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


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


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


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


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]:


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


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


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


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]:


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


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


Area (%)

1 5.6 49

2 7.7 51


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


Area (%)

1 2.8 53 2 5.5 47


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


Area (%)

1 4.0 51 2 6.1 49


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


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


Area (%)

1 4.8 50.2 2 6.8 49.8

Peak


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


Area (%)

1 2.8 50 2 4.6 50


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


Area (%)

1 4.6 50 2 6.7 50


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


Area (%)

1 3.0 48.5 2 6.8 51.5


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


Area (%)

1 4.9 49.9 2 8.2 50.1


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


Area (%)

1 2.7 47 2 4.5 53


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


Area (%)

1 4.3 50 2 6.7 50

Peak


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


Area (%)

1 4.2 48.3 2 4.4 51.7


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


Area (%)

1 3.2 49.7 2 3.9 50.3


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


Area (%)

1 6.0 50.1 2 7.0 49.9


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


Area (%)

1 5.9 49.9 2 11 50.1


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)


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


Area (%)

1 4.5 50 2 6.4 50


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


Area (%)

1 4.6 49.9 2 5.8 50.1


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


Area (%)

1 5.0 49.7 2 5.4 50.3


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


Area (%)

1 4.6 49.9 2 5.8 50.1


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


Area (%)

1 3.7 50 2 6.4 50


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


Area (%)

1 4.0 49.7 2 5.9 50.3


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


Area (%)

1 4.5 50 2 6.6 50


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


Area (%)

1 4.7 50.4 2 5.3 49.6


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)


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)

Date post:	29-Dec-2021
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