Supporting Information

© Copyright Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, 2011
Supporting Information

Chiral Squaramide-Catalyzed Highly Enantioselective Michael Addition of

2-Hydroxy-1,4-naphthoquinones to Nitroalkenes

Wen Yang, and Da-Ming Du*

School of Chemical Engineering and Environment, Beijing Institute of Technology,

Beijing 100081, People’s Repulic of China
dudm@bit.edu.cn

Contents

Generel information.………….…………….……. ……………….. …………….....…….. .S1

Preparation of squaramide organocatalysts I-VIII…..……………………………………….S1

General procedure for the enantioselective Michael addition reaction..……………….……S3

Synthetic transformation of the Michael adduct 3a……………………………………..….S12

References ……………………………………….….....................…..…………...………..S13

Copies of 1H and 13C NMR spectra of new compounds…..……............…..….…………..S14

Copies of HPLC profiles of Michael addition products……………………….…....…..….S23

General information
Commercially available compounds were used without further purification. Column
chromatography was carried out using silica gel (200−300 mesh). Melting points were
measured on a XT-4 melting point apparatus without correction. The 1H NMR spectra were
recorded on Bruker Avance DRX 500 MHz spectrometers, while 13C NMR spectra were
recorded at 125 MHz. Infrared spectra were obtained on a Perkin Elmer Spectrum One
spectrometer. The ESI-MS spectra were obtained on Bruker APEX IV mass spectrometer.
Optical rotations were measured on WZZ-3 or Krüss P8000 polarimeter at the indicated
concentration with units g/100 mL. The enantiomeric excesses of the products were
determined by chiral HPLC using Agilent 1200 LC instrument on Daicel Chiralcel OJ-H
column and Chiralpak IA column.

Preparation of squaramide organocatalysts I−VIII

(1) The squaramide organocatalysts I−IV were prepared following the reported procedures.[1]
(2) Synthesis of squaramide organocatalysts V−VIII[2]

O O O O O O
NH2 37% HCHO
CH2 Cl2 98% HCO 2H
+
Ar r.t., 3 h Ar Ar N
N OCH3 N N 65 oC, 24 h N
NH2 H H
H H H N
NH 2
8 9 10
10a: Ar = 3,5-(CF3) 2C 6 H3 V: Ar = 3,5-(CF 3) 2C 6H 3
8a: Ar = 3,5-(CF3) 2C 6H 3 VI : Ar = 4-CF3 C6 H4
8b: Ar = 4-CF3 C 6H 4 10b: Ar = 4-CF 3C 6H 4

Organocatalyst V: To a solution of (1S,2S)-1,2-diaminocyclohexane 9 (228 mg, 2.0 mmol) in

10 mL CH2Cl2 was added compound 8a[1] ( 678 mg, 2.0 mmol). The reaction mixture was
stirred for 3 h and lots of white precipitate was generated. The crude product 10a was
obtained through filtration. A mixture of compound 10a, aqueous HCHO (37%, 2.5 mL) and
HCO2H (98%, 2.5 mL) was stirred at 65 oC for 12 h. The reaction mixture was basified with
aqueous NaOH (10%), and the white solid was isolated by filtration. The desired product V
was obtained as a white solid (412 mg, 48% yield) by recrystallization from MeOH and
CH2Cl2. m.p. 225 oC (decomp.), [α]D25 = +53.5 (c = 1.90, DMSO). 1H NMR (500 MHz,
d6-DMSO): δ = 10.29 (br s, 1H), 8.07 (s, 2H), 7.78 (br s, 1H), 7.65 (s, 1H), 3.86 (s, 1H), 2.43
(s, 1H), 2.20 (s, 6H), 2.14−2.12 (m, 1H), 1.86−1.68 (m, 3H), 1.36−1.23 (m, 4H). 13C NMR
(125 MHz, d6-DMSO): δ = 184.9, 180.4, 169.8, 162.6, 141.6, 131.8 (q, J = 33.2 Hz), 123.6 (q,
J = 270.1 Hz), 118.5, 115.0, 66.6, 55.2, 35.0, 24.8, 21.7. IR (KBr): ν 3214, 3152, 2949, 2867,
2791, 1792, 1671, 1584, 1473, 1378, 1277, 1196, 1176, 1123, 1066, 936, 895, 879, 699, 682
cm-1. HRMS (ESI): m/z calcd. for C20H22F6N3O2 [M + H]+ 450.16107, found 450.16103.

Organocatalyst VI: Organocatalyst VI was prepared following the procedure outlined for V
from (1S,2S)-1,2-diaminocyclohexane 9 (228 mg, 2.0 mmol) and compound 8b[1] ( 228 mg,
2.0 mmol). The desired product was obtained as a white solid (336 mg, 44% yield). m.p. 248
o
C (decomp.), [α]D25 = +70.0 (c = 1.96, DMSO). 1H NMR (500 MHz, d6-DMSO): δ = 10.05
(br s, 1H), 7.81 (br s, 1H), 7.70−7.64 (m, 4H), 3.88 (s, 1H), 2.43−2.39 (m, 1H), 2.21 (s, 6H),
2.11 (d, J = 10.0 Hz, 1H), 1.85 (d, J = 10.0 Hz, 1H), 1.76−1.74 (m, 1H), 1.69−1.67 (m, 1H),

S1
1.39−1.32 (m, 1H), 1.27−1.18 (m, 3H). 13C NMR (125 MHz, d6-DMSO): δ = 184.4, 179.6,
169.1, 162.5, 142.5, 126.5, 124.4 (q, J = 269.6 Hz), 122.2 (q, J = 31.9 Hz), 117.8, 66.2, 54.6,
39.8, 34.5, 24.3, 24.0, 21.2. IR (KBr): ν 3178, 2937, 2855, 2776, 1803, 1662, 1611, 1579,
1551, 1456, 1332, 1161, 1118, 1069, 1015, 876, 835, 765, 740, 728 cm-1. HRMS (ESI): m/z
calcd. for C19H23F3N3O2 [M + H]+ 382.17369, found 382.17382.
NH2 NH2
NaBH(OAc)3
+ OHC CHO
NH2 DCE, r.t. 3 h N

9 11
12
O O
O O NH2
CH2Cl2
Ar
+ N N
Ar N r.t. , 24 h H H
N O N
H
8 12
8a: Ar = 3, 5-(CF3)2C6H3 VII: Ar = 3, 5-(CF3)2C6H3
8b: Ar = 4-CF3C6H4 VIII: Ar = 4-CF3C6H4

Compound 12:[2] Aqueous glutaraldehyde 11 (50%, 1.0 mL) was added dropwise into a
mixture of NaBH(OAc)3 (4.24g, 20.0 mmol) and (1S,2S)-1,2-diaminocyclohexane 9 (570 mg,
5.0 mmol) in CH2ClCH2Cl (30 mL) at room temperature. The resulting mixture was stirred at
room temperature for 3h, and then quenched with aqueous NaOH (10%, 20 mL). The organic
layer was separated and the aqueous layer was extracted with CH2Cl2 (3 × 20 mL). The
combined organic layers were washed with brine (20 mL), dried over anhydrous Na2SO4, and
concentrated to give the crude product 12 as a yellow liquid (820 mg, 90% yield).

Organocatalyst VII: To a solution of compound 12 (273 mg, 1.5 mmol) in 5 mL CH2Cl2 was
added compound 8a ( 271 mg, 1.0 mmol). The reaction was stirred at room temperature for 24
h. Then the mixture was concentrated and purified by silica gel column chromatography (100
g silica gel was treated with 5 mL NH3.H2O, using CH2Cl2 as eluant) to afford the desired
product VII as a pale yellow solid ( 347 mg, 71% yield). m.p. 134−136o C, [α]D25 = +150.3 (c
= 0.62, CH2Cl2). 1H NMR (500 MHz, CDCl3): δ = 7.97 (s, 2H), 7.42 (s, 1H), 4.00 (s, 1H),
2.62 (br s, 2H), 2.35−2.27 (m, 3H), 2.18−2.16 (m, 1H), 1.89−1.87 (m, 1H), 1.78 (d, J = 10.5
Hz, 1H), 1.70 (d, J = 11.0 Hz, 1H), 1.40−1.12 (m, 10H). 13C NMR (125 MHz, CDCl3): δ =
183.5, 180.7, 171.0, 161.3, 140.3, 132.5 (q, J = 33.1 Hz), 123.0 (q, J = 271.2 Hz), 118.7,
116.2, 68.2, 56.0, 49.9, 33.9, 26.7, 25.1, 24.8, 24.7, 23.7. IR (KBr): ν 3251 3085, 2937, 2860,
2806, 1796, 1678, 1593, 1558, 1453, 1379, 1329, 1278, 1182, 1133, 1000, 930, 880, 701, 684,
668 cm-1. HRMS (ESI): m/z calcd. for C23H26F6N3O2 [M + H]+ 490.19237, found 490.19310.

Organocatalyst VIII: Organocatalyst VIII was prepared following the procedure outlined for
VII from compound 12 (273 mg, 1.5 mmol) and compound 8b ( 271 mg, 1.5 mmol). The
desired product was obtained as a white solid ( 286 mg, 68% yield). m.p. 252 oC (decomp.),
[α]D25 = +46.3 (c = 0.63, DMSO). 1H NMR (500 MHz, d6-DMSO): δ = 10.00 (s, 1H), 7.69 (d,
J = 8.5 Hz, 2H), 7.63 (d, J = 7.5 Hz, 2H), 3.93 (br s, 1H), 3.38 (d, J = Hz, 2H), 2.63 (br s, 2H),
2.29 (br s, 3H), 2.08 (d, J = 11.0 Hz, 1H), 1.86 (br s, 1H), 1.74 (br, s, 1H), 1.68 (br s, 1H),

S2
1.39−1.21 (m, 10H). 13C NMR (125 MHz, d6-DMSO): δ = 184.7, 179.8, 170.0, 162.0, 142.6,
126.2, 124.4 (q, J = 269.4 Hz), 122.1 (q, J = 31.9 Hz), 117.7, 68.3, 54.4, 54.3, 49.3, 26.3, 24.7,
24.4, 24.3, 23.3. IR (KBr): ν 3178, 2933, 2855, 2797, 1797, 1661, 1610, 1573, 1547, 1451,
1322, 1265, 1161, 1118, 1070, 1016, 870, 837, 738, 729 cm-1. HRMS (ESI): m/z calcd. for
C22H27F3N3O2 [M + H]+ 422.20499, found 422.20521.

General procedure for the enantioselective Michael addition reaction

8.4 mg organocatalyst VIII was added to dichloromethane to afford the solution of
catalyst VIII (10.0 mL, 2.0 mmol/L). To a solution of nitroalkenes 2 (0.20 mmol) in 0.25 mL
of the above catalyst VIII solution (0.0005 mmol) was added 2-hydroxy-1,4-naphthoquinones
1 (0.20 mmol). The reaction mixture was stired for 6 h or 12 h at 30 oC. Then the mixture was
concentrated and purified by silica gel column chromatography (CH2Cl2) to afford the desired
products 3.

(R)-2-Hydroxy-3-(2-nitro-1-phenylethyl)-1,4-naphthoquinone (3a)
O
OH

NO2
O Ph

Compound 3a was obtained according to the general procedure as an orange solid (61.9 mg,
96% yield); m.p. 152−153 oC. Enantiomeric excess was determined by HPLC on Daicel
Chiralcel OJ-H column (n-hexane-isopropanol 70:30 V/V, flow rate 1.0 mL/min, 254 nm),
minor enantiomer tr = 17.3 min, major enantiomer tr = 31.6 min, 98% ee; [α]D25 = −34.0 (c =
1.46, CH3COCH3). 1H NMR (500 MHz, CDCl3): δ = 8.11 (d, J = 7.5 Hz, 1H), 8.06 (d, J = 7.5
Hz, 1H), 8.00 (br s, 1H), 7.77 (dt, J1 = 1.0 Hz, J2= 7.5 Hz, 1H), 7.69 (dt, J1 = 1.0 Hz, J2 = 7.5
Hz, 1H), 7.47 (d, J = 7.5 Hz, 2H), 7.32 (t, J = 7.5 Hz, 2H), 7.28−7.25 (m, 1H), 5.48 (dd, J1 =
9.0 Hz, J2 = 13.5 Hz, 1H), 5.34−5.30 (m, 1H), 5.16 (dd, J1 = 6.5 Hz, J2 = 13.5 Hz, 1H).

(R)-2-[1-(4-Fluorophenyl)-2-nitroethyl]-3-hydroxy-1,4-naphthoquinone (3b)
O
OH

NO2
O

Compound 3b was obtained according to the general procedure as an orange solid (64.6 mg,
95% yield); m.p. 156−158 oC. Enantiomeric excess was determined by HPLC on Daicel
Chiralcel OJ-H column (n-hexane-isopropanol 70:30 V/V, flow rate 1.0 mL/min, 254 nm),
minor enantiomer tr = 15.6 min, major enantiomer tr = 24.6 min, 98% ee; [α]D25 = −41.9 (c =
1.55, CH3COCH3). 1H NMR (500 MHz, CDCl3): δ = 8.12 (d, J = 7.5 Hz, 1H), 8.07 (d, J = 7.5
Hz, 1H), 7.81−7.77 (m, 2H), 7.70 (t, J = 7.5 Hz, 1H), 7.46 (dd, J1 = 5.5 Hz, J2 = 8.5 Hz, 1H),

S3
7.00 (t, J = 9.0 Hz, 2H), 5.41 (dd, J1 = 8.5 Hz, J2 = 13.5 Hz, 1H), 5.30 (t, J = 8.0 Hz, 1H),
5.16 (dd, J1 = 7.0 Hz, J2 = 13.5 Hz, 1H).

(R)-2-[1-(4-Chlorophenyl)-2-nitroethyl]-3-hydroxy-1,4-naphthoquinone (3c)
O
OH

NO2
O

Cl
Compound 3c was obtained according to the general procedure as an orange solid (70.5 mg,
99% yield); m.p. 184−186 oC. Enantiomeric excess was determined by HPLC on Daicel
Chiralcel OJ-H column (n-hexane-isopropanol 70:30 V/V, flow rate 1.0 mL/min, 254 nm),
minor enantiomer tr = 15.9 min, major enantiomer tr = 27.0 min, 97% ee; [α]D25 = −20.8 (c =
1.19, CH3COCH3). 1H NMR (500 MHz, CDCl3): δ = 8.11 (d, J = 8.0 Hz, 1H), 8.08 (d, J = 7.5
Hz, 1H), 7.79 (t, J = 7.2 Hz, 1H), 7.71 (t, J = 7.5 Hz, 1H), 7.42 (d, J = 8.5 Hz, 2H), 7.29 (d, J
= 7.0 Hz, 2H), 7.28 (s,1H), 5.38 (dd, J1 = 8.5 Hz, J2 = 13.0 Hz, 1H), 5.31−5.28 (m, 1H), 5.18
(dd, J1 = 7.2 Hz, J2 = 13.2 Hz, 1H).

(R)-2-[1-(4-Bromophenyl)-2-nitroethyl]-3-hydroxy-1,4-naphthoquinone (3d)
O
OH

NO2
O

Br
Compound 3d was obtained according to the general procedure as an orange solid (75.5 mg,
94% yield); m.p. 52−54 oC. Enantiomeric excess was determined by HPLC on Daicel
Chiralcel OJ-H column (n-hexane-isopropanol 70:30 V/V, flow rate 1.0 mL/min, 254 nm),
minor enantiomer tr = 27.9 min, major enantiomer tr = 33.0 min, 98% ee; [α]D25 = −20.0 (c =
1.24, CH3COCH3). 1H NMR (500 MHz, CDCl3): δ = 8.12 (d, J = 7.5 Hz, 1H), 8.08 (d, J = 7.5
Hz, 1H), 7.93 (br s, 1H), 7.79 (t, J = 7.0 Hz, 1H), 7.71 (t, J = 7.0 Hz, 1H), 7.61 (s, 1H), 7.42
(d, J = 8.0 Hz, 1H), 7.39 (d, J = 8.0 Hz, 1H), 7.19 (t, J = 8.0 Hz, 1H), 5.40 (dd, J1 = 8.5 Hz, J2
= 13.5 Hz, 1H), 5.28 (t, J = 8.0 Hz, 1H), 5.17 (dd, J1 = 7.0 Hz, J2 = 13.5, 1H).

(R)-2-Hydroxy-3-[1-(4-methylphenyl)-2-nitroethyl]-1,4-naphthoquinone (3e)

S4
 O
OH

NO2
O

Me

Compound 3e was obtained according to the general procedure as an orange solid (65.8 mg,
97% yield); m.p. 162−164 oC. Enantiomeric excess was determined by HPLC on Daicel
Chiralcel OJ-H column (n-hexane-isopropanol 70:30 V/V, flow rate 1.0 mL/min, 254 nm),
minor enantiomer tr = 31.0 min, major enantiomer tr = 66.1 min, 97% ee; [α]D25 = −22.3 (c =
1.66, CH3COCH3). 1H NMR (500 MHz, CDCl3): δ = 8.11 (d, J = 7.5 Hz, 1H), 8.06 (d, J = 7.5
Hz, 1H), 7.79−7.75 (m, 2H), 7.68 (dt, J1 = 1.0 Hz, J2 = 7.5 Hz, 1H), 7.35 (d, J = 8.0 Hz, 2H),
7.12 (d, J = 8.0 Hz, 1H), 5.46 (dd, J1 = 9.0 Hz, J2 = 13.5 Hz, 1H), 5.28 (dd, J1 = 7.0, J2 = 9.0
Hz, 1H), 5.12 (dd, J1 = 7.0, J2 = 13.5 Hz, 1H), 2.30 (s, 3H).

(R)-2-Hydroxy-3-[1-(4-methoxyphenyl)-2-nitroethyl]-1,4-naphthoquinone (3f)
O
OH

NO2
O

OMe

Compound 3f was obtained according to the general procedure as an orange solid (67.1 mg,
95% yield); m.p. 158−160 oC. Enantiomeric excess was determined by HPLC on Daicel
Chiralcel OJ-H column (n-hexane-isopropanol 70:30 V/V, flow rate 1.0 mL/min, 254 nm),
minor enantiomer tr = 28.2 min, major enantiomer tr = 46.7 min, 97% ee; [α]D25 = −37.1 (c =
1.66, CH3COCH3). 1H NMR (500 MHz, CDCl3): δ = 8.11 (d, J = 7.5 Hz, 1H), 8.06 (d, J = 7.5
Hz, 1H), 7.87 (br s, 1H), 7.77 (dt, J1 = 1.0 Hz, J2 = 7.5 Hz, 1H), 7.69 (dt, J1 = 1.0 Hz, J2 = 7.5
Hz, 1H), 7.40 (d, J = 8.5 Hz, 2H), 6.84 (d, J = 8.5 Hz, 2H), 5.44 (dd, J1 = 8.5 Hz, J2 = 13.5 Hz,
1H), 5.26 (dd, J1 = 7.0, J2 = 8.5 Hz, 1H), 5.12 (dd, J1 = 7.0, J2 = 13.5 Hz, 1H), 3.76 (s, 3H).

(R)-2-[1-(2-Chlorophenyl)-2-nitroethyl]-3-hydroxy-1,4-naphthoquinone (3g)
O
OH

NO2
O Cl

Compound 3g was obtained according to the general procedure as an orange solid (65.6 mg,
92% yield); m.p. 50−52 oC. Enantiomeric excess was determined by HPLC on Daicel

S5
Chiralcel OJ-H column (n-hexane-isopropanol 70:30 V/V, flow rate 1.0 mL/min, 254 nm),
minor enantiomer tr = 17.2 min, major enantiomer tr = 23.2 min, 98% ee; [α]D25 = −119.2 (c =
1.60, CH2Cl2). 1H NMR (500 MHz, CDCl3): δ = 8.09 (dd, J1 = 8.0 Hz, J2 = 10.5 Hz, 2H), 8.04
(br s, 1H), 7.77 (t, J = 7.5 Hz, 1H), 7.70 (t, J = 7.5 Hz, 1H), 7.46−7.44 (m, 1H), 7.40−7.38 (m,
1H), 7.22 (t, J = 4.5 Hz, 2H), 5.73 (dd, J1 = 6.0 Hz, J2 = 10.0 Hz, 1H), 5.41 (dd, J1 = 10.0 Hz,
J2 = 14.0 Hz, 1H), 4.97 (dd, J1 = 6.0 Hz, J2 = 14.0 Hz, 1H); 13C NMR (125 MHz, CDCl3): δ =
183.8, 181.0, 154.3, 135.5, 134.6, 134.0, 133.3, 132.6, 130.1, 129.5, 129.1, 129.0, 127.2,
126.4, 119.4, 75.0, 37.1. IR (KBr): ν 3349, 3061, 1670, 1648, 1592, 1552, 1383, 1271, 1065,
1037, 983, 759, 728 cm-1. HRMS (ESI): m/z calcd. for C18H12ClNNaO5 [M + Na]+ 380.02962,
found 380.02943.

(R)-2-Hydroxy-3-[1-(2-methoxyphenyl)-2-nitroethyl]-1,4-naphthoquinone (3h)
O
OH

NO2
O OMe

Comound 3h was obtained according to the general procedure as an orange solid (63.3 mg,
90% yield); m.p. 51−53 oC. Enantiomeric excess was determined by HPLC on Daicel
Chiralcel OJ-H column (n-hexane-isopropanol 80:20 V/V, flow rate 1.0 mL/min, 254 nm),
minor enantiomer tr = 24.0 min, major enantiomer tr = 40.0 min, 95% ee; [α]D25 = −141.5 (c =
1.58, CH3COCH3). 1H NMR (500 MHz, CDCl3): δ = 8.09 (d, J = 7.5 Hz, 1H), 8.08 (d, J = 7.5
Hz, 1H), 7.85 (br s, 1H), 7.76 (t, J = 7.5 Hz, 1H), 7.69 (t, J = 7.5 Hz, 1H), 7.24 (t, J = 8.0 Hz,
2H), 6.88 (t, J = 8.0 Hz, 2H), 5.66 (dd, J1 = 5.5 Hz, J2 = 10.5 Hz, 1H), 5.42 (dd, J1 = 10.5 Hz,
J2 = 13.5 Hz, 1H), 4.97 (dd, J1 = 5.5 Hz, J2 = 13.5 Hz, 1H), 3.87 (s, 3H).

(R)-2-[1-(3,4-Dimethoxyphenyl)-2-nitroethyl]-3-hydroxy-1,4-naphthoquinone (3i)
O
OH

NO2
O

OMe
OMe
Compound 3i was obtained according to the general procedure as an orange solid (68 mg,
89% yield); m.p. 72−73 oC. Enantiomeric excess was determined through its O-methyl
derivative by HPLC, 96% ee; [α]D25 = −5.3 (c = 1.59, CH2Cl2). 1H NMR (500 MHz, CDCl3):
8.11 (d, J = 8.0 Hz, 1H), 8.05 (d, J = 8.0 Hz, 1H), 7.85 (br s, 1H), 7.76 (t, J = 7.5 Hz, 1H),
7.68 (t, J = 7.5 Hz, 1H), 7.04 (d, J = 8.0 Hz, 1H), 7.03 (s, 1H), 6.80 (d, J = 8.0 Hz, 1H), 5.45
(dd, J1 = 9.0 Hz, J2 = 13.0 Hz, 1H), 5.25 (t, J = 8.0 Hz, 1H), 5.15 (dd, J1 = 7.0 Hz, J2 = 13.5
Hz, 1H), 3.87 (s, 3H), 3.83 (s, 3H); 13C NMR (125 MHz, CDCl3): δ = 183.8, 181.2, 153.0,
149.1, 148.6, 135.4, 133.3, 132.6, 129.8, 129.0, 127.2, 126.3, 120.9, 120.5, 111.6, 111.3, 76.6,

S6
55.94, 55.85, 39.4. IR (KBr): ν 3330, 2937, 2838, 1668, 1645, 1593, 1552, 1515, 1463, 1373,
1268, 1145, 1026, 911, 865, 727 cm-1. HRMS (ESI): m/z calcd. for C20H18NO7 [M + H]+
384.10778, found 384.10775.

(R)-2-[1-(3,4-Dimethoxyphenyl)-2-nitroethyl]-3-methoxy-1,4-naphthoquinone (3i′)
O
OMe

NO2
O

OMe
OMe
Compound 3i′ was obtained through treating compound 3i with CH2N2 in Et2O for 30 min as
a yellow solid; m. p. 46−48 oC. Enantiomeric excess was determined by HPLC on Daicel
Chiralcel IA column (n-hexane-isopropanol 80:20 V/V, flow rate 1.0 mL/min, 254 nm), major
enantiomer tr = 16.0 min, minor enantiomer tr = 23.2 min, 96% ee; [α]D25 = −25.4 (c = 1.71,
CH2Cl2). 1H NMR (500 MHz, CDCl3): δ = 8.05−8.03 (m, 1H), 8.00−7.98 (m, 1H), 7.72−7.66
(m, 2H), 6.98−6.96 (m, 2H), 6.80 (d, J = 8.0 Hz, 1H), 5.38 (dd, J1 = 9.0 Hz, J2 = 13.0 Hz, 1H),
5.33−5.29 (m, 1H), 5.13 (dd, J1 = 6.5 Hz, J2 = 13.0 Hz, 1H), 4.20 (s, 3H), 3.87 (s, 3H), 3.83 (s,
3H); 13C NMR (125 MHz, CDCl3): δ = 184.7, 181.4, 158.0, 149.1, 148.6, 134.2, 133.6, 131.6,
131.2, 131.1, 129.9, 126.5, 126.2, 120.4, 111.6, 111.4, 77.1, 61.8, 55.94, 55.85, 39.3. IR (KBr):
ν 2954, 2838, 1673, 1652, 1594,1560, 1515, 1463, 1332, 1264, 1216, 1145, 1025, 919, 726
cm-1. HRMS (ESI): m/z calcd. for C21H20NO7 [M + H]+ 398.12343, found 398.12348.

(R)-2-[1-(2-Furanyl)-2-nitroethyl]-3-hydroxy-1,4-naphthoquinone (3j)
O
OH

NO2
O
O

Compound 3j was obtained according to the general procedure as an orange solid (57.6 mg,
92% yield); m.p. 107−109 oC. Enantiomeric excess was determined by HPLC on Daicel
Chiralcel OJ-H column (n-hexane-isopropanol 70:30 V/V, flow rate 1.0 mL/min, 254 nm),
minor enantiomer tr = 22.2 min, major enantiomer tr = 31.4 min, 97% ee; [α]D25 = −3.2 (c =
0.57, CH2Cl2). 1H NMR (500 MHz, CDCl3): δ = 8.14 (d, J = 8.0 Hz, 1H), 8.10 (d, J = 7.5 Hz,
1H), 7.82−7.78 (m, 2H), 7.72 (t, J = 7.5 Hz, 1H), 7.33 (s, 1H), 6.31 (dd, J1 = 2.0 Hz, J2 = 3.0
Hz, 1H), 6.24 (d, J = 3.5 Hz, 1H), 5.48 (t, J = 8.0 Hz, 1H), 5.28 (dd, J1 = 9.0 Hz, J2 = 13.5 Hz,
1H), 5.18 (dd, J1 = 7.0 Hz, J2 = 13.5 Hz, 1H).

(R)-2-Hydroxy-3-[2-nitro-1-(2-thienyl)ethyl]-1,4-naphthoquinone (3k)

S7
 O
OH

NO2
O
S

Compound 3k was obtained according to the general procedure as an orange solid (61.0 mg,
93% yield); m.p. 118−120 oC. Enantiomeric excess was determined by HPLC on Daicel
Chiralcel OJ-H column (n-hexane-isopropanol 70:30 V/V, flow rate 1.0 mL/min, 254 nm),
minor enantiomer tr = 23.8 min, major enantiomer tr = 41.8 min, 98% ee; [α]D25 = −62.5 (c =
1.52, CH2Cl2). 1H NMR (500 MHz, CDCl3): δ = 8.15 (d, J = 7.5 Hz, 1H), 8.07 (d, J = 8.0 Hz,
1H), 7.95 (s, 1H), 7.79 (d, J = 7.5 Hz, 1H), 7.71 (t, J = 7.5 Hz, 1H), 7.22 (dd, J1 = 1.0 Hz, J2
= 5.0 Hz, 1H), 7.14 (d, J = 3.5 Hz, 1H), 6.95 (dd, J1 = 3.5 Hz, J2 = 5.0 Hz, 1H), 5.65 (dd, J1 =
7.0 Hz, J2 = 9.0 Hz, 1H), 5.46 (dd, J1 = 9.0 Hz, J2 = 13.5 Hz, 1H), 5.18 (dd, J1 = 6.5 Hz, J2 =
13.5 Hz, 1H).

(R)-2-Hydroxy-3-[1-(nitromethyl)-3-phenylpropyl]-1,4-naphthoquinone (3l)
O
OH

NO2
O

Ph

Compound 3l was obtained according to the general procedure as an orange solid (62.6 mg,
89% yield); m.p. 138−140 oC. Enantiomeric excess was determined through its O-methyl
derivative by HPLC, 97% ee; [α]D25 = +47.3 (c = 1.42, CH2Cl2). 1H NMR (500 MHz, CDCl3):
δ = 8.11 (d, J = 7.5 Hz, 1H), 8.05 (d, J = 7.5 Hz, 1H), 7.78 (t, J = 7.5 Hz, 1H), 7.70 (t, J = 7.5
Hz, 2H), 7.16 (t, J = 7.5 Hz, 1H), 7.11−7.05 (m, 3H), 4.97 (dd, J1 = 10.0 Hz, J2 = 12.0 Hz,
1H), 4.71 (dd, J1 = 6.0 Hz, J2 = 12.5 Hz, 1H), 4.14−4.08 (m, 1H), 2.72−2.66 (m, 1H),
2.61−2.55 (m, 1H), 2.33−2.26 (m, 1H), 2.04−1.98 (m, 1H).

(R)-2-Methoxy-3-[1-(nitromethyl)-3-phenylpropyl]-1,4-naphthoquinone (3l′)
O
OCH3

NO2
O

Ph
Compound 3l′ was obtained through treating compound 3l with CH2N2 in Et2O for 30 min as
a yellow oil. Enantiomeric excess was determined by HPLC on Daicel Chiralcel OJ-H column
(n-hexane-isopropanol 80:20 V/V, flow rate 1.0 mL/min, 254 nm), minor enantiomer tr = 25.2
min, major enantiomer tr = 21.6 min, 97% ee; [α]D25 = +27.0 (c = 0.92, CH2Cl2). 1H NMR
(500 MHz, CDCl3): δ = 8.05 (d, J = 7.0 Hz, 1H), 8.02 (d, J = 6.5 Hz, 1H), 7.77−7.68 (m, 2H),

S8
7.19 (t, J = 7.5 Hz, 2H), 7.11−7.07 (m, 3H), 4.95 (dd, J1 = 9.5 Hz, J2 = 12.0 Hz, 1H), 4.69 (dd,
J1 = 6.0 Hz, J2 = 12.0 Hz, 1H), 4.14 (s, 4H), 2.70−2.64 (m, 1H), 2.59−2.53 (m, 1H), 2.26−2.18
(m, 1H), 2.04−1.97 (m, 1H).

(R)-2-(1-Cyclohexyl-2-nitroethyl)-3-hydroxy-1,4-naphthoquinone (3m)
O
OH

NO2
O

Compound 3m was obtained according to the general procedure as an orange solid (51.1 mg,
78% yield); m.p. 106−108 oC. Enantiomeric excess was determined through its O-methyl
derivative by HPLC, 96% ee; [α]D25 = +46.2 (c = 1.28, CH2Cl2). 1H NMR (500 MHz, CDCl3):
δ = 8.13 (d, J = 7.5 Hz, 1H), 8.08 (d, J = 8.0 Hz, 1H), 7.79 (t, J = 7.5 Hz, 1H), 7.72−7.69 (m,
2H), 5.09 (dd, J1 = 11.0 Hz, J2 = 12.5 Hz, 1H), 4.81 (dd, J1 = 5.0 Hz, J2 = 12.5 Hz, 1H), 3.85
−3.80 (m, 1H), 1.95−1.86 (m, 2H), 1.78 (d, J = 13.0 Hz, 1H), 1.64 (br s, 2H), 1.58 (d, J = 13.0
Hz, 1H), 1.27−1.22 (m, 1H), 1.18−1.11 (m, 3H), 1.08−0.99 (m, 1H).

(R)-2-(1-Cyclohexyl-2-nitro)ethyl-3-methoxy-1,4-naphthoquinone (3m′)
O
OCH3

NO2
O

Compound 3m′ was obtained through treating compound 3k with CH2N2 in Et2O for 30 min
as an orange solid; m.p. 94−96 oC. Enantiomeric excess was determined by HPLC on
Chiralpak IA column (n-hexane-isopropanol 95:5 V/V, flow rate 1.0 mL/min, 254 nm), minor
enantiomer tr = 9.8 min, major enantiomer tr = 8.5 min, 96% ee; [α]D25 = +29.6 (c = 0.87,
CH2Cl2). 1H NMR (500 MHz, CDCl3): δ = 8.06 (d, J = 7.0 Hz, 1H), 8.04 (d, J = 6.0 Hz, 1H),
7.75−7.69 (m, 2H), 5.01 (t, J = 11.5 Hz, 1H), 4.78 (dd, J1 = 5.0 Hz, J2 = 12.0 Hz, 1H), 4.15 (s,
3H), 3.84 (br s, 1H), 1.88 (d, J = 10.5 Hz, 2H), 1.78 (d, J = 11.5 Hz, 1H), 1.65−1.63 (m, 2H),
1.51 (d, J = 12.5 Hz, 1H), 1.27−1.22 (m, 1H), 1.20−1.06 (m, 3H), 1.01−0.94 (m, 1H).

(R)-3-Hydroxy-6-methyl-2-(2-nitro-1-phenylethyl)-1,4-naphthoquinone (3n)
O
Me OH

NO2
O Ph
Compound 3n was obtained according to the general procedure as an orange solid (64.0 mg,
95% yield); m.p. 122−124 oC. Enantiomeric excess was determined by HPLC on Daicel

S9
Chiralcel OJ-H column (n-hexane-isopropanol 70:30 V/V, flow rate 1.0 mL/min, 254 nm),
minor enantiomer tr = 18.6 min, major enantiomer tr = 32.1 min, 98% ee; [α]D25 = −25.9 (c =
1.66, CH3COCH3). 1H NMR (500 MHz, CDCl3): δ = 7.98 (d, J = 7.5 Hz, 1H), 7.84 (s, 1H),
7.76 (s, 1H), 7.54 (d, J = 7.5 Hz, 1H), 7.46 (d, J = 7.5 Hz, 2H), 7.31 (d, J = 7.5 Hz, 2H),
7.26−7.23 (m, 1H), 5.46 (dd, J1 = 9.0 Hz, J2 = 13.0 Hz, 1H), 5.31 (t, J = 8.0 Hz, 1H), 5.15 (dd,
J1 = 7.0 Hz, J2 = 13.0 Hz, 1H), 2.46 (s, 3H).

(R)-3-Hydroxy-6-methyl-2-[1-(4-methylphenyl)-2-nitroethyl]-1,4-naphthoquinone (3o)
O
Me OH

NO2
O

Me

Compound 3o was obtained according to the general procedure as an orange solid (67.4 mg,
96% yield); m.p. 134−136 oC. Enantiomeric excess was determined by HPLC on Daicel
Chiralcel OJ-H column (n-hexane-isopropanol 70:30 V/V, flow rate 1.0 mL/min, 254 nm),
minor enantiomer tr = 25.0 min, major enantiomer tr = 46.6 min, 97% ee; [α]D25 = −27.6 (c =
1.65, CH3COCH3). 1H NMR (500 MHz, CDCl3): δ = 7.96 (d, J = 7.5 Hz, 1H), 7.81 (s, 1H),
7.51 (d, J = 8.0 Hz, 1H), 7.35 (d, J = 8.0 Hz, 1H), 7.11 (d, J = 8.0 Hz, 1H), 5.43 (dd, J1 = 9.0
Hz, J2 = 13.5 Hz, 1H), 5.27 (t, J = 8.0 Hz, 1H), 5.14 (dd, J1 = 7.0 Hz, J2 = 13.5 Hz,1H), 2.44
(s, 3H), 2.28 (s, 3H).

(R)-3-Hydroxy-6-methoxy-2-(2-nitro-1-phenylethyl)-1,4-naphthoquinone (3p)
O
MeO OH

NO2
O Ph
Compound 3p was obtained according to the general procedure as an orange solid (53.0 mg,
75% yield); m.p. 130−131 oC. Enantiomeric excess was determined by HPLC on Daicel
Chiralcel OJ H column (n-hexane-isopropanol 70:30 V/V, flow rate 1.0 mL/min, 254 nm),
minor enantiomer tr = 27.8 min, major enantiomer tr = 41.6 min, 97% ee; [α]D25 = −7.5 (c =
0.88, CH2Cl2). 1H NMR (500 MHz, CDCl3): δ = 8.03 (d, J = 8.5 Hz, 1H), 7.47−7.46 (d, J =
7.5 Hz, 3H), 7.31 (t, J = 7.5 Hz, 2H), 7.24 (t, J = 7.0 Hz, 1H), 7.22 (dd, J1 = 2.5 Hz, J2 = 8.5
Hz, 1H), 5.46 (dd, J1 = 9.0 Hz, J2 = 13.5 Hz, 1H), 5.30 (t, J = 8.0 Hz, 1H), 5.16 (dd, J1 = 7.0
Hz, J2 = 13.5 Hz, 1H), 3.91 (s, 3H).

(R)-(E)-2-Hydroxy-3-[1-(nitromethyl)-3-phenyl-2-propenyl]-1,4-naphthoquinone (5)

S10
 O
OH

NO2
O

Ph

Compound 5 was obtained according to the general procedure as an orange solid (52.3 mg,
75% yield); m.p. 130−131 oC. Enantiomeric excess was determined by HPLC on Daicel
Chiralcel OJ H column (n-hexane-isopropanol 85:15 V/V, flow rate 1.0 mL/min, 254 nm),
minor enantiomer tr = 49.1 min, major enantiomer tr = 59.0 min, 95% ee; [α]D25 = +15.9 (c =
1.02, CH2Cl2). 1H NMR (500 MHz, CDCl3): δ = 8.13 (d, J = 7.0 Hz, 1H), 8.07 (d, J = 7.0 Hz,
1H), 7.80 (s, 1H), 7.77 (dt, J1 = 1.0 Hz, J2 = 7.5 Hz, 1H), 7.69 (dt, J1 = 1.0 Hz, J2 = 7.5 Hz,
1H), 7.37−7.31 (m, 2H), 7.27 (t, J = 7.5 Hz, 2H), 7.21 (t, J = 7.5 Hz, 1H), 6.67 (d, J = 15.5 Hz,
1H), 6.41 (dd, J1 = 9.0 Hz, J2 = 15.5 Hz, 1H), 5.04 (dd, J1 = 8.0 Hz, J2 = 12.0 Hz, 1H), 4.93
(dd, J1 = 7.5 Hz, J2 = 12.0 Hz, 1H), 4.87 (dd, J1 = 9.0 Hz, J2 = 16.0 Hz, 1H); 13C NMR (125
MHz, CDCl3): δ = 183.6, 181.0, 153.5, 136.2, 135.5, 134.5, 133.8, 133.4, 132.6, 129.1, 128.6,
128.1, 127.2, 126.54, 126.46, 125.6, 123.6, 119.8, 76.5, 38.4. IR (KBr): ν 3358, 1654, 1645,
1590, 1546, 1494, 1447, 1380, 1364, 1345, 1307, 1274, 1245, 972, 911, 864, 795, 749, 728,
695, 569 cm-1. HRMS (ESI): m/z calcd. for C20H15NNaO5 [M + Na]+: 372.08424, found
372.08415.

Gram-scale synthesis and synthetic transformation of the Michael adduct 3a

(R)-2-Hydroxy-3-(2-nitro-1-phenylethyl)-1,4-naphthoquinone (3a)

O O
OH OH
Ph 0.25 mol% catalyst VIII
+ NO 2
CH 2Cl2, 30 o C, 6 h NO 2
O O Ph
1a 2a 3a
10.0 mmol, 1.74 g 10.0 mmol, 1.49 g 3.12 g, 97% yield, 98% ee
β-Nitrostyrene 2a (1.49 g, 10.0 mmol) was added to a stirred solution of catalyst VIII (10.5
mg, 0.025 mmol) in CH2Cl2 (12.5 mL), then 1,4-naphthoquinone 1a (1.74 g, 10.0 mmol) was
added. The reaction mixture was stirred at 30 oC for 6 h. The mixture was concentrated and
purified by silica gel column chromatography (CH2Cl2) to afford the desired product 3a as an
orange solid (3.12 g, 97% yield, 98% ee).

(R)-2-Chloro-3-(2-nitro-1-phenylethyl)-1,4-naphthoquinone (6)

S11
 O O
OH (COCl) 2, DMF Cl

CH 2Cl2, r.t.
NO 2 NO 2
O Ph O Ph
3a 6
92% yield, 97% ee

Oxalyl dichloride (0.72 mL, 10.0 mmol) was added to a stirred solution of
(R)-2-hydroxy-3-(2-nitro-1-phenylethyl)-1,4-naphthoquinone 3a (1.62 g, 5.0 mmol) in
CH2Cl2 (70 mL), then a drop of DMF was added. The reaction mixture was stirred at room
temperature for 12 h. The reaction was quenched with water (60 mL), then the mixture was
extracted with CH2Cl2 (50 mL × 2). The combined organic layer was washed with water (60
mL × 2) and dried over anhydrous Na2SO4. The organic layers were concentrated and purified
by silica gel column chromatography (ethyl acetate-petroleum ether 1:10 V/V) to afford the
desired product 6 as a yellow solid (1.57 g, 92 % yield); m.p. 39−40 oC. Enantiomeric excess
was determined by HPLC on Chiralpak IA column (n-hexane-isopropanol 90:10 V/V, flow
rate 1.0 mL/min, 254 nm), major enantiomer tr = 12.7 min, minor enantiomer tr = 14.9 min,
97% ee; [α]D25 = −102.1 (c = 1.05, CH2Cl2). 1H NMR (500 MHz, CDCl3): δ = 8.12 (dd, J1 =
3.0 Hz, J2 = 6.0 Hz, 1H), 8.08 (dd, J1 = 3.0 Hz, J2 = 6.0 Hz, 1H), 7.78−7.73 (m, 2H), 7.45 (d,
J = 7.5 Hz, 2H), 7.35 (t, J = 7.5 Hz, 2H), 7.29 (t, J = 7.0 Hz, 1H), 5.62 (dd, J1 = 9.0 Hz, J2 =
13.5 Hz, 1H), 5.45 (dd, J1 = 6.5 Hz, J2 = 9.0 Hz, 1H), 5.21 (dd, J1 = 6.5 Hz, J2 = 13.5 Hz, 1H);
13
C NMR (125 MHz, CDCl3): δ = 182.8, 177.2, 145.6, 144.0, 135.5, 134.6, 134.3, 131.6,
130.8, 129.2, 128.4, 128.3, 127.3, 76.4, 44.7. IR (KBr): ν 3050, 2850, 1677, 1660, 1598, 1553,
1451, 1378, 1283, 966, 862, 852, 718, 700 cm-1. HRMS (ESI): m/z calcd. for C18H12ClNNaO4
[M + Na]+: 364.03471, found 364.03442.

(R)-2-Morpholino-3-(2-nitro-1-phenylethyl)-1,4-naphthoquinone (7)

O O O
Cl HN O N

NO2 EtOH, 50 oC NO2

O Ph O Ph
6 7
65% yield, 96% ee

To a solution of (R)-2-chloro-3-(2-nitro-1-phenylethyl)-1,4-naphthoquinone 6 (485 mg, 1.43

mmol) in EtOH (5 mL) was added morpholine (249 mg, 2.86 mmol). The reaction mixture
was stirred at 50 oC for 12 h. The reaction was quenched with water (20 mL), then the mixture
was extracted with CH2Cl2 (30 mL × 2). The combined organic layers were dried over
anhydrous Na2SO4, then concentrated and purified by silica gel column chromatography
(ethyl acetate-petroleum ether 1:5 V/V) to afford the product 7 as a red solid (364 mg, 65%
yield); m.p. 59−61 oC. Enantiomeric excess was determined by HPLC on Daicel Chiralcel OJ-
H column (n-hexane-isopropanol 60:40 V/V, flow rate 1.0 mL/min, 254 nm), minor
enantiomer tr = 28.7 min, major enantiomer tr = 85.5 min, 96% ee; [α]D25 = +62.0 (c = 0.10,

S12
CH2Cl2). 1H NMR (500 MHz, CDCl3): δ = 8.04−7.99 (m, 2H), 7.71−7.67 (m, 2H), 7.36−7.31
(m, 4H), 7.27−7.24 (m, 1H), 5.40−5.33 (m, 2H), 5.24−5.18 (m, 1H), 3.87−3.78 (m, 4H),
3.34−3.25 (m, 4H); 13C NMR (125 MHz, CDCl3): δ = 185.4, 183.1, 154.1, 137.7, 134.6,
134.0, 133.5, 132.1, 131.8, 129.0, 127.9, 127.7, 126.4, 126.3, 78.5, 67.3, 52.1, 43.0. IR (KBr):
ν 3049, 2855, 1669, 1595, 1551, 1377, 1334, 1284, 1112, 983, 725, 706 cm-1. HRMS (ESI):
m/z calcd. for C22H21N2O5 [M + H]+: 393.14450, found 393.14466.

References
[1] W. Yang, D.-M. Du, Org. Lett. 2010, 12, 5450.
[2] Y. Zhu, J. P. Malerich, V. H. Rawal, Angew. Chem. Int. Ed. 2010, 49, 153.

S13
 CF3
O O

F3C N N
H H N
V

CF3
O O

F3C N N
H H N
V

S14
 O O
CF3

N N
H H N
VI

O O
CF3

N N
H H N
VI

S15
 CF3
O O

F3C N N
H H N

VII

CF3
O O

F3C N N
H H N

VII

S16
 O O
CF3

N N
H H N

VIII

O O
CF3

N N
H H N

VIII

S17
 O
OH

NO2
O

OMe
3i OMe

O
OH

NO2
O

OMe
3i OMe

S18
 O
OMe

NO2
O

OMe
OMe
3i'

O
OMe

NO2
O

OMe
OMe
3i'

S19
 O
OH

NO2
O

Ph
5

O
OH

NO2
O

Ph
5

S20
 O
Cl

NO2
O Ph
6

O
Cl

NO2
O Ph
6

S21
 O O
N

NO2
O Ph
7

O O
N

NO2
O Ph
7

S22
 O
OH

NO2
O Ph

racemic

(R)-2-Hydroxy-3-(2-nitro-1-phenylethyl)-1,4-naphthoquinone (3a)

O
OH

NO2
O Ph

S23
 O
OH

NO2
O

F
racemic

(R)-2-[1-(4-Fluorophenyl)-2-nitroethyl]-3-hydroxy-1,4-naphthoquinone (3b)

O
OH

NO2
O

S24
 O
OH

NO2
O

Cl
racemic

(R)-2-[1-(4-Chlorophenyl)-2-nitroethyl]-3-hydroxy-1,4-naphthoquinone (3c)

O
OH

NO2
O

Cl

S25
 O
OH

NO2
O

Br
racemic

(R)-2-[1-(4-Bromophenyl)-2-nitroethyl]-3-hydroxy-1,4-naphthoquinone (3d)

O
OH

NO2
O

Br

S26
 O
OH

NO2
O

Me
racemic

(R)-2-Hydroxy-3-[1-(4-methylphenyl)-2-nitroethyl]-1,4-naphthoquinone (3e)

O
OH

NO2
O

Me

S27
 O
OH

NO2
O

racemic OMe

(R)-2-Hydroxy-3-[1-(4-methoxyphenyl)-2-nitroethyl]-1,4-naphthoquinone (3f)

O
OH

NO2
O

OMe

S28
 O
OH

NO 2
O Cl

racemic

(R)-2-[1-(2-Chlorophenyl)-2-nitroethyl]-3-hydroxy-1,4-naphthoquinone (3g)

O
OH

NO 2
O Cl

S29
 O
OH

NO2
O OMe

racemic

(R)-2-Hydroxy-3-[1-(2-methoxyphenyl)-2-nitroethyl]-1,4-naphthoquinone (3h)

O
OH

NO2
O OMe

S30
 O
OMe

NO 2
O

OMe
OMe
racemic

(R)-2-[1-(3,4-Dimethoxyphenyl)-2-nitroethyl]-3-methoxy-1,4-naphthoquinone (3i′)

O
OMe

NO 2
O

OMe
OMe

S31
 O
OH

NO2
O
O

racemic

(R)-2-[1-(2-Furanyl)-2-nitroethyl]-3-hydroxy-1,4-naphthoquinone (3j)

O
OH

NO2
O
O

S32
 O
OH

NO2
O
S

racemic

(R)-2-Hydroxy-3-[2-nitro-1-(2-thienyl)ethyl]-1,4-naphthoquinone (3k)

O
OH

NO2
O
S

S33
 O
OCH3

NO2
O

Ph

racemic

(R)-2-Methoxy-3-[1-(nitromethyl)-3-phenylpropyl]-1,4-naphthoquinone (3l′)

O
OCH3

NO2
O

Ph

S34
 O
OCH3

NO2
O

racemic

(R)- 2-(1-Cyclohexyl-2-nitro)ethyl-3-methoxy-1,4-naphthoquinone (3m′)

O
OCH3

NO2
O

S35
 O
Me OH

NO2
O Ph

racemic

(R)-3-Hydroxy-6-methyl-2-(2-nitro-1-phenylethyl)-1,4-naphthoquinone (3n)

O
Me OH

NO2
O Ph

S36
 O
Me OH

NO2
O

Me
racemic

(R)-3-Hydroxy-6-methyl-2-[1-(4-methylphenyl)-2-nitroethyl]-1,4-naphthoquinone (3o)

O
Me OH

NO2
O

Me

S37
 O
MeO OH

NO2
O Ph
racemic

(R)-3-Hydroxy-6-methoxy-2-(2-nitro-1-phenylethyl)-1,4-naphthoquinone (3p)

O
MeO OH

NO2
O Ph

S38
 O
OH

NO2
O

Ph
racemic

(R)-(E)-2-Hydroxy-3-[1-(nitromethyl)-3-phenyl-2-propenyl]-1,4-naphthoquinone (5)

O
OH

NO2
O

Ph

S39
 O
Cl

NO 2
O

r acemic

(R)-2-Chloro-3-(2-nitro-1-phenylethyl)-1,4-naphthoquinone (6)

O
Cl

NO2
O

S40
 O O
N

NO2
O

r acemic

(R)-2-Morpholino-3-(2-nitro-1-phenylethyl)-1,4-naphthoquinone (7)

O O
N

NO2
O

S41