Total Synthesis of cis-Reticulatacin10-ones A and B: Absolute … · 2017. 4. 2. · SI 1 Total...
Transcript of Total Synthesis of cis-Reticulatacin10-ones A and B: Absolute … · 2017. 4. 2. · SI 1 Total...
SI 1
Total Synthesis of cis-Reticulatacin-10-ones A and B: Absolute
Stereochemical Assignment
Sherif B. Abdel Ghani, Lynda J. Brown,
Bruno Figadère, and Richard C. D. Brown*
*Corresponding author [email protected]; FAX: +44 (0)23 80593781
Contents Page
1.0 General methods SI 2
2.0 Preparation of compounds SI 3
2.1 6-Bromo-N-methoxy-N-methyhexanamide (contains ~ 20% 6-chloro-N-methoxy-N-methyhexanamide) SI 3
2.2 1-Bromotridec-12-en-6-one (9) (contains ~ 20% 1-chlorotridec-12-en-6-one) SI 4
2.3 1-Bromotridec-12-en-6-ol (contains ~ 20% 1-chlorotridec-12-en-6-ol) SI 5
2.4 (±)-1-(Phenylsulfonyl)tridec-12-en-6-ol (6) SI 6
2.5 (1S,3R/S,8R/S)-1-[(2S,5R)-Tetrahydro-5-((1R)-1-hydroxytridecyl)furan-2-yl]-3-(phenylsulfonyl)pentadec-14-ene-1,8-
diolΨ SI 7
2.6 (1S,8R/S)-1-[(2S,5R)-Tetrahydro-5-((1R)1-hydroxytridecyl)furan-2-yl]pentadec-14-ene-1,8-diol (10B/A, ratio ~ 1:9) SI 8
2.7 (15S)-15-[(2S,5R)-Tetrahydro-5-((1R)1-hydroxytridecyl)furan-2-yl]-15-hydroxypentadec-1-en-8-oneΨ SI 9
2.8 (4E)-4,5-Didehydro-cis-reticulatacin-10-one B/A (11B/A, dr ~ 9:1) SI 10
2.9 cis-Reticulatacin-10-one B/A (4B/A, dr ~ 9:1) SI 12
3.0 NMR Spectra SI 3
3.1 1H NMR 6-Bromo-N-methoxy-N-methyhexanamide (contains ~ 20% 6-chloro-N-methoxy-N-methyhexanamide) SI 13
3.2 13C NMR 6-Bromo-N-methoxy-N-methyhexanamide (contains ~ 20% 6-chloro-N-methoxy-N-methyhexanamide) SI 14
3.3 1H NMR 1-Bromotridec-12-en-6-one (9) (contains ~ 20% 1-chlorotridec-12-en-6-one) SI 15
3.4 13C NMR 1-Bromotridec-12-en-6-one (9) (contains ~ 20% 1-chlorotridec-12-en-6-one) SI 16
3.5 1H NMR 1-Bromotridec-12-en-6-ol (contains ~ 20% 1-chlorotridec-12-en-6-ol) SI 17
3.6 13C NMR 1-Bromotridec-12-en-6-ol (contains ~ 20% 1-chlorotridec-12-en-6-ol) SI 18
3.7 1H NMR (±)-1-(Phenylsulfonyl)tridec-12-en-6-ol (6) SI 19
3.8 13C NMR (±)-1-(Phenylsulfonyl)tridec-12-en-6-ol (6) SI 20
3.9 1H NMR (1S,3R/S,8R/S)-1-[(2S,5R)-Tetrahydro-5-((1R)-1-hydroxytridecyl)furan-2-yl]-3-(phenylsulfonyl)pentadec-
14-ene-1,8-diolΨ SI 21
3.10 13C NMR (1S,3R/S,8R/S)-1-[(2S,5R)-Tetrahydro-5-((1R)-1-hydroxytridecyl)furan-2-yl]-3-(phenylsulfonyl)pentadec-
14-ene-1,8-diolΨ SI 22
3.11 1H NMR (1S,8R/S)-1-[(2S,5R)-Tetrahydro-5-((1R)1-hydroxytridecyl)furan-2-yl]pentadec-14-ene-1,8-diol (10A/B,
ratio ~ 1:9) SI 23
Ψ Mixture of A and B isomers in a ratio of 1:9
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SI 2
3.12 13C NMR (1S,8R/S)-1-[(2S,5R)-Tetrahydro-5-((1R)1-hydroxytridecyl)furan-2-yl]pentadec-14-ene-1,8-diol (10A/B,
ratio ~ 1:9) SI 24
3.13 1H NMR (15S)-15-[(2S,5R)-Tetrahydro-5-((1R)1-hydroxytridecyl)furan-2-yl]-15-hydroxypentadec-1-en-8-oneΨ SI 25
3.14 13C NMR (15S)-15-[(2S,5R)-Tetrahydro-5-((1R)1-hydroxytridecyl)furan-2-yl]-15-hydroxypentadec-1-en-8-oneΨ SI 26
3.15 1H NMR (4E)-4,5-Didehydro-cis-reticulatacin-10-one A/B (11A/B, dr ~ 1:9) SI 27
3.16 1H NMR (4E)-4,5-Didehydro-cis-reticulatacin-10-one A/B (11A/B, dr ~ 1:9) SI 28
3.17 13C NMR (4E)-4,5-Didehydro-cis-reticulatacin-10-one A/B (11A/B, dr ~ 1:9) SI 29
3.18 1H NMR (R,2Z,5E)-4-Nitrobenzyl 18-((2R,5S)-tetrahydro-5-((S)-1-hydroxyheptyl)furan-2-yl)-18-hydroxy-3-((S)-1-
hydroxyethyl)-11-oxooctadeca-2,5-dienoate (dr ~ 1:9) SI 30
3.19 13C NMR (R,2Z,5E)-4-Nitrobenzyl 18-((2R,5S)-tetrahydro-5-((S)-1-hydroxyheptyl)furan-2-yl)-18-hydroxy-3-((S)-1-
hydroxyethyl)-11-oxooctadeca-2,5-dienoate (dr ~ 1:9) SI 31
3.20 1H NMR cis-Reticulatacin-10-one A/B (4A/B, dr ~ 1:9) SI 32
3.21 1H NMR cis-Reticulatacin-10-one A/B (4A/B, dr ~ 1:9) SI 33
3.22 13C NMR cis-Reticulatacin-10-one A/B (4A/B, dr ~ 1:9) SI 34
3.23 1H NMR hydrazone byproduct SI 35
3.24 Mass spectrum of hydrazone byproduct SI 36
4.0 Chromatograms SI 36
4.1 Chiral HPLC chromatogram of synthetic cis-reticulatacin-10-one A/B (4A/B, dr ~ 1:9) SI 36
4.2 Chiral HPLC chromatogram of natural cis-reticulatacin-10-one A/B (4A/B) SI 37
4.3 Overlay of chiral HPLC chromatograms of natural cis-reticulatacin-10-one A/B (4A/B ) synthetic cis-reticulatacin-
10-one A/B (4A/B, dr ~ 1:9) SI 37
1.0 General methods
All reactions were carried out under an inert atmosphere in oven dried glassware. THF and Et2O were distilled
from sodium and benzophenone prior to use. Triethylamine and dichloromethane were dried by distillation from
CaH2. 1H NMR and
13C NMR spectra were recorded in CDCl3 solution using Bruker AC300, AV300 (300 and
75 MHz respectively) or Bruker DPX400 (400 and 100 MHz respectively) spectrometers. Chemical shifts are
reported in δ units using CHCl3 as an internal standard (δ 7.27 ppm 1H, δ 77.15 ppm
13C respectively). Infrared
spectra were recorded on a Nicolet 380 spectrometer fitted with a Diamond platform, as solids or neat liquids.
Melting points are uncorrected. Electron impact and chemical ionisation mass spectra were obtained using a
Fisons VG platform single quadropole mass spectrometer. Electrospray mass spectra were obtained using a
Micromass platform mass analyser with an electrospray ion source. Chiral HPLC separations were performed on
a Agilent 1120 Compact LC using a Chiral CD-Ph column (4.6 x 250 mm) eluting with isopropanol:hexane (1:4,
1 mL/min), monitored by UV detection at 210 nm.
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SI 3
2.0 Preparation of Compounds
2.1 6-Bromo-N-methoxy-N-methyhexanamide (contains ~ 20% 6-chloro-N-methoxy-N-methy
hexanamide)
4
N
OBr/Cl
OMe
To a stirred suspension of O,N-dimethylhydroxylamine hydrochloride (2.73 g, 27.98 mmol) in anhydrous
CH2Cl2 (60 mL), 6-bromohexanoyl chloride (8, 5.00 g, 23.4 mmol) was added slowly, followed by dropwise
addition of i-Pr2NEt (9 mL, 51.6 mmol) at 0 °C. The solution was allowed to warm to rt, then stirred at rt for 4 h
before dilution with CH2Cl2. The reaction mixture was washed with 1 N HCl (3 x 50 mL), brine (25 mL) and
dried (MgSO4) followed by concentration in vacuo affording the title Weinreb amide as a mixture (~4:1) with
the corresponding alkyl chloride (5.30 g, 27.7 mmol, 99%).* IR νmax (neat)/cm–1
2937 (s), 2865 (s), 1658 (s),
1460 (s), 1415 (m), 997 (s); 1H-NMR (300 MHz, CDCl3) δ 3.66 (3H, s, NOCH3), 3.39 (2H, t, J = 6.7 Hz,
CH2Br), 3.15 (3H, s, NCH3), 2.41 (2H, t, J = 7.4 Hz, CH2CON-), 1.87 (2H, quintet, J = 7.0 Hz, CH2), 1.64 (2H,
quintet, J = 7.1 Hz, CH2), 1.51-1.42 (2H, m, CH2); [selected signals for the alkyl chloride: 3.52 (2H, t, J = 6.7
Hz, CH2Cl), 1.83-1.77 (m, CH2)]; 13
C-NMR (75 MHz, CDCl3) δ 174.4 (C=O), 61.3 (OCH3), 33.6 (CH2), 32.6
(CH2), 31.6 (CH2), 27.9 (CH2), 23.7 (NCH3); [selected signals for the alkyl chloride: 44.9 (CH2), 33.5 (CH2),
32.5 (CH2), 27.7 (CH2), 23.9 (NCH3)]; LRMS (EI+) m/z 238 ([M+H]
+), 158 ([M–halide]
+); HRMS (ES
+) m/z
C8H16BrNNaO2 Calcd. 260.026, found 260.028.
*Yield calculated based on a 4:1 mixture of bromide and chloride
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SI 4
2.2 1-Bromotridec-12-en-6-one (9) (contains ~ 20% 1-chlorotridec-12-en-6-one)
4 4
9 (Br/Cl ~ 4:1)Br/Cl O
At –40 °C hept-7-enylmagnesium bromide in THF (30 mL of a 1.0 M solution, 30 mmol) was added dropwise to
a solution of 6-bromo-N-methoxy-N-methyhexanamide* (2.10 g, 9.17 mmol)* in THF (25 mL). The mixture
was left to stir at –35 ºC for 2 h. The reaction was quenched at –35 ºC by dropwise addition of cold water, then
allowed to warm to rt. The mixture was extracted with ether (3 x 30 mL). The combined organic extract was
washed with 1 N H2SO4 solution (20 mL) then water, brine, dried (MgSO4) and concentrated in vacuo to give a
colourless oil. Purification by silica gel column chromatography (Et2O/hexane, 1:19→1:9) gave the haloketones
as a colourless oil (1.452 g, 5.41 mmol, 59%).* IR νmax (neat)/cm–1
2931 (s), 2857 (s), 1712 (s), 1640 (s), 1460
(s), 1412 (m), 994 (s), 911 (s); 1H-NMR (300 MHz, CDCl3) δ 5.77 (1H, tdd, J = 6.8, 10.2, 17.0 Hz, CH=CH2),
5.02-4.87 (2H, m, CH=CH2), 3.38 (2H, t, J = 6.7 Hz, CH2Br), 2.39 (4H, q, J = 7.3 Hz, CH2C=OCH2), 2.03 (2H,
q, J = 6.8 Hz, CH2CH=CH2), 1.90-1.80 (2H, m, CH2CH2Br), 1.65-1.49 (4H, m, CH2), 1.41-1.20 (6H, m, CH2);
[selected signals for the alkyl chloride: 3.51 (2H, t, J = 6.6 Hz, CH2Cl), 1.81-1.75 (2H, m, CH2]; 13
C-NMR (75
MHz, CDCl3) δ 210.8 (C=O), 138.8 (CH=CH2), 114.4 (CH=CH2), 42.8 (CH2), 42.4 (CH2), 33.6 (CH2), 32.6
(CH2), 28.7 (CH2), 27.8 (CH2), 23.7 (CH2), 22.9 (CH2) [selected signals for the alkyl chloride: 44.8 (CH2Cl),
32.4 (CH2), 26.5 (CH2), 23.1 (CH2)]; LRMS (CI+) m/z 275 ([M+H]
+), 195 ([M–halide]
+); HRMS (ES
+) m/z
C13H23BrNaO Calcd. 297.083, found 297.083.
*Amounts and yields calculated based on a 4:1 mixture of bromide and chloride
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SI 5
2.3 1-Bromotridec-12-en-6-ol (contains ~ 20% 1-chlorotridec-12-en-6-ol)
4 4
(Br/Cl ~ 4:1)Br/Cl OH
To a solution of the ketone (9, 30 mg, 0.112 mmol)* in EtOH (1 mL) was added NaBH4 (12 mg, 0.33 mmol) at 0
°C. The reaction was left to warm to rt. After 30 min 1 N HCl was added dropwise to the reaction mixture
[CAUTION: evolution of H2 gas]. The mixture was extracted with ether (2 x 10 mL). The combined organic
extract was washed with water, brine, then dried (MgSO4) and concentrated in vacuo. Purification by silica gel
column chromatography (EtOAc/hexane, 1:19→1:9) gave the title alcohol as a colourless oil (29.9 mg, 0.112
mmol, 100%).* IR νmax (neat)/cm–1
3347 (br), 2927 (s), 2855 (s), 1640 (s), 1460 (s), 994 (s), 909 (s); 1H-NMR
(400 MHz, CDCl3) δ 5.81 (1H, tdd, J = 6.5, 10.3, 17.1 Hz, CH=CH2), 5.00 (1H, d, J = 17.1 Hz, CH=CHH), 4.94
(1H, d, J = 10.3 Hz, CH=CHH), 3.59 (1H, m, CHOH), 3.41 (2H, t, J = 6.8 Hz, CH2Br), 2.10-2.00 (2H, m,
CH2CH=CH2), 1.90-1.80 (2H, m, CH2CH2Br), 1.55-1.25 (14H, m) [selected signals for the alkyl chloride: 3.56
(2H, t, J = 6.7 Hz, CH2Cl), 1.83-1.77 (2H, m, CH2)]; 13
C-NMR (100 MHz, CDCl3) δ 139.1 (CH=CH2), 114.3
(CH=CH2), 71.9 (CHOH), 37.6 (CH2), 37.3 (CH2), 33.8 (CH2), 32.8 (CH2), 29.2 (CH2), 28.9 (CH2), 28.3 (CH2),
25.6 (CH2), 24.9 (CH2) [selected signals for the alkyl chloride: 45.2 (CH2Br), 37.4 (CH2), 32.7 (CH2), 27.1
(CH2), 25.1 (CH2)]; LRMS (EI+) m/z 277 ([M+H]
+).
*Amounts and yields calculated based on a 4:1 mixture of bromide and chloride
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SI 6
2.4 (±)-1-(Phenylsulfonyl)tridec-12-en-6-ol (6)
6
4 4PhO2S OH
To a stirred solution of the 1-bromotridec-12-en-6-ol (120 mg, 0.45 mmol)* in dry DMF (2 mL) at rt, was added
PhSO2Na (78 mg, 0.47 mmol). The reaction mixture was heated a 60 °C for 5 h. The cooled reaction mixture
was partitioned between ether and water. The combined ether extract was washed with 1 N HCl (aq), water,
brine, then dried (MgSO4) and concentrated in vacuo to give a cloudy oil. Purification by silica gel column
chromatography (EtOAc/hexane, 2:8→3:7) gave the title sulfone as a colourless oil (125 mg, 0.37 mmol, 82%).
IR νmax (neat)/cm–1
3526 (br), 2927 (s), 2855 (s), 1639 (s), 1447 (s), 1303 (s), 1144 (s), 1086 (s); 1H-NMR (400
MHz, CDCl3) δ 7.90 (2H, d, J = 7.8 Hz), 7.65 (1H, t, J = 7.5 Hz), 7.56 (2H, t, J = 7.5 Hz), 5.80 (1H, m, tdd, J =
6.8, 10.0, 17.1 Hz, CH=CH2), 4.98 (1H, d, J = 17.1 Hz, CH=CHH), 4.92 (1H, d, J = 10.0 Hz, CH=CHH), 3.53
(1H, m, CHOH), 3.07 (2H, m, CH2SO2), 2.03 (2H, q, J = 6.8 Hz, CH2CH=CH2), 1.77-1.67 (2H, m, CH2CH2S),
1.48-1.20 (14H, m); 13
C-NMR (100 MHz, CDCl3) δ 139.3 (CSO2), 139.1 (CH=CH2), 133.6 (CH), 129.3 (CH),
128.1 (CH), 114.3 (CH=CH2), 71.6 (CHOH), 56.2 (CH2), 37.5 (CH2), 37.0 (CH2), 33.7 (CH2), 29.1 (CH2), 28.9
(CH2), 28.3 (CH2), 25.5 (CH2), 25.1 (CH2), 22.7 (CH2); LRMS (CI+) m/z 361.2 ([M+Na]
+).
*Amounts calculated based on a 4:1 mixture of bromide and chloride
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SI 7
2.5 (1S,3R/S,8R/S)-1-[(2S,5R)-Tetrahydro-5-((1R)-1-hydroxytridecyl)furan-2-yl]-3-
(phenylsulfonyl)pentadec-14-ene-1,8-diol (mixture of B/A isomers ~1:9)
44
C11H23
HO
O
OHHH OH
SO2Ph
44
C11H23
HO
O
OHHH OH
SO2Ph
Ratio ~ 9:1
To a solution of the sulfone 6 (300 mg, 0.891 mmol) in dry THF (10 mL) at –78 °C, was added n-BuLi (730 µL
of 2.45 M in hexane, 1.76 mmol) dropwise. The reaction mixture left to stir at –78 °C for 30 min before adding
BF3•Et2O (225 µL, 1.76 mmol). The mixture was left to stir at –78 °C for 30 min, then a solution of enantiomeric
epoxides (5 B/A, er ~ 9:1, 138.6 mg, 0.444 mmol) in THF (1 mL) was added dropwise. The mixture was left to
stir at –78 °C for 1 h, then the cooling bath was removed and the reaction was allowed to warm to rt. Aqueous 1
N HCl (10 mL) was added dropwise, and the mixture was extracted with EtOAc (3 x 20 mL). The combined
organic extract was washed with water, brine, then dried (MgSO4) and concentrated in vacuo. Purification by
silica gel column chromatography (EtOAc/hexane, 2:8→3:7) gave a mixture of diastereoisomeric sulfones as a
colourless oil (160 mg, 0.246 mmol, 55%). ΙR νmax (neat)/cm–1
3381 (br), 2923 (s), 2853 (s), 1464 (s), 1447 (s),
1301 (s), 1143 (s), 1084 (s); 1Η-ΝΜR (300 ΜΗz, CDCl3) δ 7.89 (2Η, d, J = 7.7 Ηz), 7.64 (1Η, t, J = 6.9 Ηz),
7.55 (2Η, t, J = 7.4 Ηz), 5.80 (1Η, m, CΗ=CΗ2), 5.02-4.91 (2Η, m, CΗ=CΗ2), 3.90-3.70 (2Η, m, CΗΟ x 2),
3.60-3.48 (2Η, m, CΗΟΗ x 2), 3.47-3.30 (2Η, m), 2.10-1.70 (10Η, m), 1.55-1.20 (39Η, m), 0.92 (3H, t, J = 6.4
Hz, CH3); 13
C-NMR (75 MHz, CDCl3) [multiple signals observed due to the presence of diastereoisomers] δ
139.1 (C), 138.0 (CH), 133.6 (CH), 129.2 (2CH), 128.9 (2CH), 114.3 (CH2), 82.6 (CH), 82.4 (CH), 82.3 (CH),
74.1 (CHOH), 72.0 (CHOH), 71.8 (CHOH), 71.6 (CHOH), 71.2 (CHOH), 60.9 (CHSO2), 37.7 (CH2), 37.6
(CH2), 34.7 (CH2), 33.8 (CH2), 32.7 (CH2), 32.0 (CH2), 29.7 (CH2), 29.4 (CH2), 29.2 (CH2), 28.9 (CH2), 28.9
(CH2), 28.1 (CH2), 26.6 (CH2), 25.4 (CH2), 25.3 (CH2), 22.7 (CH2), 14.2 (CH3); LRMS (ES+) m/z 651.5
([M+H]+), 673.5 ([M+Na]
+).
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SI 8
2.6 (1S,8R/S)-1-[(2S,5R)-Tetrahydro-5-((1R)1-hydroxytridecyl)furan-2-yl]pentadec-14-ene-
1,8-diol (10B) (+ 10A, ratio ~ 9:1)
10B
4 4
C11H23
HO
O
OHHH
OH
10A
4 4
C11H23
HO
O
OHHH
OH
Ratio 10B/10A ~ 9:1
Τo a solution of 1-tetrahydro-5-(1-hydroxytridecyl)furan-2-yl)-3-(phenylsulfonyl)pentadec-14-ene-1,8-diol (A/B
isomers, ratio ~ 1:9) (130 mg, 0.200 mmol) in dry MeOH (5 mL) at 0 °C, was added Na2HPO4 (80 mg, 0.56
mmol) and stirred for 2 min before the addition of Na/Hg amalgam 10% (600 mg). The reaction was allowed to
warm to rt, left to stir for 3 h, then diluted with ether and dropwise addition of saturated NH4Cl (aq). The mixture
was extracted with EtOAc (4 x 10 mL) and the combined organic solution washed with water, brine, dried
(MgSO4) and concentrated in vacuo. Purification by silica gel column chromatography (EtOAc-hexane,
1:4→1:1) gave the title isomeric triols as a white solid (83 mg, 0.162 mmol, 81%). [α]27
D –0.07 (CHCl3, c 1.00);
Mp 55-58 °C; IR νmax (neat)/cm–1
3381 (br), 2917(s), 2849 (s), 1466 (s), 1308 (s), 1086 (s), 1026 (s); 1H-NMR
(400 MHz, CDCl3) δ 5.81 (1H, tdd, J = 6.8, 10.0, 17.1 Hz, CH=CH2), 4.99 (1H, qd, J = 1.8, 17.1 Hz, CH=CHH),
4.93 (1H, tdd, J = 1.3, 1.8, 10.0, CH=CHH), 3.85-3.78 (2H, m, CHO x 2), 3.62-3.54 (1H, m, CHOH), 3.45-3.38
(2H, m, CHOH x 2), 2.42 (3H, br, OH), 2.05 (2H, tq, J = 1.3, 6.8, CH2CH=CH2), 1.98-1.88 (2H, m, CH2 THF),
1.80-1.71 (2H, m, CH2 THF) 1.56-1.2 (42H, m), 0.88 (3H, t, J = 6.9 Hz, CH3); 13
C-NMR (100 MHz, CDCl3) δ
139.2 (CH), 114.3 (CH2), 82.8 (2 x CH), 74.5 (CH), 74.4 (CH), 72.1 (CH), 37.5 (CH), 34.2 (CH2), 34.1 (CH2),
33.8 (CH2), 32.0 (CH2), 29.8 (CH2), 29.8 (CH2), 29.7 (CH2), 29.4 (CH2), 29.3 (CH2), 29.0 (CH2), 28.3 (CH2),
25.8 (CH2), 25.7 (CH2), 25.7 (CH2), 25.6 (CH2), 22.8 (CH2), 14.2 (CH3); LRMS (ES+) m/z 511.5 ([M+H]
+),
533.5 ([M+Na]+); HRMS (ES
+) m/z C32H62NaO4 Calcd. 533.455, found 533.453.
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SI 9
2.7 (15S)-15-[(2S,5R)-Tetrahydro-5-((1R)1-hydroxytridecyl)furan-2-yl]-15-hydroxypentadec-
1-en-8-one (+ A isomer, dr ~ 9:1)
4 4
C11H23
HO
O
OHHH
O4 4
C11H23
HO
O
OHHH
O
Ratio ~ 9:1
At 0 °C, Dess-Martin periodinane (51.1 mg, 0.117 mmol) was added in two batches to a solution of the triols
(10B/A ratio ~ 9:1, 60 mg, 0.117 mmol) in dry CH2Cl2 (2 mL). After 5 h, the mixture was diluted with ether and
filtered through a plug of silica eluting with 30% EtOAc in hexane and then concentrated in vacuo. Purification
by silica gel column chromatography (EtOAc-hexane, 1:4→1:1) gave the title ketones as a white solid (33 mg,
0.064 mmol, 56%). The starting triols (10B/A ratio ~9:1, 20mg, 0.039mmol, 33%) were also recovered. [α]27
D –
0.06 (CHCl3, c 1.00); Mp 54-57 °C; IR νmax (neat)/cm–1
3441 (br), 2918 (s), 2849 (s), 1708 (s), 1640 (s), 1467 (s),
1414 (s), 1310 (s), 1079 (s), 1027 (s); 1H-NMR (400 MHz, CDCl3) δ 5.80 (1H, tdd, J = 6.5, 10.3, 16.8 Hz,
CH=CH2), 4.99 (1H, d, J = 16.8 Hz, CH=CHH), 4.94 (1H, d, J = 10.3, CH=CHH), 3.85-3.75 (2H, m, CHO x 2),
3.45-3.35 (2H, m, CHOH x 2), 2.43 (2H, br, OH), 2.38 (4H, t, J = 7.4 Hz, CH2C=OCH2), 2.08-2.01 (2H, m,
CH2CH=CH2), 1.98-1.88 (2H, m, CH2 THF), 1.80-1.71 (2H, m, CH2 THF) 1.56-1.2 (40H, m), 0.88 (3H, t, J =
6.7 Hz, CH3); 13
C-NMR (100 MHz, CDCl3) δ 211.6 (C=O), 139.0 (CH), 114.4 (CH2), 82.8 (CH x 2), 74.5 (CH),
74.4 (CH), 42.9 (CH2), 42.9 (CH2), 34.2 (CH2), 34.1 (CH2), 33.7 (CH2), 32.0 (CH2), 29.8 (CH2), 29.8 (CH2), 29.8
(CH2), 29.5 (CH2), 29.4 (CH2), 29.3 (CH2), 28.8 (CH2), 28.8 (CH2), 28.2 (CH2), 25.8 (CH2), 25.6 (CH2), 23.9
(CH2), 23.8 (CH2), 22.8 (CH2), 14.2 (CH3); LRMS (ES+) m/z 531.5 ([M+Na]
+); HRMS (ES
+) m/z C32H60NaO4
Calcd. 531.439, found 531.438.
Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2010
SI 10
2.8 (4E)-4,5-Didehydro-cis-reticulatacin-10-one B/A (11B/A, dr ~ 9:1)
6 4
C11H23
HO
O
OHHH
O
O
O6 4
C11H23
HO
O
OHHH
O
O
O
11B 11A
Ratio 11B/11A ~ 9:1
To a stirred solution of (15S)-15-[(2S,5R)-tetrahydro-5-((1R)1-hydroxytridecyl)furan-2-yl]-15-hydroxypentadec-
1-en-8-one (+ A isomer, dr ~ 9:1) (26 mg, 0.051 mmol) and alkyne (7, 14.0 mg, 0.056 mmol) in DMF (3 mL)
was added CpRu(MeCN)3PF6 (2.2 mg, 0.005 mmol, 10 mol %). The reaction was stirred at rt for 1 h, then
diluted with ether and filtered through a plug of silica eluting with 40 % EtOAc in hexane. The solvents were
removed in vacuo. Purification by silica gel column chromatography (EtOAc/hexane, 1:4→3:2) gave the title
butenolide (21.8 mg, 0.036 mmol, 71 %) as a white solid, and the uncyclised nitrobenzyl ester byproduct (3 mg,
0.004 mmol, 8 %). Data for 11B/A: [α]26
D +10.4 (CHCl3, c 1.0); Mp 63-66 °C; IR νmax (neat)/cm–1
3431 (w),
3321 (s), 2918 (s), 2849 (s), 1737 (s), 1703 (s), 1469 (s), 1409 (s), 1377 (s), 1323 (s), 1086 (s); 1H-NMR (400
MHz, CDCl3) δ 7.00 (1H, q, J = 1.5 Hz, CH=C), 5.59-5.43 (2H, m, CH=CHCH2C), 5.00 (1H, dq, J = 1.5, 6.9
Hz, CHCH3), 3.85-3.77 (2H, m, CHO x 2), 3.45-3.34 (2H, m, CHOH x 2), 2.95 (2H, d, J = 6.5 Hz, =CHCH2C),
2.44 (2H, br s, OH x 2), 2.40 (2H, t, J = 7.5 Hz, CH2C=OCH2), 2.38 (2H, t, J = 7.5 Hz, CH2C=OCH2), 2.07-1.99
(2H, m, CH2CH=CH),1.98-1.89 (2H, m, CH2 THF), 1.81-1.71 (2H, m, CH2 THF), 1.54-1.20 (34H, m), 1.41 (3H,
d, J = 6.9 Hz, CH3CH), 0.89 (3H, t, J = 6.8 Hz, CH3CH2); 13
C-NMR (100 MHz, CDCl3) δ 211.4 (C), 173.6 (C),
149.6 (CH=C), 134.3 (CH=CH), 133.7 (CH=C), 124.4 (CH=CH), 82.8 (CH), 82.7 (CH), 77.7 (CH), 74.5 (CH),
74.4 (CH), 42.9 (CH2C=OCH2), 42.6 (CH), 34.2 (CH2), 34.1 (CH2), 32.3 (CH2), 32.0 (CH2), 30.5 (CH2), 29.8
(CH2), 29.8 (CH2), 29.8 (CH2), 29.8 (CH2), 29.7 (CH2), 29.5 (CH2), 29.4 (CH2), 29.3 (CH2), 28.9 (CH2), 28.5
(CH2), 28.2 (CH2), 25.8 (CH2), 25.6 (CH2), 23.9 (CH2), 23.4 (CH2), 22.8 (CH2), 19.2 (CH3), 14.2 (CH3); LRMS
(ES+) m/z 628 ([M + Na]
+).
Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2010
SI 11
Data for (R,2Z,5E)-4-nitrobenzyl 18-((2R,5S)-tetrahydro-5-((S)-1-hydroxyheptyl)furan-2-yl)-18-
hydroxy-3-((S)-1-hydroxyethyl)-11-oxooctadeca-2,5-dienoate (+ A isomer, dr ~ 9:1)
6 4
C11H23
HO
O
OHHH
ORatio ~ 9:1
OH
O
O
NO2 6 4
C11H23
HO
O
OHHH
O OH
O
O
NO2
IR νmax (neat)/cm–1
3384 (br), 2922 (s), 2852 (s), 1738 (s), 1719 (s), 1457 (s), 1346 (s), 1148 (s), 1071 (s); 1H-
NMR (300 MHz, CDCl3) δ 8.23 (2H, d, J = 8.7 Hz ArH), 7.54 (2H, d, J = 8.7 Hz ArH), 6.14 (1H, s, CH=C),
5.57-5.36 (2H, m, CH=CHCH2C), 5.25 (2H, s, OCH2Ar), 4.37 (1H, m, CHOHCH3), 3.86-3.75 (2H, m, CHO x
2), 3.63 (1H, dd, J = 5.4, 13.4 Hz, =CHCHHC=), 3.45-3.35 (2H, m, CHOH x 2), 3.07 (1H, dd, J = 6.2, 13.4 Hz,
=CHCHHC=), 2.46 (2H, br s, OH), 2.42-2.37 (4H, m, CH2C=OCH2), 2.02-1.88 (4H, m, CH2), 1.82-1.65 (2H, m,
CH2), 1.52-1.17 (40H, m, CH2), 1.34 (3H, d, J = 6.4 Hz, CH3CHOH), 0.88 (3H, t, J = 6.6 Hz, CH3CH2); 13
C-
NMR (75 MHz, CDCl3) δ 211.8 (C=O), 166.0 (C), 143.7 (CH), 132.5 (CH), 128.4 (CH), 126.9 (CH), 123.9
(CH), 112.9 (CH), 82.8 (CH), 82.7 (CH), 74.5 (CH), 74.4 (CH), 70.5 (CH), 64.3 (CH2), 42.9 (CH2C=OCH2),
42.5 (CH2C=OCH2), 34.2 (CH2), 34.1 (CH2), 33.0 (CH2), 32.1 (CH2), 32.0 (CH2), 28.2 (CH2), 25.8 (CH2), 25.5
(CH2), 23.8 (CH2), 23.1 (CH2), 22.8 (CH2), 22.4 (CH2), 14.2 (CH3); LRMS (ES+) m/z 780 ([M+Na]
+).
Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2010
SI 12
2.9 cis-Reticulatacin-10-one B/A (4B/A, dr ~ 9:1)
6 4
C11H23
HO
O
OHHH
O
O
O6 4
C11H23
HO
O
OHHH
O
O
O
4B 4A
Ratio 4B/4A ~ 9:1
To a solution of (4E)-4,5-didehydro-cis-reticulatacin-10-one B/A (11B/A, dr ~ 9:1, 10 mg, 0.0165 mmol) and
NsNHNH2 (30.4 mg, 0.14 mmol) in THF (3 mL) was added a solution of NaOAc (11.5 mg, 0.14 mmol) in H2O
(1 mL). The mixture was stirred at rt for 36 h before EtOAc (10 mL) and brine (3 mL) were added. The organic
phase was separated, re-extracting the aqueous solution with EtOAc (2 x 10 mL) and the combined organics was
dried (MgSO4), and concentrated in vacuo. 1H NMR analysis of the crude product indicated that the reduction
had not proceeded to completion, so the crude material was heated in THF (1 mL) containing TsNHNH2 (6.0
mg, 0.032 mmol) and NaOAc (6.0 mg, 0.032 mmol) for 24 h. Following the same work-up procedure described
above, the obtained residue was dissolved in ether and washed with 1 M HCl (aq), brine, saturated KHCO3 (aq),
then dried (MgSO4). Purification by preparative normal phase HPLC (EtOAc/hexane, 35:65) gave cis-
reticulatacin-10-ones B/A (4B/A, dr ~ 9:1) (7 mg, 0.0115 mmol, 69 %) as a white solid along with the hydrazone
byproduct* (3.5 mg, 0.004 mmol, 25%). [α]26
D +13.7 (CHCl3, c 0.5); Mp 68-72 °C; IR νmax (neat)/cm–1
3449
(br), 2918 (s), 2849 (s), 1743 (s), 1703 (s), 1470 (s), 1458 (s), 1412 (s), 1321 (s); 1H-NMR (400 MHz, CDCl3) δ
6.98 (1H, q, J = 1.5 Hz, CH=C), 4.99 (1H, dq, J = 1.5, 6.8 Hz, CHCH3), 3.85-3.77 (2H, m, CHO x 2), 3.45-3.38
(2H, m, CHOH x 2), 2.43 (2H, br, s, OH), 2.26 (4H, t, J = 7.4 Hz, CH2C=OCH2), 2.26 (2H, t, J = 7.8 Hz,
CH2C=), 1.98-1.89 (2H, m, CH2 THF), 1.80-1.69 (2H, m, CH2 THF), 1.62-1.20 (48H, m), 1.41 (3H, d, J = 6.8
Hz, CH3CH), 0.87 (3H, t, J = 6.7 Hz, CH3CH2); 13
C-NMR (100 MHz, CDCl3) δ 211.6 (C), 174.0 (C) 149.0
(CH), 134.3 (C), 82.8 (CH), 82.7 (CH), 77.5 (CH), 74.5 (CH), 74.4 (CH), 42.9 (CH2C=OCH2), 42.8
(CH2C=OCH2), 34.2 (CH2), 34.1 (CH2), 32.0 (CH2), 29.8 (CH2), 29.8 (CH2), 29.5 (CH2), 29.4 (CH2), 29.3 (CH2),
29.2 (CH2), 29.1 (CH2), 28.2 (2CH2), 27.4 (CH2), 25.8 (CH2), 25.6 (CH2), 25.2 (CH2), 23.9 (CH2), 23.8 (CH2),
22.8 (CH2), 19.3 (CH3), 14.2 (CH3); LRMS (ES+) m/z 630 ([M+Na]
+); HRMS (ES
+) m/z C37H66Na O6 Calcd.
629.476, found 629.476.
*The hydrazone byproduct (12 mg, 0.014 mmol) was converted to the mixture of cis-reticulaticin-10-ones B/A
(dr ~ 9:1) by dissolving in THF (1 mL), water (0.2 mL) and AcOH (0.2 mL). The reaction mixture was left to
stir at rt for 3 days. The mixture was neutralised with saturated NaHCO3 (aq) and extracted with EtOAc (3 x 10
mL), dried (MgSO4) and purified by silica gel column chromatography (20 % to 50 % EtOAc/hexane, 1:41:1) to
give the diastereomeric mixture of acetogenins 4B/A (7 mg, 0.011 mmol, 78%).
Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2010
SI 13
3.0 NMR Spectra
3.1 1H NMR 6-Bromo-N-methoxy-N-methyhexanamide (contains ~ 20% 6-chloro-N-methoxy-N-methyhexanamide)
4
N
OBr/Cl
OMe
1.4
95
5
0.1
97
1
0.8
51
3
1.4
85
8
1.0
00
0
1.0
84
9
1.0
61
9
1.0
21
6
Inte
gra
l
7.2
70
0
3.6
63
03
.54
23
3.5
20
43
.49
78
3.4
17
33
.39
42
3.3
71
6
3.1
55
2
2.4
41
42
.41
70
2.3
92
01
.92
02
1.8
97
01
.87
32
1.8
48
21
.82
57
1.8
11
61
.78
79
1.7
62
91
.74
03
1.6
95
81
.67
20
1.6
45
21
.61
96
1.5
95
81
.51
96
1.5
02
61
.49
40
1.4
82
51
.47
09
1.4
53
21
.44
16
1.4
22
1
(ppm)
0.51.01.52.02.53.03.54.04.55.05.56.06.57.07.5
shbf4719/2 big scale crude amide
3.4
17
3
3.3
94
2
3.3
71
6
(ppm)
3.5
42
3
3.5
20
4
3.4
97
8
(ppm)
3.503.55
2.4
41
4
2.4
17
0
2.3
92
0
(ppm)
2.32.4
1.9
20
21
.89
70
1.8
73
21
.84
82
1.8
25
71
.81
16
1.7
87
9
1.7
62
91
.74
03
1.6
95
8
1.6
72
0
1.6
45
2
1.6
19
6
1.5
95
8
1.5
19
61
.50
26
1.4
94
01
.48
25
1.4
70
91
.45
32
1.4
41
61
.42
21
(ppm)
1.401.501.601.701.801.90
Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2010
SI 14
3.2 13
C NMR 6-Bromo-N-methoxy-N-methyhexanamide (contains ~ 20% 6-chloro-N-methoxy-N-methyhexanamide) 4
N
OBr/Cl
OMe
17
4.3
91
5
77
.57
49
77
.15
00
76
.72
51
61
.28
25
44
.91
69
33
.67
19
33
.50
34
32
.63
90
32
.47
05
32
.32
40
31
.67
93
27
.99
45
27
.70
88
26
.71
25
23
.89
21
23
.76
76
(ppm)
102030405060708090100110120130140150160170
shbf4719/2 crude amide
Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2010
SI 15
3.3 1H NMR 1-Bromotridec-12-en-6-one (9) (contains ~ 20% 1-chlorotridec-12-en-6-one)
1.0
000
2.0
768
0.4
012
1.7
668
4.4
415
2.2
146
1.9
764
4.5
745
6.8
063
Inte
gra
l
7.2
700
5.8
466
5.8
240
5.8
124
5.8
021
5.7
899
5.7
673
5.7
558
5.7
448
5.7
332
5.7
113
5.0
059
5.0
005
4.9
425
4.9
383
4.9
041
3.5
356
3.5
136
3.4
917
3.4
094
3.3
869
3.3
649
2.4
231
2.4
005
2.3
761
2.3
518
2.0
652
2.0
427
2.0
189
1.9
951
1.8
982
1.8
750
1.8
513
1.8
263
1.8
037
1.7
897
1.7
659
1.7
409
1.7
184
1.6
885
1.6
343
1.6
111
1.5
867
1.5
611
1.5
367
1.5
129
1.4
642
1.4
386
1.4
148
1.3
849
1.3
599
1.3
313
1.3
246
1.3
002
1.2
776
1.2
618
1.2
484
(ppm)
0.51.01.52.02.53.03.54.04.55.05.56.06.57.07.5
shbf4719/9 Ketone
5.8
240
5.8
124
5.8
021
5.7
899
5.7
673
5.7
558
5.7
448
5.7
332
5.7
113
(ppm)
5.7
5.0
059
5.0
005
4.9
425
4.9
383
4.9
041
(ppm)
4.95.0
3.5
356
3.5
136
3.4
917
3.4
094
3.3
869
3.3
649
(ppm)
3.43.5
2.4
231
2.4
005
2.3
761
2.3
518
(ppm)
2.4
2.0
652
2.0
427
2.0
189
1.9
951
(ppm)
2.00
4 4
9 (Br/Cl ~ 4:1)Br/Cl O
Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2010
SI 16
3.4 13C NMR 1-Bromotridec-12-en-6-one (9) (contains ~ 20% 1-chlorotridec-12-en-6-one)
210.8
735
138.8
837
114.4
525
77.5
749
77.1
500
76.7
251
44.8
583
42.8
584
42.4
774
33.6
206
32.6
463
28.7
637
28.7
344
27.8
333
26.5
660
23.7
529
22.9
324
(ppm)
102030405060708090100110120130140150160170180190200210
shbf4719/9 Ketone
4 4
9 (Br/Cl ~ 4:1)Br/Cl O
Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2010
SI 17
1.0
00
0
2.1
21
8
1.5
97
3
1.8
49
9
2.3
12
2
2.3
74
2
0.0
32
4
18
.24
1
Inte
gra
l
7.2
70
0
5.8
63
2
5.8
46
9
5.8
38
1
5.8
29
9
5.8
21
1
5.8
04
2
5.7
95
4
5.7
87
3
5.7
78
5
5.7
62
2
5.0
18
9
4.9
76
3
4.9
52
4
4.9
26
7
3.5
95
8
3.5
60
0
3.5
43
1
3.5
26
8
3.4
35
2
3.4
18
3
3.4
01
3
2.0
81
1
2.0
64
1
2.0
46
6
2.0
29
6
1.8
96
0
1.8
79
1
1.8
62
2
1.8
45
2
1.8
10
7
1.7
93
2
1.7
76
2
1.6
32
6
1.4
71
4
1.4
62
6
1.4
54
5
1.4
41
9
1.4
23
1
1.4
06
8
1.3
89
9
1.3
72
3
1.3
39
1
1.2
61
3
(ppm)
0.51.01.52.02.53.03.54.04.55.05.56.06.57.07.5
4921/21 Br-6-OH-13-tri5
.86
32
5.8
46
9
5.8
38
1
5.8
29
9
5.8
21
1
5.8
04
2
5.7
95
4
5.7
87
3
5.7
78
5
5.7
62
2
(ppm)
5.85
5.0
18
9
4.9
76
3
4.9
52
4
4.9
26
7
(ppm)
4.95.0
3.5
95
8
3.5
60
0
3.5
43
1
3.5
26
8
(ppm)
3.60
3.4
35
2
3.4
18
3
3.4
01
3
(ppm)
3.40
2.0
46
6
2.0
29
6
1.8
96
0
1.8
79
1
1.8
62
2
1.8
45
2
1.8
10
7
1.7
93
2
1.7
76
2
(ppm)
1.82.0
3.5 1H NMR 1-Bromotridec-12-en-6-ol (contains ~ 20% 1-chlorotridec-12-en-6-ol)
4 4
(Br/Cl ~ 4:1)Br/Cl OH
Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2010
SI 18
3.6 13
C NMR 1-Bromotridec-12-en-6-ol (contains ~ 20% 1-chlorotridec-12-en-6-ol)
13
9.1
56
1
11
4.3
78
8
77
.45
91
77
.15
00
76
.83
12
71
.90
47
45
.15
68
37
.62
22
37
.37
10
37
.34
20
33
.97
08
33
.82
59
32
.86
95
32
.69
57
29
.25
68
28
.98
63
28
.32
94
27
.05
44
25
.60
54
25
.07
41
24
.94
85
(ppm)
102030405060708090100110120130140
4921/21 Br-6-OH-13-tri
4 4
(Br/Cl ~ 4:1)Br/Cl OH
Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2010
SI 19
3.7 1
H NMR (±)-1-(Phenylsulfonyl)tridec-12-en-6-ol (6)
6
4 4PhO2S OH
2.0
00
0
1.0
37
7
2.1
78
4
0.8
17
4
1.9
07
7
1.4
34
2
3.0
70
0
2.6
57
0
3.2
75
3
23
.67
8
Inte
gra
l7
.90
91
7.8
89
17
.66
89
7.6
50
17
.63
19
7.5
81
17
.56
23
7.5
43
5
7.2
70
0
5.8
46
25
.82
93
5.8
20
55
.80
36
5.7
86
65
.77
79
5.7
70
35
.76
16
5.7
44
6
5.0
03
34
.96
06
4.9
36
84
.91
17
3.5
31
8
3.0
99
03
.07
90
3.0
58
9
2.0
60
42
.04
41
2.0
26
52
.00
96
1.7
39
91
.72
17
1.7
03
51
.39
61
1.3
65
41
.30
58
1.2
92
7
(ppm)
0.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.0
4719/66.1-sulphone-6-OH-tride-
13-ene
7.9
09
1
7.8
89
1
(ppm)
7.6
68
97
.65
01
7.6
31
9
7.5
81
17
.56
23
7.5
43
5
(ppm)
7.6
5.8
46
25
.82
93
5.8
20
55
.80
36
5.7
86
65
.77
79
5.7
70
35
.76
16
5.7
44
6
(ppm)
5.80
5.0
03
3
4.9
60
6
4.9
36
8
4.9
11
7
(ppm)
4.95.0
3.0
99
03
.07
90
3.0
58
9
(ppm)
2.0
60
42
.04
41
2.0
26
52
.00
96
(ppm)
2.00
1.7
39
91
.72
17
1.7
03
5
(ppm)
1.71.8
Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2010
SI 20
3.8 13
C NMR (±)-1-(Phenylsulfonyl)tridec-12-en-6-ol (6)
6
4 4PhO2S OH
139.3
494
139.0
982
133.6
984
129.3
418
128.1
150
114.3
402
77.4
688
77.1
500
76.8
312
71.6
826
56.2
849
37.5
835
37.0
329
33.7
679
29.1
892
28.9
284
28.3
778
25.5
378
25.1
417
22.7
075
(ppm)
102030405060708090100110120130140150160170
4719/66
Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2010
SI 21
3.9 1
H NMR (1S,3R/S,8R/S)-1-[(2S,5R)-Tetrahydro-5-((1R)-1-hydroxytridecyl)furan-2-yl]-3-(phenylsulfonyl)pentadec-14-ene-1,8-diol (mixture of
A and B isomers in a ratio of 1:9)
2.2
55
5
3.5
54
8
1.0
00
0
2.1
90
7
3.2
09
4
5.4
00
4
11
.98
3
50
.93
4
4.2
92
0
Inte
gra
l
7.9
07
67
.88
20
7.6
43
17
.62
05
7.5
82
17
.55
65
7.5
32
7
7.2
70
0
5.8
71
05
.84
96
5.8
16
15
.79
29
5.7
60
05
.73
75
5.0
18
14
.95
29
4.9
15
1
3.8
15
43
.74
65
3.7
11
23
.52
52
3.4
13
7
3.0
84
5
2.0
54
32
.03
23
2.0
09
81
.89
88
1.8
35
41
.81
35
1.6
34
31
.38
31
1.2
60
6
0.8
99
70
.87
96
0.8
57
0
(ppm)
0.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.5
shbf4719/100 pure reticulata thf sulfon 6OL 13 ene
7.9
07
6
7.8
82
0
(ppm)
7.6
43
17
.62
05
7.5
82
17
.55
65
7.5
32
7
(ppm)
5.8
71
05
.84
96
5.8
16
15
.79
29
5.7
60
05
.73
75
(ppm)
5.75.8
5.0
18
1
4.9
52
94
.91
51
(ppm)
3.8
15
43
.74
65
3.7
11
2
3.5
25
2
3.4
13
7
(ppm)
3.6
0.8
99
7
0.8
79
6
0.8
57
0
(ppm)
0.90
2.0
54
32
.03
23
2.0
09
8
1.8
98
81
.83
54
1.8
13
5
(ppm)
2.0
44
C11H23
HO
O
OHHH OH
SO2Ph
44
C11H23
HO
O
OHHH OH
SO2Ph
Ratio ~ 9:1
Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2010
SI 22
3.10 13
C NMR (1S,3R/S,8R/S)-1-[(2S,5R)-Tetrahydro-5-((1R)-1-hydroxytridecyl)furan-2-yl]-3-(phenylsulfonyl)pentadec-14-ene-1,8-diol (mixture
of A and B isomers in a ratio of 1:9)
139.1
328
138.0
413
133.6
971
133.6
385
129.2
065
128.9
794
114.3
646
82.6
296
82.3
952
82.2
707
77.5
749
77.1
500
76.7
251
74.0
805
72.0
806
71.9
707
71.7
876
71.6
191
71.2
308
71.1
429
71.0
550
60.9
602
37.7
743
37.6
937
37.5
619
37.1
443
36.9
758
36.9
172
34.7
195
34.5
290
33.8
258
32.7
562
32.0
310
29.7
673
29.4
596
29.2
765
28.9
981
28.2
802
28.1
117
26.7
858
26.6
612
25.9
067
25.6
356
25.4
671
25.3
060
22.7
932
14.2
148
(ppm)
102030405060708090100110120130140
shbf4719/100 pure reticulata thf sulfon 6OL 13 ene
44
C11H23
HO
O
OHHH OH
SO2Ph
44
C11H23
HO
O
OHHH OH
SO2Ph
Ratio ~ 9:1
Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2010
SI 23
10B
4 4
C11H23
HO
O
OHHH
OH
10A
4 4
C11H23
HO
O
OHHH
OH
Ratio 10B/10A ~ 9:1
3.11 1
H NMR (1S,8R/S)-1-[(2S,5R)-Tetrahydro-5-((1R)1-hydroxytridecyl)furan-2-yl]pentadec-14-ene-1,8-diol (10A/B, ratio ~ 1:9)
1.0
00
0
2.3
43
8
2.5
39
5
1.2
61
3
2.6
61
3
1.5
87
8
2.8
87
3
2.9
31
2
3.3
36
6
62
.96
0
4.4
99
1
Inte
gra
l5
.77
72
5.7
60
35
.02
46
5.0
20
25
.01
52
5.0
11
44
.98
13
4.9
77
54
.97
25
4.9
68
84
.95
31
4.9
50
64
.94
74
4.9
44
94
.94
18
4.9
28
04
.92
48
4.9
22
34
.91
98
4.9
16
73
.83
79
3.8
26
03
.81
22
3.8
00
33
.58
07
3.5
73
23
.56
25
3.4
40
93
.42
89
3.4
14
53
.39
88
2.5
69
72
.07
86
2.0
61
62
.04
53
2.0
42
82
.02
90
2.0
25
92
.02
27
1.9
68
21
.96
38
1.9
51
91
.93
99
1.9
33
71
.92
68
1.9
22
41
.90
86
1.9
04
21
.89
54
1.7
93
21
.78
19
1.7
76
91
.76
49
1.7
60
61
.75
30
1.7
46
81
.73
55
1.7
24
81
.71
92
1.7
08
51
.47
96
1.4
67
61
.45
13
1.4
35
71
.40
30
1.3
87
41
.36
92
1.3
21
51
.31
34
1.2
60
70
.90
00
0.8
83
10
.86
55
(ppm)
0.51.01.52.02.53.03.54.04.55.05.56.06.57.07.5
4921/ HPLC F-2
5.8
61
9
5.8
45
05
.83
62
5.8
28
75
.81
99
5.8
02
35
.79
35
5.7
86
05
.77
72
5.7
60
3
(ppm)
5.765.805.84
5.0
24
65
.02
02
5.0
15
25
.01
14
4.9
81
34
.97
75
4.9
72
54
.96
88
4.9
53
14
.95
06
4.9
47
44
.94
49
4.9
41
84
.92
80
4.9
24
84
.92
23
4.9
19
84
.91
67
(ppm)
4.924.965.00
3.8
37
93
.82
60
3.8
12
23
.80
03
(ppm)
3.5
80
73
.57
32
3.5
62
5
3.4
40
93
.42
89
3.4
14
53
.39
88
(ppm)
3.43.53.6
0.9
00
0
0.8
83
1
0.8
65
5
(ppm)
0.90
Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2010
SI 24
3.12 13
C NMR (1S,8R/S)-1-[(2S,5R)-Tetrahydro-5-((1R)1-hydroxytridecyl)furan-2-yl]pentadec-14-ene-1,8-diol (10A/B, ratio ~ 1:9)
10B
4 4
C11H23
HO
O
OHHH
OH
10A
4 4
C11H23
HO
O
OHHH
OH
Ratio 10B/10A ~ 9:1
139.2
045
114.3
498
82.8
493
77.4
688
77.1
500
76.8
312
74.4
742
74.4
453
72.0
593
37.5
835
34.2
509
34.1
736
33.8
549
32.0
485
29.7
977
29.7
784
29.7
494
29.4
886
29.3
051
29.0
153
28.2
522
25.8
469
25.7
406
25.6
923
25.6
344
22.8
137
14.2
455
(ppm)
102030405060708090100110120130140
4921/6
desulphonated-6-OH-13ene
Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2010
SI 25
3.13 1
H NMR (15S)-15-[(2S,5R)-Tetrahydro-5-((1R)1-hydroxytridecyl)furan-2-yl]-15-hydroxypentadec-1-en-8-one (mixture of A and B isomers in
a ratio of 1:9)
4 4
C11H23
HO
O
OHHH
O4 4
C11H23
HO
O
OHHH
O
Ratio ~ 9:1
1.0
00
0
2.1
77
7
2.1
45
4
2.3
93
6
6.7
11
0
2.4
88
9
2.4
98
0
2.4
51
6
49
.98
5
3.7
44
0
Inte
gra
l
7.2
70
0
5.8
50
0
5.8
33
7
5.8
24
9
5.8
17
4
5.8
08
0
5.7
91
0
5.7
82
2
5.7
74
7
5.7
65
3
5.7
49
0
5.0
15
2
4.9
72
5
4.9
51
2
4.9
26
1
3.8
23
5
3.8
14
7
3.4
35
8
3.4
23
3
3.4
08
9
3.3
95
7
2.4
34
2
2.4
05
3
2.3
86
5
2.3
68
3
2.0
74
8
2.0
57
2
2.0
39
7
2.0
22
1
1.9
70
0
1.9
38
7
1.9
27
4
1.7
66
8
1.7
55
5
1.7
39
2
1.6
48
9
1.6
11
9
1.5
93
1
1.5
74
3
1.5
55
5
1.4
70
2
1.4
56
4
1.4
36
3
1.4
16
2
1.3
96
8
1.3
79
2
1.3
61
0
1.2
63
2
0.9
01
9
0.8
85
6
0.8
68
7
(ppm)
0.51.01.52.02.53.03.54.04.55.05.56.06.57.0
shbf/4921/8
5.8
33
7
5.8
24
9
5.8
17
4
5.8
08
0
5.7
91
0
5.7
82
2
5.7
74
7
5.7
65
3
5.7
49
0
(ppm)
5.85
5.0
15
2
4.9
72
5
4.9
51
2
4.9
26
1
(ppm)
4.905.00
2.4
34
2
2.4
05
3
2.3
86
5
2.3
68
3
(ppm)
2.40
2.0
74
8
2.0
57
2
2.0
39
7
2.0
22
1
1.9
70
0
1.9
38
7
1.9
27
4
1.7
66
8
1.7
55
5
1.7
39
2
(ppm)
1.71.81.92.0
0.9
01
9
0.8
85
6
0.8
68
7
(ppm)
0.850.90
Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2010
SI 26
21
1.6
23
8
13
8.9
91
9
11
4.4
94
7
82
.79
13
77
.46
88
77
.15
00
76
.83
12
74
.48
39
74
.42
59
42
.89
64
42
.85
78
34
.25
09
34
.14
47
33
.70
03
32
.04
85
29
.83
64
29
.80
74
29
.75
91
29
.55
63
29
.48
86
29
.31
48
28
.84
14
28
.80
28
28
.25
22
25
.84
69
25
.64
40
23
.91
49
23
.81
83
22
.81
37
14
.24
55
(ppm)
102030405060708090100110120130140150160170180190200210
shbf/4921/83
4.2
50
9
34
.14
47
33
.70
03
32
.04
85
29
.83
64
29
.80
74
29
.75
91
29
.55
63
29
.48
86
29
.31
48
28
.84
14
28
.80
28
28
.25
22
25
.84
69
25
.64
40
23
.91
49
23
.81
83
22
.81
37
(ppm)
222324252627282930313233343536
3.14 13
C NMR (15S)-15-[(2S,5R)-Tetrahydro-5-((1R)1-hydroxytridecyl)furan-2-yl]-15-hydroxypentadec-1-en-8-one (mixture of A and B isomers
in a ratio of 1:9
4 4
C11H23
HO
O
OHHH
O4 4
C11H23
HO
O
OHHH
O
Ratio ~ 9:1
Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2010
SI 27
3.15 1
H NMR (4E)-4,5-Didehydro-cis-reticulatacin-10-one A/B (11A/B, dr ~ 1:9)
6 4
C11H23
HO
O
OHHH
O
O
O6 4
C11H23
HO
O
OHHH
O
O
O
11B 11A
Ratio 11B/11A ~ 9:1
1.0
054
2.1
163
1.0
000
2.1
890
2.2
532
2.2
325
6.6
710
2.4
611
2.5
298
2.5
432
6.7
038
6.1
027
4.9
483
33.1
85
3.9
973
Inte
gra
l
7.2
700
7.0
097
7.0
066
5.5
909
5.5
753
5.5
527
5.5
364
5.5
213
5.5
094
5.4
937
5.4
774
5.4
555
5.4
392
5.0
164
5.0
127
4.9
995
4.9
957
3.8
210
3.8
147
3.4
478
3.4
352
3.4
227
3.4
064
3.3
938
2.9
636
2.9
485
2.4
448
2.4
141
2.4
028
2.3
959
2.3
846
2.3
777
2.3
664
2.0
717
2.0
541
2.0
365
2.0
196
1.9
700
1.9
550
1.9
381
1.9
268
1.9
105
1.7
675
1.7
555
1.7
392
1.6
508
1.6
125
1.5
937
1.5
749
1.5
561
1.5
373
1.4
702
1.4
551
1.4
231
1.4
056
1.3
855
1.3
673
1.3
479
1.2
613
0.9
000
0.8
837
0.8
662
(ppm)
0.51.01.52.02.53.03.54.04.55.05.56.06.57.0
4921/10 (F-1)didehydro reticulatacin-10-one
7.0
097
7.0
066
(ppm)
7.00
5.5
909
5.5
753
5.5
527
5.5
364
5.5
213
5.5
094
5.4
937
5.4
774
5.4
555
5.4
392
(ppm)
5.505.60
5.0
164
5.0
127
4.9
995
4.9
957
(ppm)
5.00
3.8
210
3.8
147
(ppm)
3.80
3.4
478
3.4
352
3.4
227
3.4
064
3.3
938
(ppm)
3.45
2.4
448
2.4
141
2.4
028
2.3
959
2.3
846
2.3
777
2.3
664
(ppm)
2.42.5
0.9
000
0.8
837
0.8
662
(ppm)
0.9
1.4
231
1.4
056
(ppm)
Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2010
SI 28
3.16 1
H NMR (4E)-4,5-Didehydro-cis-reticulatacin-10-one A/B (11A/B, dr ~ 1:9)
6 4
C11H23
HO
O
OHHH
O
O
O6 4
C11H23
HO
O
OHHH
O
O
O
11B 11A
Ratio 11B/11A ~ 9:1
5.4
94
45
.49
12
5.4
80
65
.47
81
5.4
74
95
.47
18
5.4
56
15
.45
36
5.4
39
85
.43
73
5.0
39
05
.03
46
5.0
29
65
.02
21
5.0
17
05
.01
27
5.0
07
65
.00
51
5.0
00
14
.99
57
4.9
90
74
.98
76
4.9
83
24
.97
88
4.9
73
8
3.8
39
13
.83
35
3.8
28
53
.82
22
3.8
15
33
.80
90
3.8
04
03
.79
77
3.7
92
13
.44
90
3.4
36
53
.42
39
3.4
19
53
.41
20
3.4
06
43
.39
32
2.9
69
82
.96
54
2.9
62
92
.95
85
2.9
49
12
.44
55
2.4
14
72
.40
41
2.3
96
62
.38
53
2.3
77
72
.36
64
2.0
72
92
.05
47
2.0
36
52
.02
09
2.0
18
31
.42
31
1.4
06
20
.90
06
0.8
84
30
.86
68
(ppm)
0.51.01.52.02.53.03.54.04.55.05.56.06.57.0
4921/10 (F-1)
28
06
.80
28
05
.30
28
03
.54
28
02
.03
(ppm)
7.00
15
36
.16
15
33
.90
15
31
.89
15
29
.38
15
26
.62
15
24
.11
15
22
.10
15
19
.59
15
17
.33
(ppm)
3.803.85
11
88
.32
11
86
.56
11
85
.56
11
83
.80
11
80
.03
(ppm)
2.922.96
97
8.5
1
96
6.2
19
61
.94
95
8.9
39
54
.41
95
1.4
09
46
.89
(ppm)
2.40
Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2010
SI 29
3.17 13
C NMR (4E)-4,5-Didehydro-cis-reticulatacin-10-one A/B (11A/B, dr ~ 1:9)
6 4
C11H23
HO
O
OHHH
O
O
O6 4
C11H23
HO
O
OHHH
O
O
O
11B 11A
Ratio 11B/11A ~ 9:1
21
1.4
78
9
17
3.6
22
3
14
9.6
66
0
13
3.5
63
1
13
3.4
95
5
12
4.9
75
6
82
.82
03
82
.78
17
77
.75
86
77
.46
88
77
.35
29
77
.15
00
76
.83
12
74
.48
39
74
.42
59
42
.95
44
42
.65
49
34
.26
06
34
.15
43
32
.33
83
32
.04
85
29
.82
67
29
.80
74
29
.78
81
29
.76
88
29
.74
94
29
.55
63
29
.47
90
29
.31
48
28
.93
80
28
.55
16
28
.25
22
25
.84
69
25
.65
37
23
.91
49
23
.39
33
22
.81
37
19
.26
86
14
.24
55
(ppm)
102030405060708090100110120130140150160170180190200210
4921/10 (F-1)
29
.82
67
29
.80
74
29
.78
81
29
.76
88
29
.74
94
29
.55
63
29
.47
90
29
.31
48
28
.93
80
28
.55
16
28
.25
22
25
.84
69
25
.65
37
23
.91
49
23
.39
33
22
.81
37
(ppm)
2122232425262728293031
Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2010
SI 30
3.18 1
H NMR (R,2Z,5E)-4-Nitrobenzyl 18-((2R,5S)-tetrahydro-5-((S)-1-hydroxyheptyl)furan-2-yl)-18-hydroxy-3-((S)-1-hydroxyethyl)-11-oxoocta
deca-2,5-dienoate (dr ~ 1:9)
6 4
C11H23
HO
O
OHHH
ORatio ~ 9:1
OH
O
O
NO2 6 4
C11H23
HO
O
OHHH
O OH
O
O
NO2
1.9
989
2.0
000
0.9
702
2.5
025
2.0
119
1.0
310
2.3
838
1.2
158
2.6
241
1.3
403
7.1
095
1.1
072
5.5
797
2.5
960
58.9
40
5.1
570
Inte
gra
l
8.2
466
8.2
179
7.5
602
7.5
309
7.2
700
6.1
404
5.5
521
5.5
320
5.5
009
5.4
808
5.4
625
5.4
436
5.4
241
5.3
924
5.3
723
5.2
571
4.3
890
4.3
683
3.8
270
3.8
105
3.6
593
3.6
404
3.6
136
3.5
972
3.5
124
3.4
929
3.4
246
3.0
272
3.0
046
2.9
815
2.9
614
2.3
963
2.3
731
2.3
542
2.1
890
2.0
049
1.9
829
1.9
433
1.9
281
1.7
696
1.7
537
1.5
946
1.5
605
1.5
361
1.5
099
1.4
709
1.4
495
1.4
294
1.4
075
1.3
514
1.3
301
1.2
630
0.9
076
0.8
869
0.8
637
(ppm)
0.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.5
shbf4921/10 F2 the opend product8.2
466
8.2
179
(ppm)
8.20
7.5
602
7.5
309
(ppm)
5.5
521
5.5
320
5.5
009
5.4
808
5.4
625
5.4
436
5.4
241
5.3
924
5.3
723
(ppm)
5.45.5
4.3
890
4.3
683
(ppm)
4.35
0.9
076
0.8
869
0.8
637
(ppm)
1.3
514
1.3
301
(ppm)
3.8
270
3.8
105
3.6
593
3.6
404
3.6
136
3.5
972
3.5
124
3.4
929
3.4
246
(ppm)
3.43.63.8
Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2010
SI 31
3.19 13
C NMR (R,2Z,5E)-4-Nitrobenzyl 18-((2R,5S)-tetrahydro-5-((S)-1-hydroxyheptyl)furan-2-yl)-18-hydroxy-3-((S)-1-hydroxyethyl)-11-oxoocta
deca-2,5-dienoate (dr ~ 1:9)
211.8
258
166.0
255
143.8
066
132.5
983
128.4
226
126.9
062
123.9
027
112.9
507
82.7
981
82.7
468
74.5
054
74.4
395
70.4
983
64.3
227
42.9
682
42.5
214
34.2
726
34.1
261
33.0
639
32.1
775
32.0
603
28.2
509
25.8
334
25.5
770
23.8
188
23.1
302
22.8
225
22.4
563
(ppm)
020406080100120140160180200220
shbf4921/10 F2 the opend product
211.8
258
166.0
255
143.8
066
132.5
983
128.4
226
126.9
062
123.9
027
112.9
507
82.7
981
82.7
468
(ppm)
90100110120130140150160170180190200210
74.4
395
70.4
983
64.3
227
42.9
682
42.5
214
34.2
726
34.1
261
33.0
639
32.1
775
32.0
603
28.2
509
25.8
334
25.5
770
23.8
188
23.1
302
22.8
225
22.4
563
(ppm)
203040506070
6 4
C11H23
HO
O
OHHH
ORatio ~ 9:1
OH
O
O
NO2 6 4
C11H23
HO
O
OHHH
O OH
O
O
NO2
Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2010
SI 32
3.20 1
H NMR cis-Reticulatacin-10-one A/B (4A/B, dr ~ 1:9)
6 4
C11H23
HO
O
OHHH
O
O
O6 4
C11H23
HO
O
OHHH
O
O
O
4B 4A
Ratio 4B/4A ~ 9:1
1.0
42
9
1.0
00
0
2.0
98
7
2.2
24
7
6.3
34
4
2.5
72
4
2.4
32
2
2.4
51
7
16
.90
9
4.6
85
7
38
.74
5
4.6
28
0
Inte
gra
l
7.2
70
0
6.9
89
6
5.0
22
1
5.0
05
1
4.9
92
6
4.9
88
2
4.9
75
7
3.8
25
3
3.8
17
2
3.4
39
0
3.4
25
8
3.4
10
8
3.3
98
2
2.4
05
3
2.3
87
1
2.3
68
3
2.2
85
5
2.2
66
1
2.2
46
6
1.9
73
8
1.9
58
8
1.9
41
2
1.9
30
5
1.9
13
6
1.7
70
6
1.7
58
7
1.7
42
4
1.5
62
4
1.5
51
7
1.4
72
0
1.4
58
9
1.4
43
2
1.4
20
0
1.4
03
0
1.3
15
9
1.2
63
8
0.9
02
5
0.8
86
8
0.8
69
3
(ppm)
0.51.01.52.02.53.03.54.04.55.05.56.06.57.07.5
4921/18Reticulatacin-10-one6
.98
96
(ppm)
7.00
5.0
22
1
5.0
05
1
4.9
92
6
4.9
88
2
4.9
75
7
(ppm)
5.00
3.8
25
3
3.8
17
2
3.4
39
0
3.4
25
8
3.4
10
8
3.3
98
2(ppm)
3.43.63.8
2.4
05
3
2.3
87
1
2.3
68
3
(ppm)
2.40
2.2
85
5
2.2
66
1
2.2
46
6
(ppm)
2.25
1.4
20
0
1.4
03
0
(ppm)
1.40
0.9
02
5
0.8
86
8
0.8
69
3
(ppm)
0.90
Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2010
SI 33
3.21 1
H NMR cis-Reticulatacin-10-one A/B (4A/B, dr ~ 1:9)
6 4
C11H23
HO
O
OHHH
O
O
O6 4
C11H23
HO
O
OHHH
O
O
O
4B 4A
Ratio 4B/4A ~ 9:1
6.9
97
26
.99
34
6.9
89
66
.98
59
2.4
06
02
.38
71
2.3
69
0
1.4
20
61
.40
30
(ppm)
0.51.01.52.02.53.03.54.04.55.05.56.06.57.07.5
4921/18
27
99
.77
27
98
.27
27
96
.76
27
95
.26
(ppm)
6.99
Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2010
SI 34
3.22 13
C NMR cis-Reticulatacin-10-one A/B (4A/B, dr ~ 1:9)
6 4
C11H23
HO
O
OHHH
O
O
O6 4
C11H23
HO
O
OHHH
O
O
O
4B 4A
Ratio 4B/4A ~ 9:1
211.6
818
174.0
183
149.0
671
134.3
842
82.8
203
82.7
816
77.5
557
77.4
688
77.1
500
76.8
312
74.5
032
74.4
452
42.9
254
42.8
578
34.2
702
34.1
640
32.0
581
29.8
364
29.8
170
29.5
659
29.4
983
29.3
244
29.2
278
29.2
085
29.1
119
28.2
618
27.4
890
25.8
565
25.6
537
25.2
866
23.9
246
23.8
956
22.8
234
19.3
555
14.2
551
(ppm)
102030405060708090100110120130140150160170180190200210
4921/18
211.6
818
174.0
183
149.0
671
134.3
842
82.8
203
82.7
816
(ppm)
90100110120130140150160170180190200210
34.2
702
34.1
640
32.0
581
29.8
364
29.8
170
29.5
659
29.4
983
29.3
244
29.2
278
29.2
085
29.1
119
28.2
618
27.4
890
25.8
565
25.6
537
25.2
866
23.9
246
23.8
956
22.8
234
(ppm)
242628303234
Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2010
SI 35
3.23 1H NMR Hydrazone byproduct
11.0 10.5 10.0 9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0
Chemical Shift (ppm)
6.94
42.87
18.60
14.62
4.30
2.41
2.04
1.00
1.14
4.33
2.22
7.84
7.81
7.38
7.35
7.31
7.29
7.28
7.27
7.01
7.01
5.02
5.01
5.00
4.99
3.82
3.50
3.43
2.43
2.41
2.39
2.29
2.26
2.24
2.17
2.07
1.95
1.53
1.43
1.41
1.40
1.26
0.91
0.89
0.86
0.08
Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2010
SI 36
3.24 Mass spectrum Hydrazone byproduct
4.0 Chromatograms
4.1 Chiral HPLC chromatogram of synthetic cis-reticulatacin-10-one A/B (4A/B, dr ~ 1:9)
Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2010
SI 37
4.2 Chiral HPLC chromatogram of natural cis-reticulatacin-10-one A/B (4A/B)
4.3 Overlay of chiral HPLC chromatograms of ── natural cis-reticulatacin-10-one A/B (4A/B )
── synthetic cis-reticulatacin-10-one A/B (4A/B, dr ~ 1:9)
Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2010