17
12 2.08 (m, 1H) 2.07 (dd, J = 14.4, 3.0 Hz, 1H) 103.1 103.05
13 2.00, 1.98 2.03 – 1.97 (m, 2H) 86.3 86.27
10
14 1.80 (m, 1H) 1.78 (ddd, J = 13.8, 11.4, 2.6 Hz, 2H) 47.7 47.63
15 1.50 (d, 10.0, 1H) 1.50 (d, J = 10.2 Hz, 1H) 43.8 43.74
16 1.30 (s, 3H) 1.30 (s, 3H) 40.7 40.62
17 1.00 (s, 3H) 1.00 (s, 3H) 38.5 38.39
18 -- -- 35.2 35.15
19 -- -- 30.1 30.01
21 -- -- 27.7 27.60
22 -- -- 26.5 26.42
23 -- -- 24.7 24.65
24 -- -- 23.3 23.20
1H and 13C comparison of reported and synthesized Guapsidial A (3):
S.N.
1H-NMR data of 3(400 MHz, CDCl3)from natural source
(Chem. Eur. J. 2015, 21, 9022 – 9027)
1H-NMR data of 3(400 MHz, CDCl3)
synthesized(current manuscript)
13C-NMR data of 3(100 MHz, CDCl3)from natural source
(Chem. Eur. J. 2015, 21, 9022 – 9027)
13C-NMR data of 3(100 MHz, CDCl3)
synthesized(current manuscript)
1 13.69 (s, 1H) 13.69 (s, 1H) 199.8 199.73
2 13.60 (s, 1H) 13.60 (s, 1H) 191.9 191.80
3 10.00 (s, 1H) 10.00 (d, J = 3.7 Hz, 1H) 169.6 169.53
4 7.61 (d, 7.5, 1H)7.61 (d, 7.5, 1H) 7.61 (br d, J = 7.0 Hz, 2H) 167.0 166.88
5 7.51 (t, 7.5, 1H) 7.51 (br t, J = 7.4 Hz, 1H) 162.2 162.08
6 7.41 (t, 7.5, 1H)7.41 (t, 7.5, 1H) 7.41 (br t, J = 7.6 Hz, 2H) 152.1 152.04
7 4.92 (br s, 1H) 4.92 (br s, 1H) 140.9 140.84
8 4.89 (br s, 1H) 4.89 (br s, 1H) 131.6 131.58
9 2.70 (dd, 11.0, 10.6, 1H) 2.71 (dd, J = 11.2, 10.6 Hz, 1H) 128.2 128.15
10 2.48 (m, 1H)2.45 (m, 1H) 2.53 – 2.39 (m, 2H) 127.9 127.87
11 2.20 (m, 2H) 2.20 (m, 2H) 110.7 110.61
12 2.17 (2H) 2.12 (br d, 2H) 104.3 104.20
13 1.97 (m, 1H)1.92 (m, 1H) 2.01 – 1.88 (m, 2H) 103.0 102.89
14
1.78 (m, 1H)1.74 (m, 2H)1.71 (m, 2H)1.47 (m, 1H)
1.78 (m, 1H)1.74 (m, 2H)1.6 (m, 2H)1.47 (m, 1H)
101.4 101.36
15 1.24 (s, 3H) 1.24 (s, 3H) 84.5 84.42
16 0.99 (s, 6H) 1.0 (s, 6H) 53.5 53.39
17 -- -- 42.0 41.90
11
18 -- -- 38.1 38.00
19 -- -- 36.6 36.48
20 -- -- 35.4 35.36
21 -- -- 34.0 33.93
22 -- -- 34.0 33.88
23 -- -- 33.8 33.68
24 -- -- 30.4 30.33
25 -- -- 24.9 24.80
26 -- -- 22.7 22.59
27 -- -- 22.3 22.29
28 -- -- 21.4 21.31
1H and 13C comparison of reported and synthesized Psiguajadial D (4):
S.N.
1H-NMR data of 4(400 MHz, CDCl3)from natural source(Sci. Rep. 2017, 7, 1-15)
1H-NMR data of 4(400 MHz, CDCl3)synthesized by us
(current manuscript)
13C-NMR data of 4(100 MHz, CDCl3)from natural source(Sci. Rep. 2017, 7, 1-15)
13C-NMR data of 4(100 MHz, CDCl3)synthesized by us
(current manuscript)
1 13.71 (s, 1H) 13.70 (s, 1H) 200.3 200.25
2 13.23 (s, 1H) 13.23 (s, 1H) 192.1 192.04
3 10.23 (s, 1H) 10.23 (s, 1H) 168.9 168.76
4 7.47 (m, 1H) 7.46 (dd, J = 9.0, 4.7 Hz, 1H) 167.3 167.16
5 7.40 (m, 2H)7.39 (m, 2H) 7.39 (m, 4H) 162.2 162.09
6 4.83 (br s, 1H) 4.83 (br s, 1H) 152.0 151.90
7 4.80 (br s, 1H) 4.80 (br s, 1H) 142.5 142.35
8 2.61 (dd, J = 16.6, 5.4 Hz, 1H) 2.61 (dd, J = 16.6, 5.4 Hz, 1H) 130.2 130.12
9 2.26 (m, 2H) 2.41 – 2.20 (m, 2H) 127.7 127.63
10 2.03 (m, 1H) 2.08 – 1.97 (m, 2H) 126.7 126.62
11 1.82 (m, 1H) 1.86 – 1.77 (m, 1H) 110.3 110.21
12
1.66 (m, 2H)1.61 (m, 2H)1.60 (m, 2H)1.57 (m, 2H)1.49 (m, 1H)
1.72 – 1.41 (m, 9H) 104.2 104.08
13 1.00 (s, 3H) 1.00 (s, 3H) 103.7 103.55
14 0.93 (s, 3H) 0.93 (s, 3H) 100.9 100.63
15 0.87 (s, 3H) 0.87 (s, 3H) 84.6 84.49
16 -- -- 53.2 53.06
12
17 -- -- 41.5 41.36
18 -- -- 37.5 37.36
19 -- -- 36.4 36.21
20 -- -- 35.0 34.88
21 -- -- 33.7 33.54
22 -- -- 33.5 33.43
23 -- -- 33.2 33.02
24 -- -- 30.2 30.09
26 -- -- 24.3 24.18
27 -- -- 22.1 21.98
28 -- -- 20.4 20.32
13
1H and 13C NMR Spectra of Guadial B (1):
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.511.512.513.5f1 (ppm)
S#454958
3.77
3.83
4.18
1.82
1.36
2.65
1.45
1.37
1.25
1.17
1.24
1.32
1.94
1.18
1.14
1.25
1.27
1.01
1.06
1.28
1.50
1.50
1.54
1.56
1.56
1.92
1.93
2.09
2.11
2.13
2.98
3.00
3.02
4.24
7.08
7.10
7.18
7.20
7.22
7.28
7.30
10.0
310
.19
13.2
1
13.5
3
OCH3
CH3
CH3
OH
OH
O
O
Guadial B (1)
14
0102030405060708090100110120130140150160170180190200210f1 (ppm)
S#601343
22.9
427
.63
27.9
729
.25
36.6
139
.19
40.2
940
.69
41.2
4
56.3
7
89.0
1
101.
5910
3.78
104.
10
126.
7712
7.47
128.
73
142.
61
166.
4616
8.90
169.
45
191.
6819
2.23
OCH3
CH3
CH3
OH
OH
O
O
Guadial B (1)
1H and 13C NMR Spectra of Guadial C (2):
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.511.512.513.5f1 (ppm)
S#461393
3.01
1.34
2.19
2.04
1.31
1.08
1.23
1.11
1.17
1.13
2.05
1.16
2.14
2.01
1.00
1.01
1.00
1.48
1.51
1.80
1.98
1.99
2.08
2.11
2.12
2.15
2.30
2.40
2.42
2.44
2.45
3.97
3.99
4.00
4.01
7.12
7.14
7.19
7.21
7.23
7.23
7.23
7.27
7.28
7.30
10.1
1
13.1
3
13.5
1
OOH
OH
CH3
CH3
O
O
Guadial C (2)
15
0102030405060708090100110120130140150160170180190200f1 (ppm)
S#601411
23.2
024
.65
26.4
227
.60
29.7
830
.01
35.1
538
.39
40.6
243
.74
47.6
3
86.2
7
103.
0510
4.17
104.
53
126.
3812
6.85
128.
64
144.
46
164.
7316
8.70
169.
56
191.
6619
2.28
OOH
OH
CH3
CH3
O
O
Guadial C (2)
1H and 13C NMR Spectra of Compound 7:
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.511.512.513.5f1 (ppm)
S#700970
1.19
2.19
1.14
2.11
1.13
1.00
5.90
7.37
7.39
7.41
7.49
7.51
7.53
7.55
7.55
7.57
10.0
2
13.4
6
OH
OH OH
H
O
O
7
16
0102030405060708090100110120130140150160170180190200f1 (ppm)
S#723103
94.6
9
103.
8310
4.52
117.
41
127.
9112
8.16
131.
79
140.
55
192.
23
198.
96
OH
OH OH
H
O
O
7
1H and 13C NMR Spectra of Compound 11:
01234567891011121314f1 (ppm)
S#574611
3.27
5.06
1.03
1.00
1.05
1.03
2.00
7.54
7.62
7.64
8.56
10.1
6
10.7
8
13.1
3
OH
OH OH
H
O O
CH3
11
17
0102030405060708090100110120130140150160170180190200f1 (ppm)
S#703308
6.58
29.7
8
127.
9112
9.75
132.
90
166.
22
192.
33
OH
OH OH
H
O O
CH3
11
1H and 13C NMR Spectra of Guapsidial A (3):
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.511.512.513.5f1 (ppm)
S#683746
6.07
3.35
1.61
2.73
2.69
1.18
2.45
2.30
2.23
2.47
1.30
0.99
0.99
2.47
1.24
2.31
1.04
0.97
1.00
1.00
1.24
1.59
1.61
1.63
1.64
1.66
1.69
1.71
1.74
1.76
1.77
1.78
1.92
1.94
1.95
1.96
2.11
2.14
2.16
2.17
2.19
2.20
2.44
2.46
2.47
2.48
2.70
2.72
4.89
4.92
7.39
7.41
7.43
7.49
7.51
7.53
7.60
7.62
9.99
13.6
013
.69
O
O
CH3
CH3
H H
CH3
CH2 OH
OH
O
Guapsidial A (3)
18
0102030405060708090100110120130140150160170180190200f1 (ppm)
S#699713
21.3
122
.29
22.5
924
.80
30.3
333
.68
33.8
833
.93
35.3
636
.48
38.0
041
.90
53.3
9
84.4
2
101.
3610
2.89
104.
20
110.
61
127.
8712
8.15
131.
58
140.
84
152.
04
162.
0816
6.88
169.
53
191.
80
199.
73
O
O
CH3
CH3
H H
CH3
CH2 OH
OH
O
Guapsidial A (3)
1H and 13C NMR Spectra of Psiguajadial D (4):
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.511.512.513.5f1 (ppm)
S#689023
3.75
3.61
3.57
9.36
1.54
2.58
2.58
1.15
1.11
1.03
4.00
1.07
1.16
1.32
1.35
0.87
0.93
1.00
1.52
1.54
1.54
1.56
1.58
1.61
1.64
1.65
1.66
1.99
2.02
2.03
2.06
2.26
2.34
2.58
2.60
2.63
2.64
4.80
4.83
7.39
7.40
7.44
7.46
7.47
7.48
10.2
3
13.2
3
13.7
0
OCH3
CH3
H H
CH3
CH2 OH
OH
O
O
Psiguajadial D (4)
19
0102030405060708090100110120130140150160170180190200210f1 (ppm)
S#699667
20.5
422
.20
24.4
029
.79
30.3
133
.24
33.6
533
.76
35.1
036
.43
37.5
841
.58
53.2
8
84.7
1
100.
8510
3.77
104.
30
110.
43
126.
8412
7.85
130.
33
142.
57
152.
12
162.
3116
7.38
168.
98
192.
26
200.
47
OCH3
CH3
H H
CH3
CH2 OH
OH
O
O
Psiguajadial D (4)