cascade annulations of benzimidates with alkenes …S1 Synthesis of polydisubstituted 3-aminoindenes...

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Synthesis of polydisubstituted 3-aminoindenes via rhodium-catalysed [3 + 2] cascade annulations of benzimidates with alkenes

Binjie Wu, Zi Yang, Hong Zhang, Lianhui wang, and Xiuling Cui*

Engineering Research Center of Molecular Medicine of Ministry of Education, Key Laboratory of

Fujian Molecular Medicine, Key Laboratory of Xiamen Marine and Gene Drugs, School of

Biomedical Sciences, Huaqiao University, Xiamen 361021, P. R. China, *e-mail: [email protected]

Contents

1.General Information.......................................................................................................................22.Typical procedure for synthesis of 3a............................................................................................23.Conversion of 3a ...........................................................................................................................24.Characterization data of the products ............................................................................................35.X-ray Crystallographic data of 3a................................................................................................126.Reference .....................................................................................................................................197.NMR Spectra of the Products ......................................................................................................208.HRMS spectra of the intermediate E ...........................................................................................44

Electronic Supplementary Material (ESI) for ChemComm.This journal is © The Royal Society of Chemistry 2019

mailto:[email protected]

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1. General Information

Unless otherwise stated, all commercial materials and solvents were used directly

without further purification. Commercially available chemicals were obtained from

Energy Chemical, TCI, Alfa Aesar, J&K. Melting points were determined in open

glass capillaries and were uncorrected. 1H NMR spectra were recorded on 400 MHz

spectrometers, and 13C NMR spectra were recorded on a 100 MHz spectrometer.

High-resolution mass spectra (HRMS) were equipped with an ESI source and a TOF

detector. Column chromatography was performed on silica gel (70-230 mesh ASTM)

using the reported eluents. Thin-layer chromatography (TLC) was carried out on 4×15

cm plates with a layer thickness of 0.2 mm (silica gel 60 F254). Benzimidates[1] and

α,β-unsaturated ketones[2] were synthesized according to the previously reported

procedure.

2. Typical procedure for synthesis of 3a

R1NH

OR2

R4

R3R3

NH2

R4+ R1

[Cp*Rh(MeCN)3](SbF6)2 (5 mol%)1-Ada-CO2H (1 equiv)

DCE, 120℃

1 2 336h, air

To a test tube equipped with magnetic stir bar, alkene (2, 0.40 mmol),

[Cp*Rh(MeCN)3](SbF6)2 (0.01 mmol, 8.3 mg), 1-Ada-CO2H (0.2 mmol, 36.0 mg),

DCE (2ml) and benzimidate (1, 0.20 mmol) were added sequentially under air

atmosphere. The reaction mixture was stirred at 120°C for 36 h. After cooled to room

temperature, Na2CO3 (0.2 mmol, 21.2mg) was added. The resulting mixture was

stirred at room temperature for another 1 h. After removal of the solvent under

reduced pressure, purification was performed by flash column chromatography on

silica gel with petroleum ether/ethyl acetate (gradient mixture ratio from 5:1 to 2:1) as

eluent to afford the desired product 3.

3. Conversion of 3aNH2

O

PhPh

PhNHNH2·HCl+NN Ph

Ph

Ph

EtOH

100℃

3a 4, 95%

12 h

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To a test tube equipped with magnetic stir bar, 3a (0.1 mmol), phenylhydrazine

hydrochloride (0.3 mmol) and dry ethanol (1 ml) were added sequentially under air

atmosphere. The reaction mixture was stirred at 100°C for 12 h and cooled to room

temperature. After evaporation of solvent, the residue was dissolved in ethyl acetate,

and the organic layer was washed subsequently with H2O and then dried with

anhydrous MgSO4. After concentration under reduced pressure, the residue was

purified by column chromatography on silica gel to afford the product 4 in 95%

yield.[3]

4. Characterization data of the products

3-Amino-1-phenyl-1H-inden-2-yl)(phenyl)methanone (3a)

NH2

O

yellow solid, 88% yield, mp: 209-210°C. 1H NMR (400 MHz, DMSO) δ 8.71 (s, 2H),

8.07-8.01 (m, 1H), 7.44-7.34 (m, 4H), 7.28-7.17 (m, 3H), 7.17-7.07 (m, 1H), 6.99-

6.89 (m, 3H), 6.81-6.73 (m, 2H), 5.28(s, 1H). 13C NMR (100 MHz, DMSO) δ 191.3,

161.9, 150.6, 142.8, 142.3, 136.6, 130.8, 129.4, 128.3, 128.0, 127.6, 127.4, 127.2,

126.2, 125.1, 122.0, 110.8, 52.7. HRMS (ESI) Calcd for C22H17NO [M+H]+ 312.1383;

found 312.1386.

3-Amino-6-chloro-1-phenyl-1H-inden-2-yl)(phenyl)methanone (3b)

NH2

OCl


8.07 (d, J = 8.2 Hz, 1H), 7.52-7.46 (m, 1H), 7.42-7.35 (m, 2H), 7.29-7.17 (m, 3H),

7.11 (d, J = 1.9 Hz, 1H), 7.02-6.92 (m, 3H), 6.84-6.76 (m, 2H), 5.31 (s,1H). 13C NMR

(100 MHz, DMSO) δ 191.4, 160.6, 152.4, 142.6, 141.5, 135.6, 135.4, 129.6, 128.5,

128.0, 127.8, 127.6, 127.2, 126.5, 125.0, 123.7, 110.8, 52.5. HRMS (ESI) Calcd for

C22H16ClNO [M+H]+ 346.0993; found 346.0994.

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3-Amino-6-bromo-1-phenyl-1H-inden-2-yl)(phenyl)methanone (3c)

NH2

OBr


8.00 (d, J = 8.2 Hz, 1H), 7.66-7.59 (m, 1H), 7.41-7.36 (m, 2H), 7.28-7.18 (m, 4H),

7.02-6.92 (m, 3H), 6.85-6.78 (m, 2H), 5.31 (s,1H). 13C NMR (100 MHz, DMSO) δ

191.4, 160.7, 152.6, 142.6, 141.4, 135.9, 130.6, 129.6, 128.5, 128.0, 127.9, 127.6,

127.2, 126.6, 124.1, 124.0, 110.7, 52.5. HRMS (ESI) Calcd for C22H16BrNO [M+H]+

390.0488; found 390.0488.

3-Amino-6-methyl-1-phenyl-1H-inden-2-yl)(phenyl)methanone (3d)

NH2

O


7.91 (d, J = 7.8 Hz, 1H), 7.39-7.33 (m, 2H), 7.26-7.17 (m, 4H), 6.99-6.89 (m, 4H),

6.80-6.73 (m, 2H), 5.21 (s,1H), 2.28 (s, 3H). 13C NMR (100 MHz, DMSO) δ 191.0,

162.2, 151.0, 142.9, 142.5, 140.9, 134.0, 129.3, 128.4, 128.3, 127.9, 127.6, 127.2,

126.2, 125.5, 121.8, 110.5, 52.5, 21.8. HRMS (ESI) Calcd for C23H19NO [M+H]+

326.1539; found 326.1540.

3-Amino-6-methoxy-1-phenyl-1H-inden-2-yl)(phenyl)methanone (3e)

NH2

OMeO


7.96 (d, J = 8.6 Hz, 1H), 7.40-7.27 (m, 2H), 7.26-7.15 (m, 3H), 7.02-6.89 (m, 4H),

6.79-6.73 (m, 2H), 6.62 (d, J = 2.3 Hz, 1H), 5.20 (s,1H), 3.70 (s, 3H). 13C NMR (100

MHz, DMSO) δ 190.4, 162.3, 162.1, 153.1, 143.0, 142.6, 129.2, 129.1, 128.3, 127.9,

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127.6, 127.2, 126.2, 123.4, 113.8, 110.3, 110.2, 55.9, 52.5. HRMS (ESI) Calcd for

C23H19NO2 [M+H]+ 342.1489; found 342.1490.

3-Amino-5-methyl-1-phenyl-1H-inden-2-yl)(phenyl)methanone (3f)

NH2

O


7.86 (s, 1H), 7.40-7.35 (m, 2H), 7.27-7.17 (m, 4H), 7.01-6.88 (m, 4H), 6.79-6.71 (m,

2H), 5.21 (s, 1H). 13C NMR (100 MHz, DMSO) δ 191.2, 162.1, 148.0, 142.8, 142.5,

136.8, 136.7, 131.7, 129.4, 128.3, 127.9, 127.5, 127.2, 126.2, 124.8, 122.2, 111.2,

52.3, 21.5. HRMS (ESI) Calcd for C23H19NO [M+H]+ 326.1539; found 326.1539.

3-Amino-5-methoxy-1-phenyl-1H-inden-2-yl)(phenyl)methanone (3g)

NH2

O

MeO


7.70 (d, J = 2.0 Hz, 1H), 7.39-7.35 (m, 2H), 7.27-7.17 (m, 3H), 7.00-6.88 (m, 5H),

6.77-6.71 (m, 2H), 5.19 (s, 1H), 3.81 (s, 3H). 13C NMR (100 MHz, DMSO) δ 191.2,

161.9, 159.3, 143.0, 142.8, 142.5, 137.8, 129.4, 128.3, 127.9, 127.5, 127.3, 126.1,

125.8, 117.9, 111.8, 106.3, 55.9, 52.0. HRMS (ESI) Calcd for C23H19NO2 [M+H]+

342.1489; found 342.1489.

3-Amino-1-(4-fluorophenyl)-1H-inden-2-yl)(phenyl)methanone (3h)

NH2

O

F


8.09-8.01 (m, 1H), 7.45-7.36 (m, 4H), 7.29-7.19 (m, 3H), 7.15-7.06 (m, 1H), 6.77 (d,

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J = 7.14 Hz, 4H), 5.29 (s,1H). 13C NMR (100 MHz, DMSO) δ 191.4, 161.9, 160.8 (d,

JCF= 241.6 Hz),150.5, 142.8, 138.3 (d, JCF= 3.0 Hz), 136.5, 130.9, 129.5, 129.3 (d,

JCF= 8.0 Hz), 128.0, 127.6, 127.2, 125.1, 122.1, 115.0 (d, JCF= 21.3 Hz), 110.8, 51.8.

19F NMR (376 MHz, DMSO) δ -117.25. HRMS (ESI) Calcd for C22H16FNO [M+H]+

330.1289; found 330.1290.

3-Amino-1-(4-chlorophenyl)-1H-inden-2-yl)(phenyl)methanone (3i)

NH2

O

Cl


8.09-8.00 (m, 1H), 7.46-7.36 (m, 4H), 7.32-7.18 (m, 3H), 7.15-7.07 (m, 1H), 7.06-

6.97 (m, 2H), 6.81-6.74 (m, 2H), 5.31 (s, 1H). 13C NMR (100 MHz, DMSO) δ 191.2,

162.0, 150.2, 142.7, 141.4, 136.5, 131.0, 130.6, 129.5, 129.4, 128.3, 128.1, 127.6,

127.2, 125.1, 122.1, 110.5, 51.9. HRMS (ESI) Calcd for C22H16ClNO [M+H]+

346.0993; found 346.0994.

3-Amino-1-(4-nitrophenyl)-1H-inden-2-yl)(phenyl)methanone (3j)

NH2

O

NO2


8.13-8.06 (m, 1H), 7.88-7.80 (m, 2H), 7.48-7.35 (m, 4H), 7.28-7.18 (m, 3H), 7.12 (d,

J = 7.4 Hz, 1H), 7.08-6.98 (m, 2H), 5.48 (s, 1H). 13C NMR (100 MHz, DMSO) δ

191.1, 162.1, 151.1, 149.4, 146.0, 142.6, 136.7, 131.2, 129.6, 128.9, 128.2, 128.0,

127.1, 125.2, 123.6, 122.4, 110.3, 52.1. HRMS (ESI) Calcd for C22H16N2O3 [M+H]+

357.1234; found 357.1236.

3-Amino-1-(p-tolyl)-1H-inden-2-yl)(phenyl)methanone (3k)

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NH2

O


8.06-7.96 (m, 1H), 7.46-7.33 (m, 4H), 7.31-7.17 (m, 3H), 7.14-7.06 (m, 1H), 6.78 (d,

J = 8.32 Hz, 2H), 6.71-6.61 (m, 2H), 5.26 (s, 1H), 2.09 (s, 3H). 13C NMR (100 MHz,

DMSO) δ 191.2, 161.9, 150.8, 142.7, 139.2, 136.5, 135.1, 130.8, 129.5, 129.0, 128.0,

127.5, 127.4, 127.3, 125.1, 121.9, 110.7, 52.3, 21.0. HRMS (ESI) Calcd for

C23H19NO [M+H]+ 326.1539; found 326.1541.

3-Amino-1-(m-tolyl)-1H-inden-2-yl)(phenyl)methanone (3l)

NH2

O


8.07-8.02 (m, 1H), 7.43-7.35 (m, 4H), 7.29-7.19 (m, 3H), 7.15-7.08 (m, 1H), 6.85 (t, J

= 7.5 Hz, 1H), 6.73 (d, J = 7.5 Hz, 1H), 6.58-6.51 (m, 2H), 5.21 (s, 1H). 13C NMR

(100 MHz, DMSO) δ 191.4, 161.8, 150.6, 142.9, 142.1, 137.1, 136.7, 130.8, 129.3,

128.3, 128.2, 127.9, 127.4, 127.2, 126.9, 125.1, 124.8, 122.0, 110.9, 52.6, 21.3.

HRMS (ESI) Calcd for C23H19NO [M+H]+ 326.1539; found 326.1542.

3-Amino-1-(3-methoxyphenyl)-1H-inden-2-yl)(phenyl)methanone (3m)

NH2

O

OMe


8.07-7.98 (m, 1H), 7.48-7.35 (m, 4H), 7.32-7.19 (m, 3H), 7.19-7.11 (m, 1H), 6.88 (t, J

= 7.9 Hz, 1H), 6.54-6.47 (m, 1H), 6.41-6.28 (m, 2H), 5.25 (s, 1H), 3.55 (s, 3H). 13C

NMR (100 MHz, DMSO) δ 191.3, 161.9, 159.2, 150.4, 143.9, 142.8, 136.5, 130.8,

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129.5, 129.4, 128.0, 127.5, 127.3, 125.0, 121.9, 119.6, 113.6, 111.7, 110.6, 55.2, 52.6.

HRMS (ESI) Calcd for C23H19NO2 [M+H]+ 342.1489; found 342.1492.

3-Amino-1-(3-nitrophenyl)-1H-inden-2-yl)(phenyl)methanone (3n)

NH2

O

NO2


8.12-8.06 (m, 1H), 7.83-7.78 (m, 1H), 7.57-7.53 (m, 1H), 7.49-7.40 (m, 2H), 7.36-

7.31 (m, 2H), 7.28-7.11 (m, 6H), 5.47 (s, 1H). 13C NMR (100 MHz, DMSO) δ 191.3,

162.0, 149.6, 147.6, 144.9, 142.7, 136.8, 134.4, 131.2, 129.9, 129.4, 128.1, 128.0,

127.0, 125.2, 122.6, 122.3, 121.4, 110.5, 51.77. HRMS (ESI) Calcd for C22H16N2O3

[M+H]+ 357.1234; found 357.1236.

3-Amino-1-phenyl-1H-inden-2-yl)(4-fluorophenyl)methanone (3o)

NH2

O

F


8.08-8.02 (m, 1H), 7.51-7.37 (m, 4H), 7.13-7.09 (m, 1H), 7.05-6.91 (m, 5H), 6.85-

6.76 (m, 2H), 5.29 (s,1H). 13C NMR (100 MHz, DMSO) δ 189.9, 162.8 (d, JCF= 245.7

Hz), 162.2, 150.6, 142.2, 139.3 (d, JCF= 3.1 Hz), 136.5, 130.9, 129.8 (d, JCF= 8.6 Hz),

128.4, 127.6, 127.5, 126.4, 125.1, 122.0, 114.8 (d, JCF= 21.3 Hz), 110.6, 52.6. 19F

NMR (376 MHz, DMSO) δ -111.98. HRMS (ESI) Calcd for C22H16FNO [M+H]+

330.1289; found 330.1288.

3-Amino-1-phenyl-1H-inden-2-yl)(4-chlorophenyl)methanone (3p)

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NH2

O

Cl


8.17-7.97 (m, 1H), 7.54-7.32 (m, 4H), 7.31-7.19 (m, 2H), 7.17-7.06 (m, 1H), 7.06-

6.89(m, 3H), 6.89-6.72 (m, 2H), 5.28 (s, 1H). 13C NMR (100 MHz, DMSO) δ 189.7,

162.4, 150.6, 142.1, 141.4, 136.4, 134.1, 131.0, 129.2, 128.4, 128.0, 127.6, 127.5,

126.4, 125.1, 122.1, 110.5, 52.47. HRMS (ESI) Calcd for C22H16ClNO [M+H]+

346.0993; found 346.0993.

3-Amino-1-phenyl-1H-inden-2-yl)(p-tolyl)methanone (3q)

NH2

O


8.04-7.99 (m, 1H), 7.43-7.34 (m, 4H), 7.15-7.10 (m, 1H), 7.05-6.92 (m, 5H), 6.87-

6.80 (m, 2H), 5.33 (s, 1H), 2.24 (s,3H). 13C NMR (100 MHz, DMSO) δ 190.9, 161.8,

150.5, 142.4, 139.9, 139.1, 136.6, 130.7, 128.5, 128.4, 127.6, 127.5, 127.4, 126.3,


found 326.1542.

3-Amino-1-phenyl-1H-inden-2-yl)(4-methoxyphenyl)methanone (3r)

NH2

O

OMe


8.03-7.97 (m, 1H), 7.54-7.47 (m, 2H), 7.43-7.34 (m, 2H), 7.16-7.10 (m, 1H), 7.04-

6.91 (m, 3H), 6.91-6.85 (m, 2H), 6.79-6.73 (m, 2H), 5.38 (s, 1H), 3.72 (s, 3H). 13C

NMR (100 MHz, DMSO) δ 190.0, 161.7, 160.5, 150.4, 142.5, 136.6, 135.1, 130.6,

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129.6, 128.4, 127.5, 127.4, 126.4, 125.0, 121.8, 113.2, 110.5, 55.6, 52.8. HRMS (ESI)

Calcd for C23H19NO2 [M+H]+ 342.1489; found 342.1491.

(3-Amino-1-ethyl-1H-inden-2-yl)(phenyl)methanone (3s)NH2

O


7.98 (d, J = 7.52 Hz, 1H), 7.67-7.59 (m, 2H), 7.56-7.39 (m, 6H), 4.30-4.18 (m, 1H),

1.74-1.62 (m, 1H), 1.17-1.05 (m, 1H), 0.19 (t, J = 7.44 Hz, 3H). 13C NMR (100 MHz,

DMSO) δ 190.7, 161.6, 149.4, 143.3, 137.6, 130.4, 129.9, 128.6, 127.2, 127.1, 124.2,


found 264.1386.

1-(3-Amino-1-phenyl-1H-inden-2-yl)ethan-1-one (3t)NH2

O


7.97-7.92 (m, 1H), 7.40-7.33 (m, 2H), 7.30-7.23 (m, 2H), 7.22-7.10 (m, 4H), 4.96 (s,

1H), 1.76 (s, 3H). 13C NMR (100 MHz, DMSO) δ 193.7, 159.1, 149.8, 142.8, 136.9,

130.4, 129.1, 127.8, 127.4, 127.0, 125.1, 121.9, 111.3, 52.2, 28.7. HRMS (ESI) Calcd

for C17H15NO [M+H]+ 250.1226; found 250.1228.

3-Amino-1-phenyl-1H-inden-2-yl)(naphthalen-2-yl)methanone (3u)

NH2

O


8.12-8.06 (m, 2H), 7.95-7.91 (m, 1H), 7.85-7.81 (m, 1H), 7.73 (d, J = 8.5 Hz, 1H),

7.55-7.49 (m, 3H), 7.47-7.37 (m, 2H), 7.17-7.10 (m, 1H), 6.90-6.81 (m, 5H), 5.51

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(s,1H). 13C NMR (100 MHz, DMSO) δ 190.7, 162.3, 150.7, 142.5, 139.7, 136.5,

133.5, 132.4, 130.9, 129.1, 128.4, 127.8, 127.6, 127.5, 127.4, 127.3, 127.2, 126.6,

126.3, 125.2, 125.1, 122.0, 110.9, 52.7. HRMS (ESI) Calcd for C26H19NO [M+H]+

362.1539; found 362.1538.

2-Nitro-1-phenyl-1H-inden-3-amine (3v)NH2

NO2


8.99 (s, 1H), 8.21-8.14 (m, 1H), 7.53-7.45 (m, 2H), 7.30-7.24 (m, 2H), 7.23-7.17 (m,

2H), 7.16-7.09 (m, 2H), 5.14 (s, 1H). 13C NMR (100 MHz, DMSO) δ 156.1, 147.1,

140.4, 134.2, 132.6, 129.0, 128.2, 127.7, 127.2, 125.5, 123.4, 122.4, 50.6. HRMS

(ESI) Calcd for C15H12N2O2 [M+H]+ 253.0972; found 253.0976.

2,3,4-Triphenyl-2,4-dihydroindeno[1,2-c]pyrazole (4)

NN Ph

Ph

Ph

white solid, 95% yield, mp: 188-189°C. 1H NMR (400 MHz, CDCl3) δ 7.98-7.90 (m,

1H), 7.43-7.12 (m, 16H), 6.98-6.90 (m, 2H), 5.05 (s, 1H). 13C NMR (100 MHz,

CDCl3) δ 159.7, 153.4, 141.7, 140.8, 137.9, 133.6, 130.0, 129.9, 129.1, 128.9, 128.6,

128.2, 128.1, 128.0, 127.7, 127.6, 127.2, 126.9, 126.0, 125.4, 120.4, 47.8. HRMS

(ESI) Calcd for C28H20N2 [M+H]+ 385.1699; found 385.1699.

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5. X-ray Crystallographic data of 3a

X-ray molecular structure of 3a

Table 1 Crystal data and structure refinement for 3a.

Identification code 3a

Empirical formula C22H17NO

Formula weight 311.36

Temperature/K 293(2)

Crystal system orthorhombic

Space group P212121

a/Å 9.8259(6)

b/Å 12.3491(8)

c/Å 13.8190(9)

α/° 90

β/° 90

γ/° 90

Volume/Å3 1676.82(18)

Z 4

ρcalcg/cm3 1.233

μ/mm-1 0.588

F(000) 656.0

Crystal size/mm3 0.18 × 0.16 × 0.15

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Radiation CuKα (λ = 1.54184)

2Θ range for data collection/° 9.606 to 142.272

Index ranges -11 ≤ h ≤ 11, -13 ≤ k ≤ 15, -16 ≤ l ≤ 16

Reflections collected 6963

Independent reflections 3192 [Rint = 0.0307, Rsigma = 0.0408]

Data/restraints/parameters 3192/0/226

Goodness-of-fit on F2 1.043

Final R indexes [I>=2σ (I)] R1 = 0.0404, wR2 = 0.0944

Final R indexes [all data] R1 = 0.0477, wR2 = 0.1006

Largest diff. peak/hole / e Å-3 0.13/-0.12

Flack parameter -0.1(3)

Table 2 Fractional Atomic Coordinates (×104) and Equivalent Isotropic

Displacement Parameters (Å2×103) for 3a. Ueq is defined as 1/3 of of the trace of

the orthogonalised UIJtensor.

Atomx y z U(eq)

C1 -918(3) 3718(2) 3194(2) 45.6(6)

C2 -1712(3) 4333(3) 2584(2) 51.7(7)

C3 -1253(3) 5319(3) 2238(2) 55.5(7)

C4 11(3) 5709(2) 2493(2) 52.7(6)

C5 821(3) 5105(2) 3103.5(18) 42.2(6)

C6 362(3) 4109(2) 3445.4(18) 40.3(5)

C7 1430(2) 3650.4(19) 4061.0(17) 37.8(5)

C8 2501(3) 4380(2) 4130.8(18) 39.3(5)

C9 2235(3) 5359(2) 3491.4(19) 43.3(6)

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C10 3277(3) 5524(2) 2700(2) 49.3(7)

C11 3636(4) 4687(3) 2091(2) 64.8(8)

C12 4596(4) 4828(4) 1363(3) 85.0(12)

C13 5207(4) 5822(5) 1249(3) 92.5(15)

C14 4881(5) 6649(4) 1847(3) 93.7(15)

C15 3911(4) 6515(3) 2572(3) 71.2(10)

C16 3654(2) 4202.2(19) 4713.7(17) 39.2(5)

C17 4673(3) 5095(2) 4836.8(18) 41.3(5)

C18 5986(3) 4970(3) 4490(2) 55.6(7)

C19 6929(4) 5787(3) 4603(3) 69.3(9)

C20 6579(4) 6716(3) 5083(3) 72.4(10)

C21 5288(4) 6845(3) 5444(3) 67.4(9)

C22 4330(3) 6036(2) 5321(2) 52.7(7)

N1 1367(3) 2678.8(18) 4468.5(18) 46.8(5)

O1 3857(2) 3324.2(15) 5144.2(15) 51.6(5)

Table 3 Anisotropic Displacement Parameters (Å2×103) for 3a. The Anisotropic

displacement factor exponent takes the form: -2π2[h2a*2U11+2hka*b*U12+…].

Atom U11 U22 U33 U23 U13 U12

C1 42.8(14) 47.5(14) 46.4(14) -2.8(11) 1.3(11) -2.5(11)

C2 36.7(13) 67.7(17) 50.8(15) -4.9(14) -1.5(11) -0.4(13)

C3 45.8(15) 70.1(18) 50.5(15) 11.0(13) -7.2(12) 8.4(13)

C4 51.7(14) 54.3(15) 52.2(14) 14.8(13) -4.9(13) 2.1(13)

C5 41.3(14) 42.0(13) 43.2(13) 4.6(10) -0.4(10) 1.8(10)

C6 39.2(12) 41.0(12) 40.6(12) -0.3(10) 2.8(10) 2.3(10)

C7 35.9(12) 38.2(11) 39.4(12) 1.0(9) 5.6(10) 2.4(10)

C8 40.2(13) 36.8(11) 40.8(12) 6.7(10) 1.8(10) 0.5(10)

C9 44.4(14) 39.7(13) 45.9(13) 7.6(10) -5.5(11) -1.3(10)

S15

C10 42.1(13) 56.8(16) 49.1(15) 17.5(12) -10.1(11) -6.0(12)

C11 59.1(19) 78(2) 57.2(17) 7.3(16) 0.7(15) -4.3(16)

C12 68(2) 129(4) 58(2) 8(2) 3.5(18) 9(2)

C13 52(2) 159(5) 66(2) 50(3) 0.4(17) -15(3)

C14 80(3) 107(3) 94(3) 47(3) -2(2) -33(3)

C15 71(2) 68(2) 74(2) 27.0(18) -3.9(18) -20.1(17)

C16 38.9(12) 39.0(12) 39.9(12) 2.8(10) 2.8(10) 5.6(10)

C17 41.5(13) 44.3(13) 38.0(12) 5.3(10) -4.7(10) 0.2(11)

C18 49.9(16) 58.3(17) 58.6(17) -4.8(13) 7.0(13) -4.2(13)

C19 54.2(18) 78(2) 76(2) -3.7(19) 10.8(16) -16.4(17)

C20 73(2) 66(2) 78(2) -2.5(17) -3.6(19) -27.2(18)

C21 81(2) 50.0(16) 71(2) -10.5(14) -7.6(19) -4.0(16)

C22 51.4(15) 50.9(15) 55.9(16) -2.1(12) -2.6(13) 3.1(12)

N1 42.1(13) 39.9(11) 58.4(14) 12.7(10) -0.1(11) -2.4(10)

O1 45.4(10) 45.5(10) 63.8(12) 15.1(8) -8.1(9) 4.0(8)

Table 4 Bond Lengths for 3a.

Atom Atom Length/Å Atom Atom Length/Å

C1 C2 1.377(4) C10 C15 1.385(4)

C1 C6 1.392(4) C11 C12 1.390(5)

C2 C3 1.384(4) C12 C13 1.376(7)

C3 C4 1.378(4) C13 C14 1.352(7)

C4 C5 1.380(4) C14 C15 1.393(5)

C5 C6 1.393(4) C16 C17 1.499(4)

C5 C9 1.522(3) C16 O1 1.253(3)

C6 C7 1.465(3) C17 C18 1.384(4)

C7 C8 1.389(3) C17 C22 1.383(4)

S16

C7 N1 1.327(3) C18 C19 1.379(4)

C8 C9 1.521(3) C19 C20 1.369(5)

C8 C16 1.407(3) C20 C21 1.371(5)

C9 C10 1.512(4) C21 C22 1.384(4)

C10 C11 1.379(5)

Table 5 Bond Angles for 3a.

Atom Atom Atom Angle/˚ Atom Atom Atom Angle/˚

C2 C1 C6 118.2(3) C11 C10 C9 120.9(3)

C1 C2 C3 120.8(3) C11 C10 C15 118.1(3)

C4 C3 C2 120.9(3) C15 C10 C9 121.0(3)

C3 C4 C5 119.2(3) C10 C11 C12 121.4(4)

C4 C5 C6 119.9(3) C13 C12 C11 119.4(4)

C4 C5 C9 129.1(3) C14 C13 C12 120.0(4)

C6 C5 C9 111.0(2) C13 C14 C15 120.8(4)

C1 C6 C5 121.0(2) C10 C15 C14 120.3(4)

C1 C6 C7 131.2(2) C8 C16 C17 119.2(2)

C5 C6 C7 107.8(2) O1 C16 C8 122.4(2)

C8 C7 C6 109.4(2) O1 C16 C17 118.4(2)

N1 C7 C6 124.3(2) C18 C17 C16 120.1(2)

N1 C7 C8 126.3(2) C22 C17 C16 120.6(2)

C7 C8 C9 110.2(2) C22 C17 C18 119.2(3)

C7 C8 C16 123.3(2) C19 C18 C17 120.4(3)

C16 C8 C9 126.5(2) C20 C19 C18 119.9(3)

C8 C9 C5 101.4(2) C19 C20 C21 120.4(3)

C10 C9 C5 113.0(2) C20 C21 C22 120.1(3)

S17

C10 C9 C8 114.2(2) C17 C22 C21 120.0(3)

Table 6 Hydrogen Bonds for 3a.

D H A d(D-H)/Å d(H-A)/Å d(D-A)/Å D-H-A/°

N1 H1A O1 0.84(3) 2.11(3) 2.737(3) 131(3)

N1 H1B O11 0.93(3) 1.91(3) 2.811(3) 164(3)

1-1/2+X,1/2-Y,1-Z

Table 7 Torsion Angles for 3a.

A B C D Angle/˚ A B C D Angle/˚

C1 C2 C3 C4 0.2(4) C8 C16 C17 C22 66.5(3)

C1 C6 C7 C8 -176.8(3) C9 C5 C6 C1 179.1(2)

C1 C6 C7 N1 4.2(4) C9 C5 C6 C7 -0.5(3)

C2 C1 C6 C5 1.1(4) C9 C8 C16 C17 8.0(4)

C2 C1 C6 C7 -179.5(3) C9 C8 C16 O1 -172.7(2)

C2 C3 C4 C5 -0.2(5) C9 C10 C11 C12 -179.8(3)

C3 C4 C5 C6 0.7(4) C9 C10 C15 C14 179.2(3)

C3 C4 C5 C9 -179.6(3) C10 C11 C12 C13 0.3(5)

C4 C5 C6 C1 -1.1(4) C11 C10 C15 C14 -0.1(5)

C4 C5 C6 C7 179.3(2) C11 C12 C13 C14 0.5(6)

C4 C5 C9 C8 178.6(3) C12 C13 C14 C15 -1.1(7)

C4 C5 C9 C10 -58.7(4) C13 C14 C15 C10 0.9(6)

C5 C6 C7 C8 2.7(3) C15 C10 C11 C12 -0.5(5)

C5 C6 C7 N1 -176.3(2) C16 C8 C9 C5 -177.0(2)

C5 C9 C10 C11 -64.7(3) C16 C8 C9 C10 61.1(3)

S18

C5 C9 C10 C15 116.1(3) C16 C17 C18 C19 -179.9(3)

C6 C1 C2 C3 -0.6(4) C16 C17 C22 C21 178.9(3)

C6 C5 C9 C8 -1.7(3) C17 C18 C19 C20 1.8(6)

C6 C5 C9 C10 121.0(2) C18 C17 C22 C21 0.8(4)

C6 C7 C8 C9 -3.9(3) C18 C19 C20 C21 -0.8(6)

C6 C7 C8 C16 176.5(2) C19 C20 C21 C22 -0.2(6)

C7 C8 C9 C5 3.4(3) C20 C21 C22 C17 0.2(5)

C7 C8 C9 C10 -118.5(2) C22 C17 C18 C19 -1.8(5)

C7 C8 C16 C17 -172.5(2) N1 C7 C8 C9 175.1(2)

C7 C8 C16 O1 6.9(4) N1 C7 C8 C16 -4.5(4)

C8 C9 C10 C11 50.5(3) O1 C16 C17 C18 65.2(3)

C8 C9 C10 C15 -128.7(3) O1 C16 C17 C22 -112.9(3)

C8 C16 C17 C18 -115.4(3)

Table 8 Hydrogen Atom Coordinates (Å×104) and Isotropic Displacement

Parameters (Å2×103) for 3a.

Atomx y z U(eq)

H1 -1230 3058 3431 55

H2 -2568 4083 2402 62

H3 -1805 5724 1828 67

H4 314 6372 2256 63

H9 2192 6011 3895 52

H11 3227 4013 2169 78

H12 4822 4255 957 102

H13 5846 5925 761 111

H14 5309 7315 1773 112

S19

H15 3687 7094 2973 85

H18 6233 4332 4180 67

H19 7802 5708 4353 83

H20 7219 7263 5165 87

H21 5058 7477 5771 81

H22 3454 6125 5564 63

H1A 2000(30) 2530(20) 4850(20) 44(8)

H1B 570(30) 2280(30) 4490(20) 53(8)

6. References

[1] V. Yadav and K. Babu, Eur. J. Org. Chem. 2005, 452-456.

[2] T. Lei, C. Zhou, M. Huang, L. Zhao, B. Yang, C. Ye, H. Xiao, Q. Meng, V.

Ramamurthy, C. Tung and L. Wu, Angew. Chem. Int. Ed. 2017, 56, 15407-15410.

[3] L. Calvo, A. Gonzalez-Nogal, A. Gonzalez-Ortega and M. Sanudo, Tetrahedron

Lett. 2001, 42, 8981.

S20

7. NMR Spectra of the Products1H, 13C spectra of 3a

-1.0-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.511.0

f1 (ppm)

1.00

2.01

2.98

1.00

2.99

3.97

0.99

1.79

5.28

6.75

6.76

6.76

6.77

6.77

6.78

6.78

6.90

6.90

6.90

6.91

6.92

6.92

6.93

6.93

6.94

6.95

6.96

6.96

6.97

6.98

6.98

7.07

7.08

7.10

7.10

7.11

7.11

7.12

7.13

7.18

7.19

7.19

7.20

7.21

7.22

7.23

7.23

7.24

7.25

7.25

7.26

7.27

7.27

7.27

7.35

7.36

7.36

7.38

7.38

7.39

7.39

7.40

7.40

7.41

7.41

7.43

7.43

8.03

8.03

8.04

8.05

8.05

8.71

-100102030405060708090100110120130140150160170180190200210

f1 (ppm)

39.38

39.59

39.80

40.01

40.22

40.42

40.63

52.66

110.78

121.98

125.08

126.24

127.23

127.44

127.57

127.96

128.33

129.43

130.80

136.56

142.25

142.79

150.60

161.91

191.33

NH2

O

NH2

O

S21

1H, 13C spectra of 3b

-1.0-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.511.0

f1 (ppm)

1.00

2.00

3.02

0.97

3.06

1.98

0.97

1.00

1.76

5.31

6.78

6.79

6.79

6.79

6.80

6.81

6.81

6.94

6.95

6.96

6.96

6.96

6.97

6.98

6.98

6.98

6.99

7.00

7.00

7.11

7.11

7.18

7.19

7.19

7.20

7.20

7.21

7.22

7.22

7.23

7.24

7.24

7.25

7.25

7.26

7.27

7.27

7.28

7.37

7.38

7.38

7.39

7.39

7.40

7.40

7.48

7.49

7.50

7.51

8.06

8.08

8.71

-100102030405060708090100110120130140150160170180190200210

f1 (ppm)

39.38

39.59

39.79

40.00

40.21

40.42

40.63

52.53

110.81

123.70

125.03

126.54

127.19

127.56

127.82

128.00

128.49

129.58

135.36

135.56

141.48

142.57

152.43

160.62

191.40

NH2

OCl

NH2

OCl

S22

1H, 13C spectra of 3c

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.5

f1 (ppm)

1.00

2.00

3.04

4.00

1.98

0.98

0.99

1.90

5.31

6.79

6.79

6.80

6.80

6.81

6.81

6.95

6.96

6.96

6.97

6.97

6.98

6.98

6.99

7.00

7.19

7.20

7.21

7.22

7.23

7.24

7.24

7.25

7.25

7.37

7.37

7.38

7.38

7.39

7.39

7.62

7.62

7.64

7.64

7.99

8.01

8.70

-100102030405060708090100110120130140150160170180190200210

f1 (ppm)

39.39

39.60

39.81

40.01

40.22

40.43

40.64

52.53

110.69

123.97

124.12

126.55

127.18

127.57

127.93

128.00

128.50

129.59

130.62

135.92

141.44

142.56

152.61

160.67

191.42

NH2

OBr

NH2

OBr

S23

1H, 13C spectra of 3d

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.5

f1 (ppm)

2.99

1.00

1.98

4.04

4.04

2.00

1.00

1.84

2.28

5.21

6.74

6.75

6.75

6.76

6.77

6.77

6.77

6.89

6.90

6.91

6.91

6.92

6.93

6.93

6.94

6.94

6.96

6.96

6.97

6.98

6.98

7.17

7.18

7.18

7.19

7.20

7.21

7.22

7.22

7.23

7.23

7.24

7.25

7.25

7.26

7.35

7.35

7.36

7.37

7.37

7.37

7.91

7.93

8.69

-100102030405060708090100110120130140150160170180190200210

f1 (ppm)

21.83

39.38

39.59

39.80

40.01

40.22

40.42

40.63

52.49

110.54

121.83

125.48

126.19

127.19

127.62

127.92

128.31

128.35

129.31

133.98

140.85

142.45

142.88

151.00

162.17

191.01

NH2

O

NH2

O

S24

1H, 13C spectra of 3e

0.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.511.0

f1 (ppm)

3.03

1.00

1.01

1.98

4.07

3.01

1.95

0.94

0.96

3.70

5.20

6.61

6.62

6.74

6.75

6.76

6.76

6.77

6.77

6.78

6.90

6.91

6.91

6.91

6.92

6.93

6.94

6.94

6.95

6.95

6.96

6.97

6.98

6.98

6.99

6.99

7.01

7.01

7.17

7.17

7.18

7.19

7.19

7.20

7.21

7.21

7.22

7.22

7.23

7.24

7.34

7.34

7.35

7.35

7.36

7.36

7.95

7.97

8.45

8.91

-100102030405060708090100110120130140150160170180190200210

f1 (ppm)

39.37

39.58

39.79

40.00

40.21

40.41

40.62

52.54

55.89

110.15

110.25

113.84

123.38

126.23

127.17

127.59

127.91

128.32

129.11

129.22

142.55

142.99

153.10

162.13

162.28

190.38

NH2

OMeO

NH2

OMeO

S25

1H, 13C spectra of 3f

0.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.511.0

f1 (ppm)

2.97

1.00

1.99

4.06

4.05

2.04

0.99

1.96

2.37

5.21

6.73

6.73

6.74

6.74

6.75

6.76

6.88

6.89

6.89

6.90

6.91

6.91

6.92

6.92

6.93

6.94

6.95

6.96

6.96

6.97

6.99

7.17

7.18

7.19

7.20

7.20

7.21

7.21

7.22

7.23

7.23

7.24

7.25

7.25

7.26

7.26

7.27

7.36

7.37

7.37

7.38

7.38

7.39

7.86

8.68

-100102030405060708090100110120130140150160170180190200210

f1 (ppm)

21.52

39.38

39.59

39.79

40.00

40.21

40.42

40.63

52.29

111.18

122.19

124.81

126.15

127.23

127.53

127.94

128.27

129.38

131.73

136.69

136.75

142.47

142.81

148.02

162.05

191.24

NH2

O

NH2

O

S26

1H, 13C spectra of 3g

-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.5

f1 (ppm)

3.04

1.00

1.97

5.04

3.09

2.01

1.00

1.91

3.81

5.19

6.72

6.73

6.73

6.74

6.74

6.75

6.75

6.89

6.90

6.91

6.92

6.92

6.93

6.94

6.94

6.95

6.96

6.96

6.97

6.99

7.18

7.18

7.18

7.20

7.20

7.21

7.22

7.23

7.23

7.23

7.24

7.25

7.27

7.36

7.36

7.37

7.37

7.38

7.38

7.69

7.70

8.66

-100102030405060708090100110120130140150160170180190200210

f1 (ppm)

39.37

39.58

39.79

40.00

40.21

40.42

40.63

51.96

55.89

106.28

111.78

117.88

125.76

126.12

127.25

127.48

127.93

128.27

129.39

137.81

142.52

142.79

142.95

159.29

161.88

191.20

NH2

O

MeO

NH2

O

MeO

S27

1H, 13C, 19F spectraspectra of 3h

-1.0-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.5

f1 (ppm)

1.00

3.96

1.00

2.98

3.93

0.97

1.99

5.29

6.74

6.76

6.78

7.08

7.09

7.10

7.11

7.11

7.20

7.21

7.21

7.22

7.23

7.24

7.25

7.25

7.26

7.26

7.27

7.28

7.28

7.29

7.37

7.37

7.39

7.39

7.39

7.40

7.41

7.41

7.42

7.42

7.44

7.44

7.45

8.01

8.02

8.03

8.04

8.05

8.06

8.07

8.73

-100102030405060708090100110120130140150160170180190200210

f1 (ppm)

39.37

39.58

39.79

39.99

40.20

40.41

40.62

51.78

110.77

114.89

115.10

122.06

125.05

127.15

127.55

128.01

129.27

129.35

129.45

130.90

136.51

138.32

138.35

142.80

150.46

159.57

161.85

161.97

191.35

NH2

O

F

NH2

O

F

S28

-210-200-190-180-170-160-150-140-130-120-110-100-90-80-70-60-50-40-30-20-10010

f1 (ppm)

-117.28

-117.26

-117.25

-117.23

-117.21

1H, 13C spectra of 3i

-1.0-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.511.0

f1 (ppm)

1.00

1.98

2.00

1.03

3.07

4.05

1.02

1.93

5.31

6.76

6.76

6.77

6.78

6.78

6.79

6.99

7.00

7.00

7.01

7.02

7.02

7.08

7.09

7.10

7.11

7.11

7.21

7.21

7.22

7.23

7.24

7.25

7.26

7.26

7.27

7.27

7.28

7.29

7.30

7.30

7.30

7.38

7.39

7.39

7.40

7.40

7.41

7.41

7.42

7.42

7.43

7.44

7.45

7.45

7.46

8.02

8.03

8.03

8.04

8.05

8.05

8.07

8.72

NH2

O

F

NH2

O

Cl

S29

-100102030405060708090100110120130140150160170180190200210

f1 (ppm)

39.38

39.59

39.80

40.01

40.22

40.42

40.63

51.85

110.48

122.10

125.05

127.20

127.63

128.05

128.27

129.40

129.54

130.61

130.95

136.54

141.44

142.72

150.16

161.96

191.19

1H, 13C spectra of 3j

-1.0-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.511.0

f1 (ppm)

1.00

2.02

0.99

3.01

4.00

1.97

0.99

1.99

5.48

7.01

7.02

7.04

7.11

7.13

7.19

7.20

7.22

7.22

7.23

7.24

7.25

7.25

7.26

7.27

7.27

7.28

7.28

7.37

7.38

7.39

7.40

7.41

7.42

7.43

7.44

7.44

7.46

7.46

7.48

7.83

7.83

7.84

7.85

8.08

8.10

8.10

8.79

NH2

O

Cl

NH2

O

NO2

S30

-100102030405060708090100110120130140150160170180190200210

f1 (ppm)

39.38

39.59

39.80

40.01

40.22

40.42

40.63

52.12

110.28

122.35

123.56

125.15

127.11

127.97

128.15

128.90

129.59

131.15

136.72

142.62

146.04

149.35

151.13

162.13

191.13

1H, 13C spectra of 3k

-1.0-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0

f1 (ppm)

2.97

1.00

1.99

1.97

1.05

3.02

4.22

1.07

1.96

2.08

5.26

6.66

6.66

6.67

6.68

6.77

6.79

7.08

7.09

7.09

7.10

7.10

7.10

7.20

7.20

7.21

7.22

7.22

7.23

7.24

7.24

7.24

7.25

7.25

7.25

7.26

7.26

7.27

7.28

7.29

7.29

7.29

7.35

7.35

7.37

7.37

7.38

7.38

7.39

7.40

7.40

7.41

7.41

7.42

7.43

7.43

7.43

7.44

8.00

8.01

8.01

8.02

8.03

8.68

NH2

O

NO2

NH2

O

S31

-100102030405060708090100110120130140150160170180190200210

f1 (ppm)

20.96

39.36

39.57

39.78

39.99

40.20

40.41

40.61

52.30

110.73

121.90

125.05

127.35

127.40

127.54

127.98

128.98

129.54

130.75

135.05

136.47

139.18

142.73

150.77

161.91

191.19

1H, 13C spectra of 3l

-1.0-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.511.0

f1 (ppm)

2.98

1.00

2.00

1.01

1.02

1.05

3.07

4.02

0.99

1.77

2.03

5.21

6.53

6.53

6.54

6.56

6.72

6.74

6.83

6.85

6.87

7.10

7.11

7.12

7.12

7.20

7.20

7.22

7.22

7.23

7.24

7.25

7.25

7.25

7.27

7.36

7.36

7.37

7.38

7.38

7.39

7.40

7.40

7.41

7.41

8.03

8.03

8.04

8.05

8.05

8.69

NH2

O

NH2

O

S32

-100102030405060708090100110120130140150160170180190200210

f1 (ppm)

21.31

39.60

39.81

40.02

40.23

40.44

52.60

110.93

121.95

124.77

125.09

126.91

127.21

127.42

127.94

128.19

128.25

129.34

130.77

136.66

137.14

142.10

142.87

150.59

161.75

191.42

1H, 13C spectra of 3m

-1.0-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.5

f1 (ppm)

2.89

1.00

1.95

0.97

0.98

1.00

3.08

3.98

0.97

1.76

3.55

5.26

6.31

6.31

6.32

6.33

6.33

6.34

6.37

6.38

6.38

6.38

6.48

6.48

6.49

6.49

6.50

6.50

6.51

6.51

6.86

6.88

6.90

7.13

7.14

7.15

7.15

7.15

7.16

7.21

7.21

7.21

7.23

7.23

7.24

7.24

7.25

7.25

7.26

7.26

7.27

7.27

7.28

7.29

7.29

7.29

7.37

7.37

7.39

7.39

7.39

7.40

7.40

7.41

7.41

7.42

7.42

7.43

7.43

8.01

8.02

8.02

8.03

8.04

8.69

NH2

O

NH2

O

OMe

S33

-100102030405060708090100110120130140150160170180190200210

f1 (ppm)

39.35

39.56

39.77

39.98

40.19

40.40

40.61

52.61

55.17

110.57

111.68

113.63

119.58

121.94

125.03

127.30

127.47

127.98

129.36

129.49

130.80

136.53

142.77

143.91

150.38

159.20

161.88

191.25

1H, 13C spectra of 3n

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.5

f1 (ppm)

1.00

6.09

1.95

2.05

0.99

0.98

1.00

1.94

5.47

7.12

7.12

7.14

7.14

7.14

7.15

7.15

7.17

7.17

7.19

7.20

7.21

7.21

7.22

7.24

7.26

7.28

7.32

7.33

7.34

7.34

7.35

7.41

7.41

7.42

7.43

7.44

7.45

7.45

7.46

7.47

7.48

7.49

7.54

7.55

7.55

7.79

7.79

7.79

7.80

7.81

7.81

7.82

7.82

8.08

8.08

8.08

8.10

8.10

8.77

NH2

O

OMe

NH2

O

NO2

S34

-100102030405060708090100110120130140150160170180190200210

f1 (ppm)

39.38

39.59

39.80

40.01

40.22

40.43

40.64

51.77

110.48

121.37

122.32

122.59

125.23

126.97

127.97

128.07

129.42

129.89

131.19

134.43

136.77

142.74

144.92

147.59

149.57

161.98

191.29

1H, 13C, 19F spectraspectra of 3o

-1.0-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0

f1 (ppm)

1.00

1.98

5.05

0.99

4.08

1.00

1.99

5.29

6.78

6.79

6.79

6.80

6.81

6.81

6.84

6.92

6.92

6.93

6.93

6.94

6.95

6.95

6.96

6.96

6.97

6.99

6.99

7.01

7.03

7.03

7.04

7.09

7.10

7.11

7.12

7.12

7.37

7.37

7.39

7.39

7.39

7.40

7.41

7.41

7.42

7.43

7.44

7.45

7.46

7.46

7.47

7.48

7.49

7.50

7.50

8.02

8.03

8.04

8.04

8.05

8.06

8.07

8.75

NH2

O

NO2

NH2

O

F

S35

-100102030405060708090100110120130140150160170180190200210

f1 (ppm)

39.38

39.59

39.79

40.00

40.21

40.42

40.63

52.60

110.60

114.67

114.89

122.04

125.06

126.35

127.48

127.60

128.40

129.74

129.82

130.90

136.45

139.26

139.29

142.15

150.60

161.55

162.19

163.99

189.86

-210-200-190-180-170-160-150-140-130-120-110-100-90-80-70-60-50-40-30-20-10010

f1 (ppm)

-111.99

-111.98

-111.97

NH2

O

F

NH2

O

F

S36

1H, 13C spectra of 3p

-1.5-1.0-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.511.0

f1 (ppm)

1.00

2.00

2.97

1.05

1.98

3.98

1.01

1.84

5.28

6.79

6.80

6.80

6.81

6.82

6.86

6.93

6.94

6.94

6.95

6.96

6.96

6.97

6.97

6.98

6.99

7.00

7.01

7.02

7.10

7.11

7.12

7.12

7.24

7.24

7.26

7.38

7.39

7.40

7.40

7.42

7.43

7.44

8.03

8.04

8.04

8.05

8.05

8.06

8.07

8.77

-100102030405060708090100110120130140150160170180190200210

f1 (ppm)

39.38

39.59

39.80

40.01

40.22

40.43

40.64

52.47

110.54

122.10

125.07

126.39

127.51

127.61

128.00

128.42

129.23

130.99

134.06

136.35

141.43

142.11

150.62

162.41

189.65

NH2

O

Cl

NH2

O

Cl

S37

1H, 13C spectra of 3q

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.5

f1 (ppm)

2.99

1.00

2.00

5.02

1.00

4.00

0.99

1.83

2.24

5.33

6.83

6.83

6.83

6.84

6.85

6.85

6.94

6.95

6.96

6.96

6.97

6.98

6.99

6.99

7.00

7.01

7.01

7.03

7.11

7.11

7.12

7.13

7.36

7.36

7.38

7.38

7.39

7.40

7.40

7.40

8.01

8.01

8.01

8.02

8.03

8.67

-100102030405060708090100110120130140150160170180190200210

f1 (ppm)

21.36

39.39

39.59

39.80

40.01

40.22

40.43

40.64

52.68

110.63

121.88

125.01

126.31

127.39

127.54

127.56

128.39

128.51

130.69

136.55

139.10

139.94

142.42

150.49

161.81

190.91

NH2

O

NH2

O

S38

1H, 13C spectra of 3r

-1.0-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.511.0

f1 (ppm)

2.94

1.00

1.97

1.96

2.98

0.97

1.99

1.95

0.97

1.75

3.72

5.38

6.74

6.75

6.76

6.77

6.77

6.78

6.86

6.87

6.87

6.88

6.88

6.89

6.89

6.93

6.93

6.94

6.94

6.95

6.96

6.96

6.97

6.97

6.99

7.00

7.01

7.01

7.03

7.03

7.03

7.11

7.12

7.13

7.13

7.14

7.14

7.14

7.15

7.36

7.36

7.37

7.38

7.38

7.39

7.40

7.40

7.40

7.42

7.42

7.49

7.49

7.50

7.51

7.52

7.52

7.98

7.99

8.00

8.00

8.01

8.02

8.63

-100102030405060708090100110120130140150160170180190200210

f1 (ppm)

39.38

39.59

39.80

40.01

40.21

40.42

40.63

52.77

55.56

110.50

113.24

121.79

124.96

126.35

127.37

127.54

128.44

129.57

130.59

135.12

136.59

142.46

150.40

160.51

161.68

190.03

NH2

O

OMe

NH2

O

OMe

S39

1H, 13C spectra of 3s

-1.0-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.5

f1 (ppm)

2.99

1.01

1.00

1.00

5.95

2.02

1.03

1.97

0.18

0.19

0.21

1.08

1.09

1.10

1.11

1.12

1.13

1.13

1.14

1.16

1.64

1.65

1.66

1.66

1.67

1.68

1.68

1.69

1.70

1.70

1.71

1.72

4.22

4.23

4.23

4.24

7.39

7.40

7.41

7.42

7.43

7.43

7.44

7.45

7.45

7.46

7.46

7.47

7.47

7.48

7.49

7.51

7.60

7.60

7.61

7.62

7.62

7.63

7.63

7.64

7.64

7.97

7.98

8.61

-100102030405060708090100110120130140150160170180190200210

f1 (ppm)

8.12

23.98

39.48

39.65

39.81

39.90

39.98

40.07

40.15

40.24

40.31

40.40

40.48

46.35

108.26

121.77

124.20

127.13

127.24

128.61

129.90

130.43

137.57

143.34

149.37

161.61

190.71

NH2O

NH2O

S40

1H, 13C spectra of 3t

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.511.0

f1 (ppm)

2.99

1.00

4.03

2.03

2.07

1.05

1.88

1.76

4.96

7.11

7.12

7.12

7.13

7.13

7.13

7.14

7.14

7.15

7.15

7.16

7.16

7.17

7.19

7.20

7.21

7.21

7.25

7.27

7.27

7.28

7.29

7.29

7.29

7.35

7.36

7.37

7.37

7.38

7.93

7.94

7.94

7.95

7.95

7.95

8.45

-100102030405060708090100110120130140150160170180190200210

f1 (ppm)

28.71

39.60

39.81

40.02

40.23

40.44

52.21

111.25

121.85

125.11

126.95

127.39

127.75

129.12

130.43

136.89

142.75

149.84

159.12

193.69

NH2

O

NH2

O

S41

1H, 13C spectra of 3u

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.511.0

f1 (ppm)

1.00

5.02

1.00

1.99

2.95

1.00

0.95

1.00

1.99

1.93

5.51

6.81

6.82

6.82

6.83

6.84

6.85

6.86

6.87

6.88

6.89

6.89

7.12

7.13

7.14

7.38

7.38

7.40

7.40

7.41

7.41

7.42

7.43

7.43

7.44

7.45

7.49

7.49

7.50

7.51

7.52

7.52

7.54

7.55

7.72

7.74

7.82

7.83

7.84

7.84

7.85

7.91

7.92

7.93

7.93

7.94

7.95

8.06

8.07

8.08

8.08

8.11

8.11

8.84

-100102030405060708090100110120130140150160170180190200210

f1 (ppm)

39.37

39.58

39.79

40.00

40.21

40.42

40.63

52.72

110.87

122.02

125.07

125.17

126.28

126.59

127.20

127.34

127.47

127.50

127.57

127.83

128.35

129.06

130.87

132.44

133.48

136.46

139.73

142.46

150.65

162.30

190.66

NH2

O

NH2

O

S42

1H, 13C spectra of 3v

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.5

f1 (ppm)

1.00

1.98

2.01

2.08

2.00

1.02

0.95

0.97

5.14

7.12

7.14

7.14

7.19

7.20

7.21

7.21

7.22

7.25

7.27

7.27

7.28

7.29

7.45

7.45

7.47

7.47

7.49

7.49

7.50

7.50

7.51

7.51

7.53

8.15

8.16

8.16

8.17

8.18

8.18

8.99

9.38

-100102030405060708090100110120130140150160170180190200210

f1 (ppm)

39.39

39.59

39.80

40.01

40.22

40.43

40.64

50.62

122.42

123.37

125.50

127.17

127.66

128.22

128.95

132.63

134.21

140.38

147.08

156.11

NH2

NO2

NH2

NO2

S43

1H, 13C spectra of 4

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.0

f1 (ppm)

1.00

2.01

16.10

1.00

5.05

6.92

6.93

6.93

6.94

6.95

6.95

7.12

7.14

7.16

7.17

7.17

7.18

7.19

7.20

7.20

7.21

7.22

7.22

7.24

7.25

7.27

7.29

7.30

7.31

7.32

7.32

7.33

7.34

7.35

7.36

7.38

7.39

7.39

7.40

7.41

7.42

7.42

7.43

7.92

7.93

7.94

7.94

7.94

7.95

7.96

7.96

-100102030405060708090100110120130140150160170180190200210

f1 (ppm)

47.78

76.73

76.77

77.05

77.08

77.36

77.40

120.37

125.44

125.98

126.90

127.16

127.55

127.67

127.95

128.16

128.20

128.60

128.91

129.11

129.91

130.02

133.64

137.89

140.77

141.65

153.37

159.70

NN Ph

Ph

Ph

NN Ph

Ph

Ph

S44

8. HRMS spectra of the intermediate E

NH2O

PhPh

EtO

H

C24H23NO2Calcd (M + H) + 358.1802Found(M + H) + 358.1803

cascade annulations of benzimidates with alkenes …S1 Synthesis of polydisubstituted 3-aminoindenes...

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Transcript of cascade annulations of benzimidates with alkenes …S1 Synthesis of polydisubstituted 3-aminoindenes...