Das et al. SI - Amazon S3
Transcript of Das et al. SI - Amazon S3
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Supporting Information
Asymmetric Catalysis of the Carbonyl-Amine Condensation: Kinetic Resolution of Primary Amines
Sayantani Das, Nilanjana Majumdar, Chandra Kanta De, Dipti Sankar Kundu, Arno Döhring, and Benjamin List*
Max-Planck-Institut für Kohlenforschung, Kaiser-Wilhelm-Platz 1, 45470 Mülheim an der Ruhr, Germany
General Information S2 1a. General Procedure for the kinetic resolution of rac-amines for Table 1 S3 1b. General Procedure for the kinetic resolution of rac-amines for Chart 1 S3 1c. Procedure for the large scale experiment S4 1d. Pyrrole formation from 1,4-diketone S5 2. Determination of s-factor S6 3. Determination of absolute configuration S6 4. Product characterization S7 5. 1H and 13C NMR spectra S14 6. HPLC traces S32
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General Information
Unless otherwise stated, all reagents were purchased from commercial suppliers and purified
prior to use. Racemic amines were purchased from Aldrich, abcr and TCI. Diketones were
purchased from Aldrich and abcr. All solvents used in the reactions were distilled from
appropriate drying agents prior to use. Reactions were monitored by thin layer
chromatography (TLC) on silica gel pre-coated plastic sheets (0.2 mm, Macherey-Nagel).
Visualization was accomplished by irradiation with UV light at 254 nm and/or KMnO4 stain.
Neutral Al2O3 (Type I) was purchased from Aldrich. Column chromatography was performed
on neutral Al2O3 (Type III). Proton and carbon NMR spectra were recorded on a Bruker AV-
500 spectrometer in deuterated solvents. Proton chemical shifts are reported in ppm (δ)
relative to tetramethylsilane (TMS) with the solvent resonance employed as the internal
standard (CDCl3 δ 7.26 and CD2Cl2 δ 5.32 ppm). Data are reported as follows: chemical shift,
multiplicity (s = singlet, d = doublet, t = triplet, q = quartet, p = pentet, s = sextet, h = heptet,
m = multiplet, br = broad), coupling constants (Hz) and integration. 13C chemical shifts are
reported in ppm from tetramethylsilane (TMS) with the solvent resonance as the internal
standard (CDCl3 δ 77.16 and CD2Cl2 δ53.84 ppm). High resolution mass spectra were
determined on a Bruker APEX III FTMS (7 T magnet). Optical rotations were determined
with an Autopol IV polarimeter (Rudolph Research Analytical) at 589 nm and 25 °C. Data are
reported as follows: [α]λtemp, concentration (c in g/100 mL), and solvent. Enantiomeric ratios
(er) were determined by HPLC analysis employing a chiral stationary phase column specified
in the individual experiment, by comparing the samples with the appropriate racemic mixtures.
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1a. General Procedure for the Kinetic Resolution of rac-Amines for Table 1
An oven-dried 2 mL GC vial was charged with catalyst 3 (5 mol%, 0.05 equiv., 0.00125
mmol) and a magnetic stirring bar. To this vial Et2O (0.25 mL) was added followed by rac-
amine (1.0 equiv., 0.025 mmol, 3.2 µL) under argon atmosphere. The mixture was then stirred
at rt for 5 min. 5Å Molecular sieve (25 mg) was then added and the mixture immediately
cooled to –78 °C. To the mixture, diketone 2 (0.55 equiv., 0.014 mmol) was added under
argon atmosphere. The reaction vial was warmed to –5 °C. After 20 h, the reaction was
quenched with triethylamine (0.5 equiv., 0.0125 mmol, 1.7 µL) and benzoic anhydride (0.45
equiv., 0.0112 mmol, 2.5 mg) was added. It was further stirred at rt for 30 min. The crude
mixture was directly purified without further work-up on SiO2 preparative TLC using 5%
Et2O/DCM (v/v) and 20% EtOAc/i-Hexane as eluents for product 4 and benzoylated
derivative 5a respectively.
1b. General Procedure for the Kinetic Resolution of rac-Amine for Chart 1
An oven-dried 4 mL vial was charged with catalyst 3c (5 mol%, 0.05 equiv., 5.36 mg) and a
magnetic stirring bar. To this vial Et2O (0.8 mL) was added followed by rac-amine (1.0 equiv.,
0.1 mmol) (Note 1) under argon atmosphere. The mixture was then stirred at rt for 5 min. 5Å
Molecular sieve (100 mg) was then added and the mixture immediately cooled to –78 °C. To
the mixture, diketone 2c (0.55 equiv., 0.055 mmol, 6.4 µL in 0.2 mL Et2O) (Note 2) was
added through the cold side-wall of the vial under argon atmosphere. The reaction vial was
warmed to –5 °C and was stirred for 24 h (Note 3). After 24 h, the reaction was quenched
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with triethylamine (0.6 equiv., 0.06 mmol, 8.4 µL) and benzoic anhydride (0.5 equiv., 0.05
mmol, 11.4 mg) was added. It was further stirred at rt for 30 min. The crude mixture was
directly purified without further work up (Note 4).
Purification was performed on neutral Al2O3 (Type III) using 25% Et2O/Pentane (v/v) to 50%
Et2O/Pentane (v/v) as eluent. The products 4 were obtained as light yellow oils and the
benzoylated products 5 were obtained as white solids.
Note 1: It was found that the rac-amines form white solids upon exposure to air. These were
freshly distilled and stored in Schlenk flasks under argon atmosphere prior to use.
Note 2: Diketones were freshly distilled and stored in Schlenk flasks under argon atmosphere
prior to use. It was found that the diketones turn yellow over time. The unknown yellow
impurities can be removed under high vacuum (5x10-2 mbar at rt for 10 min).
Note 3: A proper stirring for the reaction mixture is needed due to high loading of Molecular
sieve. Typically, the raction mixture was stirred at 400–500 rpm speed.
Note 4: Due to the low stability of the products 4 on SiO2, purification was performed using
neutral Al2O3 (Type III).
1c. Procedure for the Large Scale Experiment
An oven-dried 250 mL flask was charged with catalyst 3c (1 mol%, 0.01 equiv., 94.0 mg) and
a magnetic stirring bar. To this vial Et2O (70 mL) was added followed by rac-amine (1.0
equiv., 8.7 mmol, 1.0 g) under argon atmosphere. The mixture was then stirred at rt for 10
min. 5Å Molecular sieve (9 g) was then added and the mixture immediately cooled to –78 °C.
To the mixture, diketone 2c (0.55 equiv., 4.8 mmol, 0.56 mL in 17 mL Et2O) was added
through the cold side-wall of the vial under argon atmosphere over 10 min. The reaction flask
was warmed to –5 °C and was stirred for 5 d. After 5 d, the reaction was quenched with
triethylamine (0.6 equiv., 5.2 mmol, 0.73 mL) and benzoic anhydride (0.5 equiv., 4.3 mmol,
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0.98 g) was added. It was further stirred for 1 h and then 30 min at rt. The crude mixture was
directly purified without further work up as a solid-load over celite. Purification was
performed on neutral Al2O3 (Type III) using 20% Et2O/Pentane (v/v) to 50% Et2O/Pentane
(v/v) as eluent. The product 4g was obtained as light yellow oil in 41% isolated yield and the
benzoylated product 5g was obtained as white solid in 46% isolated yield.
Deprotection step: A 4 mL vial was charged with 4g (42.0 mg, 0.2 mmol, er = 6:94) and a
magnetic stirring bar. To this vial MeOH (0.4 mL) was added followed by NH2OH.HCl (1.2
equiv., 0.24 mml, 16.7 mg). The reaction mixture was stirried at rt for 1.5 h and MeOH was
removed. The crude product was dissolved in 0.5 ml of CH2Cl2 and Et3N (1.3 equiv., 0.26
mmol, 36.0 µL). It was then cooled to 0 °C and benzoic anhydride (1.2 equiv., 0.24 mmol, 54
mg) was added. The reaction mixture was stirried at rt for 30 min. The benzoylated product
was purified on SiO2 preparative TLC and the ee was determined by HPLC (er = 6:94).
1d. Pyrrole formation from 1,4-diketone
An oven-dried GC vial was charged with catalyst 3a (10 mol%) and a magnetic stirring bar.
To this vial PhMe (0.25 mL) was added followed by rac-amine (1.0 equiv., 0.025 mmol). To
the mixture, diketone (0.50 equiv., 0.012 mmol) was added and the vial was cooled to –20 °C
and was stirred for 13 d. The s factor was determined as above.
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2. Determination of the s-factor:
Conversion (C) was determined by measuring the ee of both the product and the benzoylated
derivative of the unreacted recovered starting material by HPLC.
eep is the enantiomeric excess of the product and eeSM is the enantiomeric excess of the
recovered unreacted starting material. The s-factor can be calculated using the calculated
conversion.1
3. Determination of the Absolute Configuration:
The absolute configuration of 4a was determined by HPLC trace comparison with the
commercially available enantio-pure (R)-1a.
The absolute configuration of 4i was determined by HPLC trace comparison with the
commercially available enantio-pure (R)-1i.
1. Kagan, H. B.; Fiaud, J. C. Top. Stereochem. 1988, 18, 249.
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4. Product Characterization
(R,Z)-3-methyl-4-((1-phenylethyl)amino)but-3-en-2-one (4a): Prepared according to the
general procedure as light yellow oil in 37% yield. 1H NMR (500 MHz,
CD2Cl2): δ (12.31, br s, 1H), 7.38–7.28 (m, 2H), 7.28–7.19 (m, 3H), 4.70 (p, J =
7.0, 1H), 2.12 (s, 3H), 1.82 (s, 3H), 1.80 (s, 3H), 1.50 (d, J = 6.9, 3H). 13C
NMR (126 MHz, CD2Cl2): δ 195.5, 161.3, 145.7, 129.1, 127.3, 126.0, 99.1,
30.5, 28.8, 25.2, 15.9, 14.9. HRMS m/z (ESI): calcd. for C14H20N1O1 [M+H]: 218.153939;
found: 218.153700. The enantiomeric ratio was measured by HPLC analysis using
ChiralpakOD-3, heptane/ i-PrOH = 90:10, flow rate = 1.0 mL/min, λ = 340 nm, tR = 3.2 min
(minor) and tR= 5.3 min (major). er = 6.5:93.5.[α]D25 = –629 (c 0.40, CH2Cl2).
4a: er = 7:93, 5a: er = 11.9:88.1. calculated conversion = 47% calculated s-factor = 30
(R,Z)-3-methyl-4-((1-phenylpropyl)amino)pent-3-en-2-one (4b): Prepared according to the
general procedure as light yellow oil in 50% yield. 1H NMR (500 MHz,
CD2Cl2): δ (12.44, br s, 1H), 7.38–7.28 (m, 2H), 7.28–7.17 (m, 3H), 4.46 (q, J =
6.8 Hz, 1H), 2.12 (s, 3H), 1.87–1.75 (m, 8H), 0.94 (t, J = 7.4 Hz, 3H). 13C NMR
(126 MHz, CD2Cl2): δ 195.4, 161.8, 144.3, 129.0, 127.3, 126.7, 99.0, 59.9, 32.1,
28.8, 15.9, 14.9, 10.9. HRMS m/z (ESI): calcd. for C15H22N1O1 [M+H]: 232.169589; found:
232.169250. The enantiomeric ratio was measured by HPLC analysis using ChiralpakOD-3,
heptane/ i-PrOH = 90:10, flow rate = 1.0 mL/min, λ = 359 nm, tR = 2.8 min (minor) and tR=
5.8 min (major). er = 11.5:88.5. [α]D25 = –486 (c 0.40, CH2Cl2).
4b: er = 11.5:88.5, 5b: er = 12.3:88.7. calculated conversion = 50% calculated s-factor = 17
(R,Z)-4-((1-(2-fluorophenyl)ethyl)amino)-3-methylpent-3-en-2-one (4c): Prepared
according to the general procedure as light yellow oil in 50% yield. 1H NMR
(500 MHz, CD2Cl2): δ 12.28 (br s, 1H), 7.29–7.19 (m, 2H), 7.17–7.09 (m, 1H),
7.09–6.99 (m, 1H), 5.03 (p, J = 7.0 Hz, 1H), 2.12 (s, 3H), 1.82 (s, 3H), 1.81 (s,
3H), 1.51 (d, J = 6.8 Hz, 3H). 13C NMR (126 MHz, CD2Cl2): δ 195.8, 160.9,
160.0 (d, J = 244 Hz), 132.4 (d, J = 13.9 Hz), 129.0 (d, J = 7.8 Hz), 127.5 (d, J = 4.2), 125.1
(d, J = 3.2 Hz), 115.7 (d, J = 22.2), 99.4, 47.2 (J = 3.1), 28.8, 23.5, 15.6, 14.9. HRMS m/z
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(ESI): calcd. for C14H19N1O1F1[M+H]: 236.144517; found: 236.144270. The enantiomeric
ratio was measured by HPLC analysis using ChiralpakOD-3, heptane/ i-PrOH = 90:10, flow
rate = 1.0 mL/min, λ = 343 nm, tR = 2.9 min (minor) and tR = 4.7 min (major). er = 7.3:92.7.
[α]D25 = –557 (c 0.40, CH2Cl2).
4c: er = 7.3:92.7, 5c: er = 9.4:90.6 calculated conversion = 49% calculated s-factor = 32
(R,Z)-3-methyl-4-((1-(m-tolyl)ethyl)amino)pent-3-en-2-one (4d): Prepared according to the
general procedure as light yellow oil in 50% yield. 1H NMR (500 MHz,
CD2Cl2): δ 12.30 (br s, 1H), 7.27–7.15 (m, 1H), 7.10–6.97 (m, 3H), 4.65 (p,
J = 6.9 Hz, 1H), 2.33 (s, 3H), 2.12 (s, 3H), 1.82 (s, 3H), 1.80 (s, 3H), 1.48 (d,
J = 6.9 Hz, 3H). 13C NMR (126 MHz, CD2Cl2): δ 195.4, 161.3, 145.6, 138.9,
129.0, 128.1, 126.7, 123.1, 98.9, 53.7, 28.8, 25.2, 21.6, 15.9, 14.9. HRMS m/z (ESI): calcd.
for C15H22N1O1 [M+H]: 232.169350; found: 232.169350. The enantiomeric ratio was
measured by HPLC analysis using ChiralpakOD-3, heptane/ i-PrOH = 90:10, flow rate = 1.0
mL/min, λ = 340 nm, tR = 2.8 min (minor) and tR = 4.6 min (major). er = 8.1:91.9. [α]D25 = –
567 (c 0.40, CH2Cl2).
4d: er = 8.1:91.9, 5d: er = 7.4:92.6 calculated conversion = 50% calculated s-factor = 31
(R,Z)-4-((1-(3-fluorophenyl)ethyl)amino)-3-methylpent-3-en-2-one (4e): Prepared
according to the general procedure as light yellow oil in 45% yield. 1H NMR
(500 MHz, CD2Cl2): δ 12.25 (br s, 1H), 7.37–7.26 (m, 1H), 7.04 (d, J = 7.9
Hz, 1H), 6.98–6.88 (m, 2H), 4.70 (p, J = 6.9 Hz, 1H), 2.13 (s, 3H), 1.81 (s,
3H), 1.80 (s, 3H), 1.49 (d, J = 6.8 Hz, 3H). 13C NMR (126 MHz, CD2Cl2): δ
195.9, 163.5 (d, J = 245 Hz), 161.0, 148.7 (d, J = 6.3 Hz), 130.8 (d, J = 8.5 Hz), 121.8 (d, J =
3.0 Hz), 114.1 (d, J = 21.2), 112.9 (d, J = 22.3), 99.4, 53.3, 28.9, 25.0, 15.9, 14.9. HRMS m/z
(ESI): calcd. for C14H19N1O1F1 [M+H]: 236.144517; found: 236.144400. The enantiomeric
ratio was measured by HPLC analysis using ChiralpakOD-3, heptane/ i-PrOH = 90:10, flow
rate = 1.0 mL/min, λ = 340 nm, tR = 3.3 min (minor) and tR = 7.3 min (major). er = 6.8:93.2.
[α]D25 = –548 (c 0.40, CH2Cl2).
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4e: er = 6.8:93.2, 5e: er = 12.4:87.6
calculated conversion = 47% calculated s-factor = 31 (R,Z)-3-methyl-4-((1-(p-tolyl)ethyl)amino)pent-3-en-2-one (4f): Prepared according to the
general procedure as light yellow oil in 45% yield. 1H NMR (500 MHz,
CD2Cl2): δ 12.29 (br s, 1H), 7.17–7.09 (m, 4H), 4.66 (p, J = 6.9 Hz, 1H),
2.31 (s, 3H), 2.11 (s, 3H), 1.82 (s, 3H), 1.80 (s, 3H), 1.74 (d, J = 6.9 Hz, 3H). 13C NMR (126 MHz, CD2Cl2): δ 195.3, 161.3, 142.6, 137.1, 129.7, 125.9,
98.9, 53.4, 28.8, 25.2, 21.1, 15.9, 14.9. HRMS m/z (ESI): calcd. for C15H22N1O1 [M+H]:
232.169589; found: 232.169320. The enantiomeric ratio was measured by HPLC analysis
using ChiralpakOD-3, heptane/ i-PrOH = 90:10, flow rate = 1.0 mL/min, λ = 340 nm, tR = 2.7
min (minor) and tR = 4.6 min (major). er =.6.5:93.5. [α]D25 = –623 (c 0.40, CH2Cl2).
4f: er = 6.5:93.5, 5f: er = 15.7:84.3 calculated conversion = 45% calculated s-factor = 23 (R,Z)-3-methyl-4-((5-methylhexan-2-yl)amino)pent-3-en-2-one (4g): Prepared according to
the general procedure as light yellow oil in 38% yield. 1H NMR (500 MHz,
CD2Cl2): δ 12.05 (br s, 1H), 3.60–3.49 (m, 1H), 2.06 (s, 3H), 1.96 (s, 3H),
1.82 (s, 3H), 1.54–1.43 (m, 3H), 1.30–1.17 (m, 2H), 1.16 (d, J = 6.5 Hz, 3H),
0.88 (d, J = 6.6 Hz, 6H). 13C NMR (126 MHz, CD2Cl2): δ 194.1, 161.4, 97.8,
49.7, 36.1, 35.6, 27.7 (1), 22.7 (0), 22.4, 15.4, 14.9. HRMS m/z (ESI): calcd. for C13H26N1O1
[M+H]: 212.200889; found: 212.200840. The enantiomeric ratio was measured by HPLC
analysis using ChiralpakOD-3, heptane/ i-PrOH = 96:4, flow rate = 1.0 mL/min, λ = 339 nm,
tR = 4.1 min (minor) and tR = 4.3 min (major). er = 4.9:95.1. [α]D25 = –94.00 (c 0.40, CH2Cl2).
4g: er = 4.9:95.1, 5g: er = 12.2:87.8. calculated conversion = 46% calculated s-factor = 44
(R,Z)-3-methyl-4-((4-phenylbutan-2-yl)amino)pent-3-en-2-one (4h): Prepared according to
the general procedure as light yellow oil in 47% yield. 1H NMR (500 MHz,
CD2Cl2): δ 12.12 (br s, 1H), 7.32–7.22 (m, 2H), 7.22–7.13 (m, 3H), 3.64–3.49
(m, 1H), 2.78–2.54 (m, 2H), 2.08 (s, 3H), 1.90 (s, 3H), 1.67–1.76 (m, 2H), 1.83
(s, 3H), 1.12 (d, J = 6.5 Hz, 3H). 13C NMR (126 MHz, CD2Cl2): δ 194.5, 161.4, 142.2, 128.8,
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128.7, 126.2, 89.1, 48.6, 39.8, 32.6, 28.6, 22.5, 15.4, 14.9. HRMS m/z (ESI): calcd. for
C16H24N1O1 [M+H]: 246.185239; found: 246.185100. The enantiomeric ratio was measured
by HPLC analysis using ChiralpakOD-3, heptane/ i-PrOH = 96:4, flow rate = 1.0 mL/min, λ =
335 nm, tR = 5.9 min (minor) and tR = 6.9 min (major). er = 8.1:91.9. [α]D25 = –190 (c 0.40,
CH2Cl2).
4h: er = 8.1:91.9, 5h: er = 10.4:89.6. calculated conversion = 49% calculated s-factor = 27
(R,Z)-4-(heptan-2-ylamino)-3-methylpent-3-en-2-one (4i): Prepared according to the
general procedure as light yellow oil in 44% yield. 1H NMR (500 MHz,
CD2Cl2): δ 12.04 (br s, 1H), 3.67–3.49 (m, 1H), 2.06 (s, 3H), 1.97 (s, 3H),
1.82 (s, 3H), 1.55–1.42 (m, 2H), 142–1.22 (m, 6H), 1.16 (d, J = 6.4 Hz, 3H),
0.88 (t, J = 7.0 Hz, 3H). 13C NMR (126 MHz, CD2Cl2): δ 194.1, 161.4, 97.7, 49.4, 38.3, 32.2,
28.6, 26.2, 23.0, 22.4, 15.4, 14.9, 14.2. HRMS m/z (ESI): calcd. C13H26N1O1 for [M+H]:
212.200889; found: 212.200810. The enantiomeric ratio was measured by HPLC analysis
using the following parameters: ChiralpakOD-3, heptane/ i-PrOH = 96:4, flow rate = 1.0
mL/min, λ = 340 nm, tR = 4.5 min (major) and tR = 6.5 min (minor). er = 90.4:9.6. [α]D25 = –
90 (c 0.40, CH2Cl2).
4i: er = 90.4:9.6, 5i: er = 5.5:94.5. calculated conversion = 52% calculated s-factor = 28
(R,Z)-3-methyl-4-(pentan-2-ylamino)pent-3-en-2-one (4j): Prepared according to the
general procedure as light yellow oil in 39% yield. 1H NMR (500 MHz,
CD2Cl2): δ 12.05 (br s, 1H), 3.67–3.51 (m, 1H), 2.06 (s, 3H), 1.97 (s, 3H), 1.81
(s, 3H), 1.56–1.26 (m, 4H), 1.16 (d, J = 6.5 Hz, 3H), 0.91 (t, J = 7.2 Hz, 3H). 13C NMR (126 MHz, CD2Cl2): δ 194.1, 161.5, 97.7, 49.1, 40.5, 28.6, 22.4, 19.6, 15.4, 14.9,
14.1. HRMS m/z (ESI): calcd. for C11H22N1O1 [M+H]: 184.169589; found: 184.169620. The
enantiomeric ratio was measured by HPLC analysis using ChiralpakOD-3, heptane/ i-PrOH =
96:4, flow rate = 1.0 mL/min, λ = 336 nm, tR = 5.1 min (major) and tR = 5.4 min (minor). er =
12.4:87.6. [α]D25 = –67 (c 0.40, CH2Cl2).
4j: er = 12.4:87.6, 5j: er = 11:89.
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calculated conversion = 51% calculated s-factor = 17
(R,Z)-3-methyl-4-((4-methylpentan-2-yl)amino)pent-3-en-2-one (4k): Prepared according
to the general procedure as light yellow oil in 38% yield. 1H NMR (500 MHz,
CD2Cl2): δ 12.02 (br s, 1H), 3.70–3.58 (m, 1H), 2.06 (s, 3H), 1.98 (s, 3H), 1.82
(s, 3H), 1.73–1.60 (m, 1H), 1.49–1.40 (m, 1H), 1.35–1.27 (m, 1H), 1.15 (d, J =
6.3 Hz, 3H), 0.91 (d, J = 6.6 Hz, 3H), 0.88 (d, J = 6.6 Hz, 3H). 13C NMR (126 MHz, CD2Cl2):
δ 194.2, 161.4, 97.8, 47.4 (8), 47.4 (6), 28.6, 25.4, 23.0, 22.9, 22.6, 15.3, 14.9. HRMS m/z
(ESI): calcd. for C12H24N1O1 [M+H]: 198.185239; found: 198.185250. The enantiomeric ratio
was measured by HPLC analysis using ChiralpakOD-3, heptane/ i-PrOH = 96:4, flow rate =
1.0 mL/min, λ = 339 nm, tR = 3.8 min (minor) and tR = 6.5 min (major). er = 6.4:93.6. [α]D25 =
–60 (c 0.40, CH2Cl2).
4k: er = 6.4:93.6, 5k: er = 14.6:85.4. calculated conversion = 45% calculated s-factor = 31
(R,Z)-3-methyl-4-((6-methylheptan-2-yl)amino)pent-3-en-2-one (4l): Prepared according
to the general procedure as light yellow oil in 39% yield. 1H NMR (500
MHz, CD2Cl2): δ 12.04 (br s, 1H), 3.64–3.52 (m, 1H), 2.06 (s, 3H), 1.97 (s,
3H), 1.82 (s, 3H), 1.59–1.40 (m, 3H), 1.40–1.24 (m, 2H), 1.22–1.10 (m, 5H),
0.87 (d, J = 6.6 Hz, 6H). 13C NMR (126 MHz, CD2Cl2): δ 194.1, 161.4, 97.8, 49.4, 39.2, 38.6,
28.6, 28.3, 24.3, 22.7 (4), 22.7 (1), 22.4, 15.4, 14.9. HRMS m/z (ESI): calcd. for C14H28N1O1
[M+H]: 226.216539; found: 226.216380.The enantiomeric ratio was measured by HPLC
analysis using ChiralpakOD-3, heptane/ i-PrOH = 96:4, flow rate = 1.0 mL/min, λ = 330 nm,
tR = 4.4 min (major) and tR = 6.5 min (minor). er = 6.9:93.1. [α]D25 = –99 (c 0.40, CH2Cl2).
4l: er = 6.9:93.1, 5l: er = 12.5:87.5 calculated conversion = 47% calculated s-factor = 30
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(S)-N-(5-methylhexan-2-yl)benzamide (5g): 1H NMR (500 MHz, CDCl3): δ 7.81–7.70 (m,
2H), 7.48 (tt, J = 1.3, 7.3 Hz, 1H), 7.44–7.37 (m, 2H), 5.95 (d, J = 7.6 Hz, 1H),
4.31–3.97 (m, 1H), 1.63–1.42 (m, 3H), 1.35–1.24 (m, 2H), 1.23 (d, J = 6.6 Hz,
3H), 0.88 (d, J = 6.7 Hz, 6H). 13C NMR (126 MHz, CDCl3): δ 166.9, 135.2,
131.3, 128.6, 126.9, 46.1, 35.3, 35.0, 28.1, 22.7, 21.2. HRMS m/z (ESI): calcd. for
C14H20N1O1 [M–H]: 218.155039; found: 218.155060. The enantiomeric ratio was measured
by HPLC analysis using ChiralpakOD-3, heptane/ i-PrOH = 85:15, flow rate = 1.0 mL/min, λ
= 248 nm, tR = 3.2 min (minor) and tR = 3.9 min (major). er = 12.2:87.8. [α]D25 = 6 (c 0.40,
CH2Cl2).
(S)-N-(4-phenylbutan-2-yl)benzamide (5h): 1H NMR (500 MHz, CDCl3): δ 7.75–7.62 (m,
2H), 7.46 (tt, J = 1.3, 7.4 Hz, 1H), 7.38 (t, J = 7.8 Hz, 2H), 7.30–7.22 (m, 2H),
7.22–7.12 (m, 3H), 5.98 (d, J = 7.9 Hz, 1H), 4.36–4.17 (m, 1H), 2.71 (t, J = 7.8
Hz, 2H), 1.97–1.81 (m, 2H), 1.27 (d, J = 6.7 Hz, 3H). 13C NMR (126 MHz,
CDCl3): δ 166.9, 141.9, 135.0, 131.4, 128.6 (1), 128.6 (0), 128.5, 126.9, 126.0, 45.8, 38.7,
32.6, 21.2. HRMS m/z (ESI): calcd. for C17H18N1O1 [M–H]: 252.139389; found: 252.139630.
The enantiomeric ratio was measured by HPLC analysis using ChiralpakOD-3, heptane/ i-
PrOH = 85:15, flow rate = 1.0 mL/min, λ = 238 nm, tR = 5.9 min (minor) and tR = 11.0 min
(major). er = 10.4:89.6. [α]D25 = 6 (c 0.25, CH2Cl2).
(S)-N-(heptan-2-yl)benzamide (5i): 1H NMR (500 MHz, CDCl3): δ 7.79–7.71 (m, 2H), 7.47
(tt, J = 1.3, 7.4 Hz, 1H), 7.43–7.36 (m, 2H), 5.98 (d, J = 7.6 Hz, 1H), 4.25–
4.10 (m, 1H), 1.60–1.44 (m, 2H), 1.43–1.24 (m, 6H), 1.22 (d, J = 6.6 Hz,
3H), 0.87 (t, J = 6.9 Hz, 3H). 13C NMR (126 MHz, CDCl3): δ 166.9, 135.2,
131.3, 128.6, 126.9, 45.9, 37.1, 31.8, 25.9, 22.7, 21.1, 14.1. HRMS m/z (ESI): calcd. for
C14H20N1O1 [M–H]: 218.155039; found: 218.155070. The enantiomeric ratio was measured
by HPLC analysis using ChiralpakOD-3, heptane/ i-PrOH = 90:10, flow rate = 1.0 mL/min, λ
= 238 nm, tR = 5.0 min (minor) and tR = 5.7 min (major). er = 5.5:94.5. [α]D25 = 3 (c 0.7,
CH2Cl2).
(S)-N-(pentan-2-yl)benzamide (5j): 1H NMR (500 MHz, CDCl3): δ 7.80–7.71 (m, 2H), 7.47
(tt, J = 1.3, 7.4 Hz, 1H), 7.41 (tt, J = 1.5, 7.6 Hz, 2H), 5.93 (d, J = 5.9 Hz, 1H),
4.29–4.12 (m, 1H), 1.62–1.45 (m, 2H), 1.45–1.34 (m, 2H), 1.23 (d, J = 6.6 Hz,
3H), 0.93 (t, J = 7.4 Hz, 3H). 13C NMR (126 MHz, CDCl3): δ 166.9, 135.2,
S13
131.4, 128.6, 126.9, 45.6, 39.4, 21.2, 19.5, 14.1. HRMS m/z (ESI): calcd. for C12H16N1O1
[M–H]: 190.123739; found: 190.123830. The enantiomeric ratio was measured by HPLC
analysis using ChiralpakOD-3, heptane/ i-PrOH = 90:10, flow rate = 1.0 mL/min, λ = 232 nm,
tR = 4.9 min (minor) and tR = 6.2 min (major). er = 11:89. [α]D25 = 20 (c 0.17, CH2Cl2).
(S)-N-(4-methylpentan-2-yl)benzamide (5k): 1H NMR (500 MHz, CDCl3): δ 7.81–7.70 (m,
2H), 7.48 (tt, J = 1.4, 7.5 Hz, 1H), 7.45–7.37 (m, 2H), 5.89 (d, J = 7.1 Hz, 1H),
4.38–4.16 (m, 1H), 1.77–1.62 (m, 1H), 1.48 (ddd, J = 6.3, 8.3, 14.2 Hz, 1H),
1.34 (ddd, J = 6.3, 8.1, 13.9 Hz, 1H),1.22 (d, J = 6.5 Hz, 3H), 0.95 (d, J = 6.7 Hz,
3H), 0.94 (d, J = 6.7 Hz, 3H). 13C NMR (126 MHz, CDCl3): δ 166.8, 135.2, 131.4, 128.6,
126.9, 46.7, 44.1, 25.3, 22.9, 22.7, 21.7. HRMS m/z (ESI): calcd. for C13H18N1O1 [M–H]:
204.139388; found: 204.139450. The enantiomeric ratio was measured by HPLC analysis
using ChiralpakOD-3, heptane/ i-PrOH = 90:10, flow rate = 1.0 mL/min, λ = 238 nm, tR = 4.0
min (minor) and tR = 5.9 min (major). er = 14.6:85.4. [α]D25 = 20 (c 0.21, CH2Cl2).
(S)-N-(6-methylheptan-2-yl)benzamide (5l): 1H NMR (500 MHz, CDCl3): δ 7.83–7.69 (m,
2H), 7.47 (tt, J = 1.3, 7.3 Hz, 1H), 7.44–7.35 (m, 2H), 5.99 (d, J = 7.6 Hz,
1H), 4.33–4.02 (m, 1H), 1.63–1.43 (m, 3H), 1.43–1.30 (m, 2H), 1.22 (d, J =
6.7 Hz, 3H), 1.21–1.10 (m, 2H), 0.86 (d, J = 6.7 Hz, 6H). 13C NMR (126
MHz, CDCl3): δ 166.9, 135.2, 131.3, 128.6, 126.9, 45.9, 38.9, 37.4, 28.0, 24.0, 22.7, 22.6 (7),
21.1. HRMS m/z (ESI): calcd. for C15H22N1O1 [M–H]: 232.170689; found: 232.170790. The
enantiomeric ratio was measured by HPLC analysis using ChiralpakOD-3, heptane/ i-PrOH =
90:10, flow rate = 1.0 mL/min, λ = 228 nm, tR = 4.9 min (minor) and tR = 5.4 min (major). er
= 12.5:87.5. [α]D25 = 13 (c 0.24, CH2Cl2).
S14
1H and 13C NMR Spectra of Product 4a
13 12 11 10 9 8 7 6 5 4 3 2 1 ppm
3.19
3.10
3.09
3.06
1.04
2.97
2.03
1.00
200 180 160 140 120 100 80 60 40 20 ppm
14
.8
71
5.
87
25
.1
72
8.
79
30
.4
9
53
.4
15
3.
62
53
.7
05
3.
84
54
.0
55
4.
27
99
.0
5
12
6.
04
12
7.
34
12
9.
10
14
5.
69
16
1.
30
19
5.
48
S15
1H and 13C NMR Spectra of Product 4b
13 12 11 10 9 8 7 6 5 4 3 2 1 ppm
3.18
8.25
3.05
1.03
3.02
2.03
1.00
200 180 160 140 120 100 80 60 40 20 ppm
10
.9
01
4.
90
15
.9
4
28
.7
73
2.
05
53
.4
15
3.
63
53
.8
45
4.
06
54
.2
85
9.
88
99
.0
3
12
6.
70
12
7.
34
12
8.
96
14
4.
29
16
1.
81
19
5.
37
S16
1H and 13C NMR Spectra of Product 4c
13 12 11 10 9 8 7 6 5 4 3 2 1 ppm
3.17
3.14
2.98
3.06
1.01
0.91
0.95
1.94
1.00
200 180 160 140 120 100 80 60 40 20 ppm
14
.9
01
5.
58
23
.4
82
8.
84
47
.1
74
7.
20
53
.4
15
3.
63
53
.8
45
4.
06
54
.2
7
99
.3
61
15
.6
11
15
.7
91
25
.0
71
25
.1
01
27
.4
91
27
.5
31
28
.9
71
29
.0
31
32
.3
11
32
.4
2
15
8.
97
16
0.
87
16
0.
92
19
5.
84
S17
1H and 13C NMR Spectra of Product 4d
2345678910111213 ppm
3.14
3.01
3.02
3.01
3.03
1.02
2.90
1.01
1.00
200 180 160 140 120 100 80 60 40 20 ppm
14
.8
81
5.
89
21
.5
82
5.
18
28
.7
8
53
.4
15
3.
62
53
.6
95
3.
84
54
.0
65
4.
27
98
.9
2
12
3.
06
12
6.
74
12
8.
10
12
8.
97
13
8.
88
14
5.
62
16
1.
34
19
5.
36
S18
1H and 13C NMR Spectra of Product 4e
2345678910111213 ppm
3.21
3.04
3.00
3.01
1.03
1.82
0.98
0.95
1.00
20406080100120140160180200 ppm
14
.8
81
5.
87
24
.9
72
8.
86
53
.3
05
3.
41
53
.6
25
3.
84
54
.0
65
4.
27
99
.4
31
12
.8
51
13
.0
31
14
.0
41
14
.2
11
21
.7
71
21
.8
01
30
.7
21
30
.7
9
14
8.
64
14
8.
69
16
0.
97
16
2.
57
16
4.
52
19
5.
94
S19
1H and 13C NMR Spectra of Product 4f
13 12 11 10 9 8 7 6 5 4 3 2 1 ppm
3.10
3.08
3.03
3.05
3.08
1.02
3.94
1.00
200 180 160 140 120 100 80 60 40 20 ppm
14
.8
71
5.
85
21
.1
22
5.
18
28
.7
7
53
.4
15
3.
63
53
.8
45
4.
06
54
.2
7
98
.9
3
12
5.
93
12
9.
73
13
7.
09
14
2.
64
16
1.
34
19
5.
34
S20
1H and 13C NMR Spectra of Product 4g
2345678910111213 ppm
6.43
3.40
2.13
4.09
3.04
3.04
3.02
1.04
1.00
200 180 160 140 120 100 80 60 40 20 ppm
15
.4
12
2.
44
22
.7
02
2.
71
28
.4
72
8.
57
35
.6
43
6.
14
49
.7
05
3.
41
53
.6
25
3.
84
54
.0
55
4.
27
97
.7
5
16
1.
43
19
4.
13
S21
1H and 13C NMR Spectra of Product 4h
13 12 11 10 9 8 7 6 5 4 3 2 1 ppm
3.15
5.19
3.05
3.05
2.11
1.07
2.91
1.96
1.00
200 180 160 140 120 100 80 60 40 20 ppm
14
.9
41
5.
35
22
.5
42
8.
65
32
.6
43
9.
83
48
.6
25
3.
41
53
.6
25
3.
84
54
.0
65
4.
27
98
.0
7
12
6.
22
12
8.
75
12
8.
77
14
2.
15
16
1.
42
19
4.
48
S22
1H and 13C NMR Spectra of Product 4i
13 12 11 10 9 8 7 6 5 4 3 2 1 ppm
3.21
3.29
6.72
2.16
3.05
3.05
3.04
1.12
1.00
200 180 160 140 120 100 80 60 40 20 ppm
14
.9
21
5.
40
22
.4
42
2.
99
26
.1
72
8.
58
32
.1
73
8.
29
49
.3
95
3.
40
53
.6
25
3.
84
54
.0
55
4.
27
97
.7
4
16
1.
41
19
4.
12
S23
1H and 13C NMR Spectra of Product 4j
13 12 11 10 9 8 7 6 5 4 3 2 1 ppm
3.15
3.19
4.40
3.08
3.03
3.06
1.03
1.00
200 180 160 140 120 100 80 60 40 20 ppm
14
.1
51
4.
91
15
.3
81
9.
64
22
.4
42
8.
56
40
.4
64
9.
10
53
.4
15
3.
62
53
.8
45
4.
06
54
.2
7
97
.7
4
16
1.
46
19
4.
12
S24
1H and 13C NMR Spectra of Product 4k
2345678910111213 ppm
3.16
3.30
1.29
1.27
1.16
3.11
3.07
3.06
1.21
1.00
200 180 160 140 120 100 80 60 40 20 ppm
14
.9
21
5.
33
22
.6
02
2.
87
22
.9
52
5.
42
28
.5
94
7.
46
47
.4
85
3.
41
53
.6
25
3.
84
54
.0
55
4.
27
97
.7
8
16
1.
37
19
4.
17
S25
1H and 13C NMR Spectra of Product 4l
2345678910111213 ppm
6.51
5.47
2.46
3.29
3.13
3.03
3.04
1.09
1.00
20406080100120140160180200 ppm
22
.4
22
2.
71
22
.7
42
4.
28
28
.2
82
8.
58
38
.5
53
9.
20
49
.4
15
3.
41
53
.6
25
3.
84
54
.0
65
4.
27
97
.7
6
16
1.
42
19
4.
13
S26
1H and 13C NMR Spectra of Benzoylated Product 5g
9 8 7 6 5 4 3 2 1 ppm
6.31
3.34
1.98
3.22
1.03
1.02
2.00
1.01
2.01
170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 ppm
21
.1
82
2.
70
28
.1
13
5.
01
35
.3
0
46
.1
1
76
.9
17
7.
16
77
.4
1
12
6.
94
12
8.
63
13
1.
35
13
5.
23
16
6.
90
S27
1H and 13C NMR Spectra of Benzoylated Product 5h
9 8 7 6 5 4 3 2 1 ppm
3.18
2.10
2.09
1.03
1.03
3.00
2.18
2.04
1.02
2.04
30405060708090100110120130140150160170 ppm
21
.1
9
32
.6
4
38
.7
0
45
.8
4
76
.9
17
7.
16
77
.4
1
12
6.
05
12
6.
93
12
8.
46
12
8.
60
12
8.
61
13
1.
40
13
5.
01
14
1.
87
16
6.
94
S28
1H and 13C NMR Spectra of Benzoylated Product 5i
9 8 7 6 5 4 3 2 1 ppm
3.08
3.13
6.30
2.10
1.02
1.02
2.03
1.01
2.00
170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 ppm
14
.1
32
1.
15
22
.6
92
5.
89
31
.8
33
7.
14
45
.8
9
76
.9
07
7.
16
77
.4
1
12
6.
93
12
8.
60
13
1.
32
13
5.
22
16
6.
92
S29
1H and 13C NMR Spectra of Benzoylated Product 5j
9 8 7 6 5 4 3 2 1 ppm
3.12
3.17
2.11
2.15
1.02
1.02
2.00
1.00
2.00
170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 ppm
14
.1
01
9.
45
21
.1
9
39
.4
0
45
.6
5
76
.9
17
7.
16
77
.4
1
12
6.
93
12
8.
63
13
1.
35
13
5.
22
16
6.
94
S30
1H and 13C NMR Spectra of Benzoylated Product 5k
9 8 7 6 5 4 3 2 1 ppm
6.30
3.24
1.10
1.08
1.10
1.03
1.04
2.02
1.00
2.02
170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 ppm
21
.7
42
2.
70
22
.9
22
5.
34
44
.1
14
6.
66
76
.9
17
7.
16
77
.4
1
12
6.
93
12
8.
64
13
1.
37
13
5.
20
16
6.
84
S31
1H and 13C NMR Spectra of Benzoylated Product 5l
9 8 7 6 5 4 3 2 1 ppm
6.26
2.01
3.33
2.17
3.16
1.04
1.04
2.01
1.00
2.02
170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 ppm
21
.1
42
2.
68
22
.7
02
4.
00
27
.9
83
7.
40
38
.9
1
45
.9
0
76
.9
17
7.
16
77
.4
1
12
6.
93
12
8.
61
13
1.
32
13
5.
25
16
6.
93
S32
HPLC Trace of 4a
Peak Retention time (min)
Area (%)
1 3.1 52
2 5.2 48
Peak Retention time (min)
Area (%)
1 3.2 7.0
2 5.3 93.0
Dataf ile Name:DAT-SB-990-pdt-RAC-Me-acac-OD3-90-10-1ml-18min.lcd
0,0 1,0 2,0 3,0 4,0 5,0 6,0 7,0 8,0 9,0 min
0
10
20
30
40
50
mAU340nm4nm (1,00)
Datafile Name:dec-dd-Me-Pdt-dil.lcd
0,0 1,0 2,0 3,0 4,0 5,0 6,0 7,0 8,0 9,0 min
0
100
200
300
400
500
mAU340nm4nm (1,00)
S33
HPLC Trace of 5b
Peak Retention time (min)
Area (%)
1 5.6 49
2 7.7 51
Peak Retention time (min)
Area (%)
1 5.6 11.9
2 7.7 88.1
Datafile Name:DAT-SC-90B-der.lcd
0,0 1,0 2,0 3,0 4,0 5,0 6,0 7,0 8,0 9,0 min
0
100
200
300
400
500
600
700mAU
228nm,4nm (1,00)
Dataf ile Name:dec-dd-Me-der-re.lcd
0,0 1,0 2,0 3,0 4,0 5,0 6,0 7,0 8,0 9,0 min
0
50
100
150
200mAU
228nm,4nm (1,00)
S34
HPLC Trace of 4b
Peak Retention time (min)
Area (%)
1 2.8 53 2 5.5 47
Peak Retention time (min)
Area (%)
1 2.8 11.5 2 5.8 88.5
Dataf ile Name:DOA-AB-077-Pdt-Etamine-OD3-90-10-1mL-15min.lcd
0,0 1,0 2,0 3,0 4,0 5,0 6,0 7,0 min
0
10
20
30
40
50
60mAU
359nm,4nm (1,00)
Dataf ile Name:dec-dd-382-alpha-Et-pdt.lcd
0,0 1,0 2,0 3,0 4,0 5,0 6,0 7,0 min
0
50
100
150
200
250mAU
359nm,4nm (1,00)
S35
HPLC Trace of 5b
Peak Retention time (min)
Area (%)
1 4.0 51 2 6.1 49
Peak Retention time (min)
Area (%)
1 4.1 12.3 2 6.2 87.7
Dataf ile Name:DOA-AB-072-OD3-85-15-1mL-15min.lcd
0,0 1,0 2,0 3,0 4,0 5,0 6,0 7,0 8,0 9,0 min
0
250
500
750
1000
mAU225nm4nm (1,00)
Dataf ile Name:dec-dd-382-alpha-Et-der.lcd
0,0 1,0 2,0 3,0 4,0 5,0 6,0 7,0 8,0 9,0 min
0
100
200
300
400
500
600mAU
225nm4nm (1,00)
S36
HPLC Trace of 4c
Peak
Retention time (min)
Area (%)
1 2.9 49.6 2 4.9 50.4
Peak
Retention time (min)
Area (%)
1 2.9 7.3 2 4.7 92.7
Dataf ile Name:2-F-pdt-rac-OD3-90-10-1ml.lcd
1,0 2,0 3,0 4,0 5,0 6,0 7,0 min
0
50
100
150
200
250mAU
343nm4nm (1,00)
Dataf ile Name:MBB-MA-201pdt.lcd
0,0 1,0 2,0 3,0 4,0 5,0 6,0 7,0 min
0
25
50
75
100
mAU343nm,4nm (1,00)
S37
HPLC Trace of 5c
Peak
Retention time (min)
Area (%)
1 4.8 50.2 2 6.8 49.8
Peak
Retention time (min)
Area (%)
1 4.9 9.4 2 6.9 90.6
Dataf ile Name:DAT-SC-63-der-RAC-2-Fluoro-OD3-85-15-1ml-15min.lcd
1,0 2,0 3,0 4,0 5,0 6,0 7,0 8,0 min
0
10
20
30
40
mAU238nm,4nm (1,00)
Dataf ile Name:MBB-MA-201der.lcd
0,0 1,0 2,0 3,0 4,0 5,0 6,0 7,0 8,0 min
0
250
500
750
1000mAU
238nm,4nm (1,00)
S38
HPLC Trace of 4d
Peak Retention time (min)
Area (%)
1 2.8 50 2 4.6 50
Peak Retention time (min)
Area (%)
1 2.8 8.1 2 4.6 91.9
Dataf ile Name:DOA-AB-087-Pdt-3Meamine-OD3-90-10-1mL-15min.lcd
0,0 1,0 2,0 3,0 4,0 5,0 6,0 min
0
100
200
300
400
mAU340nm,4nm (1,00)
Dataf ile Name:dec-dd-383-3-Me-pdt.lcd
0,0 1,0 2,0 3,0 4,0 5,0 6,0 min
0
50
100
150
200
mAU340nm,4nm (1,00)
S39
HPLC Trace of 5d
Peak Retention time (min)
Area (%)
1 4.6 50 2 6.7 50
Peak Retention time (min)
Area (%)
1 4.6 7.4 2 6.6 92.6
Datafile Name:DOA-AB-088-der-3-Meamine-OD3-85-15-1mL-15min.lcd
0,0 1,0 2,0 3,0 4,0 5,0 6,0 7,0 8,0 9,0 min
0
50
100
150
200
250
300
350
400
mAU230nm4nm (1,00)
Dataf ile Name:dec-dd-383-3-Me-der.lcd
0,0 1,0 2,0 3,0 4,0 5,0 6,0 7,0 8,0 9,0 min
0
25
50
75
100
125
150
mAU230nm,4nm (1,00)
S40
HPLC Trace of 4e
Peak Retention time (min)
Area (%)
1 3.0 48.5 2 6.8 51.5
Peak Retention time (min)
Area (%)
1 3.3 6.8 2 7.3 93.2
Dataf ile Name:DAT-SC-57-pdt-RAC-3-Fluoro-OD3-90-10-1ml-15min.lcd
0,0 1,0 2,0 3,0 4,0 5,0 6,0 7,0 8,0 9,0 min
0
25
50
75
mAU340nm,4nm (1,00)
Datafile Name:MBB-MA-202pdt-re.lcd
0,0 1,0 2,0 3,0 4,0 5,0 6,0 7,0 8,0 9,0 min
0
25
50
75
100
125
150
175
mAU340nm,4nm (1,00)
S41
HPLC Trace of 5e
Peak Retention time (min)
Area (%)
1 4.9 49.9 2 8.2 50.1
Peak Retention time (min)
Area (%)
1 5.0 12.4 2 8.2 87.6
Dataf ile Name:DAT-SC-58-der-RAC-3-Fluoro-OD3-85-15-1ml-15min.lcd
1,0 2,0 3,0 4,0 5,0 6,0 7,0 8,0 9,0 min
0
5
10
15
20
25
30
mAU231nm,4nm (1,00)
Datafile Name:MBB-MA-202der.lcd
0,0 1,0 2,0 3,0 4,0 5,0 6,0 7,0 8,0 9,0 min
0
10
20
30
40
50
60
mAU231nm,4nm (1,00)
S42
HPLC Trace of 4f
Peak Retention time (min)
Area (%)
1 2.7 47 2 4.5 53
Peak Retention time (min)
Area (%)
1 2.7 6.5 2 4.6 93.5
Dataf ile Name:DOA-AB-85-pdt-RAC-4-Meaminer-OD3-90-10-1ml-15min.lcd
0,0 0,5 1,0 1,5 2,0 2,5 3,0 3,5 4,0 4,5 5,0 5,5 min
0,0
2,5
5,0
7,5
mAU340nm,4nm (1,00)
Dataf ile Name:dec-dd-384-4-Me-pdt.lcd
0,0 0,5 1,0 1,5 2,0 2,5 3,0 3,5 4,0 4,5 5,0 5,5 min
0
10
20
30
40
50
60mAU
340nm,4nm (1,00)
S43
HPLC Trace of 5f
Peak Retention time (min)
Area (%)
1 4.3 50 2 6.7 50
Peak
Retention time (min)
Area (%)
1 4.3 15.7 2 6.7 84.3
Dataf ile Name:DOA-AB-084-der-4-Meamine-OD3-85-15-1mL-15min.lcd
0,0 1,0 2,0 3,0 4,0 5,0 6,0 7,0 8,0 9,0 min
0
250
500
750
1000
mAU220nm4nm (1,00)
Dataf ile Name:dec-dd-384-4-Me-der.lcd
1,0 2,0 3,0 4,0 5,0 6,0 7,0 8,0 9,0 min
0
250
500
750
1000
mAU220nm,4nm (1,00)
S44
HPLC Trace of 4g
Peak Retention time (min)
Area (%)
1 4.2 48.3 2 4.4 51.7
Peak Retention time (min)
Area (%)
1 4.1 4.9 2 4.3 95.1
Datafile Name:DOA-AB-091-pdt-OD3-96-4-1mL.lcd
0,0 0,5 1,0 1,5 2,0 2,5 3,0 3,5 4,0 4,5 5,0 5,5 min
0
50
100
150
200
250
mAU339nm,4nm (1,00)
Dataf ile Name:dec-dd-386-pdt.lcd
0,5 1,0 1,5 2,0 2,5 3,0 3,5 4,0 4,5 5,0 5,5 min
0
25
50
75
100
125
mAU339nm,4nm (1,00)
S45
HPLC Trace of 5g
Peak Retention time (min)
Area (%)
1 3.2 49.7 2 3.9 50.3
Peak Retention time (min)
Area (%)
1 3.2 12.2 2 3.9 87.8
Dataf ile Name:DOA-AB-092-der-OD3-85-15-1mL.lcd
1,0 2,0 3,0 4,0 5,0 6,0 7,0 min
0
250
500
750
1000
1250
1500mAU
248nm,4nm (1,00)
Dataf ile Name:dec-dd-386-der.lcd
1,0 2,0 3,0 4,0 5,0 6,0 7,0 min
0
10
20
30
40
50
60
70mAU
248nm,4nm (1,00)
S46
HPLC Trace of 4h
Peak Retention time (min)
Area (%)
1 6.0 50.1 2 7.0 49.9
Peak Retention time (min)
Area (%)
1 5.9 8.1 2 6.9 91.9
Datafile Name:DAT-SC-82-RAC-pdt-OD3-96-4-1ml.lcd
0,0 2,5 5,0 7,5 10,0 12,5 min
0
100
200
300
400
500
600mAU
335nm,4nm (1,00)
Datafile Name:dec-dd-387-pdt-new.lcd
0,0 2,5 5,0 7,5 10,0 12,5 min
0
50
100
150
200
250
mAU335nm,4nm (1,00)
S47
HPLC Trace of 5h
Peak Retention time (min)
Area (%)
1 5.9 49.9 2 11 50.1
Peak Retention time (min)
Area (%)
1 5.9 10.4 2 11 89.6
Datafile Name:DAT-SC-081-der-OD3-85-15-1mL.lcd
0,0 2,5 5,0 7,5 10,0 12,5 min
0
100
200
300
400
500
mAU237nm,4nm (1,00)
Dataf ile Name:dec-dd-387-der.lcd
0,0 2,5 5,0 7,5 10,0 12,5 min
0
50
100
150
200
250mAU
238nm,4nm (1,00)
S48
HPLC Trace of 4i
Peak Retention time (min)
Area (%)
1 4.5 50 2 6.4 50
Peak Retention time (min)
Area (%)
1 4.5 90.4 2 6.5 9.6
Dataf ile Name:DAT-SC-085-pdtr-2hepty lamine-OD3-96-4-1mL-3.lcd
1,0 2,0 3,0 4,0 5,0 6,0 7,0 8,0 9,0 min
0
100
200
300
400
500
mAU340nm,4nm (1,00)
Dataf ile Name:dec-dd-389-pdt-96-4-1ml.lcd
1,0 2,0 3,0 4,0 5,0 6,0 7,0 8,0 9,0 min
0
50
100
150
200
mAU340nm4nm (1,00)
S49
HPLC Trace of 5i
Peak Retention time (min)
Area (%)
1 4.6 49.9 2 5.8 50.1
Peak Retention time (min)
Area (%)
1 5.0 5.5 2 5.7 94.5
Dataf ile Name:DAT-SC-084-der-2hepty lamine-OD3-90-10-1mL.lcd
0,0 1,0 2,0 3,0 4,0 5,0 6,0 7,0 8,0 9,0 min
0
50
100
150
200
mAU238nm,4nm (1,00)
Datafile Name:dec-dd-389-der.lcd
0,0 1,0 2,0 3,0 4,0 5,0 6,0 7,0 8,0 9,0 min
0
25
50
75
100
125
150
mAU238nm4nm (1,00)
S50
HPLC Trace of 4j
Peak Retention time (min)
Area (%)
1 5.0 49.7 2 5.4 50.3
Peak Retention time (min)
Area (%)
1 5.1 87.6 2 5.4 12.4
Dataf ile Name:DOA-AB-101-OD3-96-4-1ml-pdt.lcd
0,0 1,0 2,0 3,0 4,0 5,0 6,0 7,0 min
0
250
500
750
mAU336nm,4nm (1,00)
Dataf ile Name:dec-dd-390-pdt-new.lcd
1,0 2,0 3,0 4,0 5,0 6,0 7,0 min
0
25
50
75
100
125
mAU336nm4nm (1,00)
S51
HPLC Trace of 5j
Peak Retention time (min)
Area (%)
1 4.6 49.9 2 5.8 50.1
Peak Retention time (min)
Area (%)
1 4.9 11 2 6.2 89
Dataf ile Name:DOA-AB-100-der-RAC-2pentamine-OD3-90-10-1ml.lcd
0,0 1,0 2,0 3,0 4,0 5,0 6,0 7,0 8,0 9,0 min
0
250
500
750
mAU232nm,4nm (1,00)
Dataf ile Name:dec-dd-390-der-new.lcd
1,0 2,0 3,0 4,0 5,0 6,0 7,0 8,0 9,0 min
0
25
50
75
100
mAU232nm4nm (1,00)
S52
HPLC Trace of 4k
Peak Retention time (min)
Area (%)
1 3.7 50 2 6.4 50
Peak Retention time (min)
Area (%)
1 3.8 6.4 2 6.5 93.6
Dataf ile Name:DOA-AB-106-Pdt-b7558-OD3-96-4-1mL-15min-re.lcd
0,0 1,0 2,0 3,0 4,0 5,0 6,0 7,0 8,0 9,0 min
0
50
100
150
200
250
300
mAU339nm,4nm (1,00)
Dataf ile Name:dec-dd-391-pdt-new001.lcd
0,0 1,0 2,0 3,0 4,0 5,0 6,0 7,0 8,0 9,0 min
0
10
20
30
40
50
60
mAU339nm,4nm (1,00)
S53
HPLC Trace of 5k
Peak Retention time (min)
Area (%)
1 4.0 49.7 2 5.9 50.3
Peak Retention time (min)
Area (%)
1 4.0 14.6 2 5.9 85.4
Datafile Name:DAT-SC-110-der-b-7558-OD3-90-10-1mL-15min.lcd
0,0 1,0 2,0 3,0 4,0 5,0 6,0 7,0 8,0 9,0 min
0
250
500
750
1000mAU
236nm4nm (1,00)
Datafile Name:dec-dd-391-der-new001.lcd
1,0 2,0 3,0 4,0 5,0 6,0 7,0 8,0 9,0 min
0
5
10
15
20
25
30
35
mAU236nm,4nm (1,00)
S54
HPLC Trace of 4l
Peak Retention time (min)
Area (%)
1 4.5 50 2 6.6 50
Peak Retention time (min)
Area (%)
1 4.4 93.1 2 6.5 6.9
Dataf ile Name:DOA-AB-pdt-b7945-OD3-96-4-1ml.lcd
1,0 2,0 3,0 4,0 5,0 6,0 7,0 8,0 9,0 min
0
50
100
150
200
250
300mAU
330nm,4nm (1,00)
Dataf ile Name:dec-dd-392-pdt-new.lcd
1,0 2,0 3,0 4,0 5,0 6,0 7,0 8,0 9,0 min
0
25
50
75
mAU330nm,4nm (1,00)
S55
HPLC Trace of 5l
Peak Retention time (min)
Area (%)
1 4.7 50.4 2 5.3 49.6
Peak Retention time (min)
Area (%)
1 4.9 12.5 2 5.4 87.5
Dataf ile Name:DAT-SC-111-der-b7945-OD3-90-10-1mL-15min.lcd
0,0 1,0 2,0 3,0 4,0 5,0 6,0 7,0 min
0
250
500
750
1000
mAU226nm4nm (1,00)
Dataf ile Name:dec-dd-392-der.lcd
1,0 2,0 3,0 4,0 5,0 6,0 7,0 min
0
25
50
75
100
125
mAU226nm,4nm (1,00)