Iodine-catalyzed Transformation of Aryl-substituted Alcohols under Solvent-free and highly concentrated Reaction Conditions

(1)

SI-1 Iodine-catalyzed transformation of aryl-substituted alcohols under solvent-free and highly concentrated reaction conditions

Marjan Jereb

^*1

and Dejan Vražič

²

1

Department of Organic Chemistry, Faculty of Chemistry and Chemical Technology, Večna pot 113, 1000 Ljubljana, Slovenia

2

Present address: Krka, d. d., Novo mesto, Šmarješka cesta 6, 8501 Novo mesto, Slovenia

*

Corresponding author

Tel.: (++386) 1 479 8577 Fax: (++386) 1 241 9144, E-mail: marjan.jereb@fkkt.uni-lj.si

Supporting Information

Copies of

¹

H and

¹³

C NMR spectra

(2)

SI-2

ppm (t1)

0.0 5.0

10.0 15.0

0 100 200 300 400

7.896 7.873 7.765 7.738 7.704 7.683 7.649 7.622 7.385 7.361 7.339 7.314 7.290 7.262 7.237 6.882 6.857 6.832 6.806 2.399 2.374 0.000

1.00 3.10

1.061.011.001.02 4.19 ppm (t1)

7.00 7.50

-50 0 50 100 150

7.8967.873 7.7657.738 7.704 7.683 7.649 7.622 7.385 7.361 7.339 7.314 7.290 7.262 7.2376.8826.8576.8326.806

1.00

1.06 1.01 1.00 1.02 4.19

Me

300 MHz, CDCl3

5a

(3)

SI-3

ppm (t1)

0 50

100 150

200

-500 0 500 1000 1500 2000 2500 3000 3500

140.749 139.344 138.511 137.711 136.564 127.570 127.290 126.837 125.014 124.793 119.755 119.561 119.434 15.304

ppm (t1) 126.850

-500 0 500 1000 1500 2000 2500 3000

126.837

5a

75 MHz, CDCl₃

(4)

SI-4

ppm (t1)

0.0 5.0

10.0 15.0

0 100 200 300 400

7.284 7.269 7.265 7.254 7.243 7.195 7.186 7.175 7.156 7.148 7.135 7.122 7.117 7.105 7.056 7.043 7.031 7.027 7.012 5.979 5.956 5.932 5.909 1.747 1.724 0.000

3.13

1.031.28 5.95 4.33

1.00

ppm (t1)

6.90 7.00 7.10 7.20 7.30 7.40 7.50

0 50 100 7.2697.284 7.265 7.254 7.243 7.195 7.186 7.175 7.156 7.148 7.135 7.122 7.117 7.105 7.0567.0317.0277.0437.012 150

1.03

1.28 5.95

300 MHz, CDCl₃ Me

5c

(5)

SI-5

ppm (t1)

0 50

100 150

200

0 50 100 150

143.054 141.685 139.856 139.355 137.129 129.803 128.617 128.501 128.092 127.175 126.852 125.965 125.581 77.423 77.000 76.577 33.721 32.133 15.339

ppm (t1)

125.950 126.000

126.050

-10 0 10 20 30 40 50 60

125.965

5c

75 MHz, CDCl₃

(6)

SI-6

ppm (t1)

0.0 5.0

10.0 15.0

0 50 100

7.487 7.459 7.270 7.246 7.194 7.168 7.129 7.105 7.012 7.001 6.784 0.000

1.00

0.93 10.89 3.88

300 MHz, CDCl3 Ph

5d

(7)

SI-7

ppm (t1)

0 50

100 150

200

-100 0 100 200 300 400 500 600

143.711 141.742 140.388 139.030 137.557 137.153 130.132 129.796 129.178 128.287 128.230 127.935 127.903 127.680 127.323 126.611 126.353 126.096 77.254 77.000 76.746 33.533 32.051 700

ppm (t1)

126.0 127.0

128.0 129.0

0 100 200 300 400

130.132 129.796 129.178 128.287 128.230 127.935 127.903 127.680 127.323 126.611 126.353 126.096

5d

125 MHz, CDCl₃

(8)

SI-8

ppm (t1)

0.0 5.0

10.0 15.0

0 100 200 300 400

7.566 7.561 7.540 7.535 7.481 7.475 7.449 7.267 7.262 7.239 7.234 7.216 7.211 7.192 7.170 7.165 7.137 7.133 7.110 7.105 7.084 7.073 7.060 7.055 7.048 7.025 7.020 6.041 6.016 5.991 5.966 2.138 2.113 0.000 500

1.00 3.16

1.021.05 6.37 ppm (t1)

7.00 7.10 7.20 7.30 7.40 7.50 7.60

-50 0 50 100 150 200 250

7.5667.5617.5407.5357.481 7.475 7.449 7.267 7.262 7.239 7.234 7.216 7.211 7.192 7.170 7.165 7.137 7.1337.1107.1057.0847.0737.0607.0557.0487.0257.020

1.02 1.05 6.37

300 MHz, CDCl₃

O Me

5e

(9)

SI-9

ppm (t1)

0.0 5.0

10.0 15.0

0 50 100 150 200 250 300

7.761 7.736 7.365 7.341 7.318 7.292 7.269 7.246 7.219 7.186 7.166 7.139 6.941 6.823 6.796 6.773 0.000

1.00 0.93

0.99 10.74

ppm (t1)

7.00 7.50

0

7.761 7.736 7.365 7.341 7.318 7.292 7.269 7.246 7.219 7.186 7.166 7.139 6.941 6.823 6.7736.796 50

1.00 0.93

0.99 10.74

O Ph

5f 300 MHz, CDCl3

(10)

SI-10

ppm (t1)

0.0 5.0

10.0 15.0

0 500 1000 1500 2000

7.244 7.215 6.899 6.870 4.280 4.258 4.237 4.215 3.808 3.195 1.430 1.408 0.000

1.00 3.19 3.10

2.99

1.981.89

Me OMe

OMe

6ha

300 MHz, CDCl₃

(11)

SI-11

ppm (t1)

0.0 5.0

10.0 15.0

0 500

7.249 7.220 6.890 6.861 4.389 4.368 4.346 4.325 3.804 3.364 3.341 3.317 3.294 1.429 1.407 1.191 1.168 1.144 0.000 1000

1.00 3.33 3.08 3.05

1.97

2.142.77

300 MHz, CDCl₃

Me OEt

OMe

6hb

(12)

SI-12

ppm (t1)

0.0 5.0

10.0 15.0

0 500 1000 1500 2000 2500

7.258 7.230 6.885 6.856 4.515 4.493 4.472 4.450 3.803 3.533 3.512 3.492 3.472 3.451 3.431 3.411 1.396 1.375 1.151 1.130 1.089 1.068 0.000 3000

1.00 0.973.06 3.09 2.973.09

1.942.11

ppm (t1)

3.400 3.450

3.500 3.550

-100 0 100 200

3.533 3.512 3.492 3.472 3.451 3.431 3.411 300

0.97

ppm (t1) 1.000 1.050 1.100 1.150 1.200

0 500 1000

1.151 1.130 1.089 1.068

2.97 3.09

Me O

OMe Me

Me

300 MHz, CDCl3

6hc

(13)

SI-13

ppm (t1)

0.0 5.0

10.0 15.0

0 500 1000 1500

7.252 7.223 6.914 6.885 4.559 4.538 4.516 4.495 3.813 3.708 3.638 3.623 3.608 3.594 3.525 1.495 1.473 0.000

1.00 2.023.10 3.11

1.941.98

ppm (t1)

3.550 3.600 3.650 3.700

-50 0 50 100 150 200 250 300 350

3.708 3.679 3.668 3.652 3.638 3.623 3.608 3.594 3.582 3.565 3.554 3.525

2.02

MeO O CF₃

OMe

300 MHz, CDCl₃ 6hd

(14)

SI-14

ppm (t1)

0 50

100 150

200

0 1000 2000 3000 4000 5000 6000 7000

159.506 133.734 129.710 127.587 126.016 122.323 118.630 114.079 79.025 77.423 77.000 76.577 66.166 65.716 65.266 64.816 55.263 23.665 8000

ppm (t1)

0 50

100 150

200

0 1000 2000 3000 4000 5000 6000 7000

159.506 133.734 129.710 127.587 126.016 122.323 118.630 114.079 79.025 77.423 77.000 76.577 66.166 65.716 65.266 64.816 55.263 23.665 8000

MeO

O

6hd 75 MHz, CDCl3

CF₃

(15)

SI-15

ppm (t1)

0.0 5.0

10.0 15.0

0 500 1000

7.306 7.277 6.891 6.862 5.882 5.860 5.838 5.816 3.800 2.044 1.532 1.508 0.000

1.00 3.45 3.02 4.88

2.15

2.05

O Me

OMe O

Me

300 MHz, CDCl3

6he

(16)

SI-16

ppm (t1)

0.0 5.0

10.0 15.0

-100 0 100 200 300 400 500 600 700

7.244 7.223 7.201 7.177 7.164 7.141 7.125 7.096 7.067 7.046 6.834 6.805 4.261 4.238 4.217 3.792 3.153 3.130 3.105 3.084 3.060 2.874 2.854 2.829 2.808 0.000

1.00

2.157.96 3.00 1.074.01

OMe Ph OMe

6ia

300 MHz, CDCl3

(17)

SI-17

ppm (t1)

0 50

100 150

200

-100 0 100 200 300 400 500 600 700

159.049 138.547 133.591 129.424 128.006 127.960 126.023 113.626 84.582 77.423 77.000 76.576 56.459 55.172 44.709

ppm (t1)

127.80 127.90 128.00 128.10 128.20

0 128.006 127.960 500

MeO

OMe

6ia 75 MHz, CDCl₃

(18)

SI-18

ppm (t1)

0.0 5.0

10.0 15.0

0 500 1000 1500 2000 2500

7.274 7.245 6.896 6.867 4.388 3.806 3.355 0.000

2.00 2.98 2.98

1.952.55

OMe

OMe 6ma

300 MHz, CDCl₃

(19)

SI-19

ppm (t1)

0.0 5.0

10.0 15.0

0 500 1000

7.281 7.257 6.890 6.861 4.437 3.801 3.548 3.525 3.501 3.478 1.251 1.228 1.205 0.000

2.00

1.99 3.20 2.95

1.992.59

300 MHz, CDCl₃

OEt

OMe

6mb

(20)

SI-20

ppm (t1)

0.0 5.0

10.0 15.0

0 500 1000

7.280 7.257 6.882 6.854 4.440 3.797 3.724 3.704 3.684 3.663 3.643 3.623 3.602 1.208 1.188 0.00000

1.003.22 6.13

1.98

1.982.47

O

OMe Me

Me

6mc

300 MHz, CDCl3

(21)

SI-21

ppm (t1)

0.0 5.0

10.0 15.0

0 100 200 300 400 500 600

7.180 7.150 7.139 7.128 6.872 6.851 6.822 3.812 3.078 3.042 2.998 2.973 2.929 1.455 0.000

1.00 3.01

3.02 1.052.93

4.98 3.94 ppm (t1)

2.950 3.000 3.050 3.100 3.150

0 50 100

3.078 3.042 2.998 2.973 2.929

1.00

1.05

2.93

300 MHz, CDCl3 OMe MeOMe Ph

6na

(22)

SI-22

ppm (t1)

0 50

100 150

200

-500 0 500 1000 1500 2000 2500

158.516 137.588 136.186 130.712 127.949 127.464 126.025 113.224 79.451 77.000 55.188 50.709 50.263 21.251 3000

75 MHz, CDCl3 OMe MeOMe Ph

6na

(23)

SI-23

ppm (t1)

0.0 5.0

10.0 15.0

0 500

7.128 7.098 7.090 7.079 7.069 6.834 6.802 6.767 6.737 3.787 3.347 3.324 3.318 3.301 3.295 3.278 3.272 3.259 3.249 3.139 3.116 3.110 3.092 3.086 3.069 3.063 3.040 2.983 2.940 2.892 2.848 1.429 1.169 1.146 1.1220.000

1.00 1.010.980.99 2.892.75

2.92

2.001.844.67

ppm (t1)

6.70 6.80 6.90 7.00 7.10

-100 -50 0 50 100 150 200 250

7.128 7.098 7.090 7.079 7.069 6.834 6.802 6.767 6.737

2.00

1.84

4.67

ppm (t1)

2.90 3.00 3.10 3.20 3.30

-100 0 100 200 300 3.3473.3243.3183.301 3.295 3.278 3.272 3.259 3.249 3.139 3.116 3.110 3.092 3.0863.0693.0633.0402.9832.9402.8922.848

1.00 1.01

0.98

0.99

300 MHz, CDCl3 OMe MeOEt Ph

6nb

(24)

SI-24

ppm (t1)

0 50

100 150

200

0 500 1000 1500

158.424 137.696 137.041 130.763 127.743 127.394 125.951 113.150 79.081 77.000 57.609 55.158 51.035 21.806 15.781

75 MHz, CDCl3 OMe MeOEt Ph

6nb

(25)

SI-25

ppm (t1)

0.0 5.0

10.0 15.0

0 100 200 300 400

7.989 7.320 7.283 7.267 7.256 7.235 7.205 7.182 7.155 7.070 7.064 7.044 7.039 6.044 6.021 5.997 3.249 3.223 3.203 3.177 3.096 3.075 3.050 3.029 0.000

1.00 1.061.02

0.97 8.30 2.01

300 MHz, CDCl3 Ph O

O H

7ba

(26)

SI-26

ppm (t1)

0 50

100 150

200

-1000 0 1000 2000 3000 4000 5000 6000 7000 8000

160.082 139.322 136.552 129.467 128.430 128.312 128.208 126.686 126.626 77.000 76.525 42.835

ppm (t1)

76.50 77.00

0 1000 2000 3000 4000 5000 6000

77.000 76.525

75 MHz, CDCl₃ Ph O

O H

7ba

(27)

SI-27

ppm (t1)

0.0 5.0

10.0 15.0

0 500 1000

8.062 7.322 7.294 6.901 6.872 6.013 5.991 5.969 5.947 3.805 1.583 1.561 0.000 1500

1.00 3.16

0.93 2.00 2.21 3.24

Me O

OMe H O

300 MHz, CDCl3

7ha

(28)

SI-28

ppm (t1)

0.0 5.0

10.0 15.0

-100 0 100 200 300 400 500 600

8.008 7.257 7.247 7.219 7.194 7.124 7.118 7.097 6.866 6.837 6.039 6.016 5.993 3.795 3.272 3.246 3.226 3.200 3.111 3.090 3.065 3.044 0.000 700

1.00 1.06

2.182.047.57 3.36

ppm (t1)

6.80 6.90 7.00 7.10 7.20 7.30 7.40

-50 0 50 100 150 200

7.257 7.247 7.219 7.194 7.124 7.118 7.097 6.866 6.837

2.18

2.04

7.57

300 MHz, CDCl₃

Ph O

O H

OMe 7ia

(29)

SI-29

ppm (t1)

0 50

100 150

200

-500 0 500 1000 1500 2000 2500

160.173 159.485 136.691 131.409 129.465 128.298 128.110 126.621 113.802 77.000 76.277 55.228 42.645 3000

75 MHz, CDCl₃

Ph O

O H

OMe 7ia

(30)

SI-30

ppm (t1)

0.0 5.0

10.0 15.0

0 500 1000 1500 2000 2500

7.085 7.056 6.820 6.791 3.856 3.774 0.000

2.016.00

3.793.80

8

ppm (t1) 3.750 3.800 3.850

-500 0 500 1000 1500 2000

3.856 3.774

2.01 6.00

MeO OMe

300 MHz, CDCl3

8

(31)

SI-31

ppm (t1)

0 50

100 150

200

0 5000 10000 15000 20000

157.910 133.714 129.712 113.851 77.000 55.251 40.120

75 MHz, CDCl3

MeO OMe

8

(32)

SI-32

ppm (t1)

0.0 5.0

10.0 15.0

0 100 200 300 400 500

7.310 7.287 7.251 7.223 7.200 7.141 7.112 7.030 7.007 6.881 6.852 6.750 6.722 6.654 6.616 6.587 6.539 3.782 3.752 3.266 3.220 3.194 3.148 2.855 2.811 2.677 2.633 0.917 0.000 600

1.001.012.00

6.03

0.933.932.012.083.047.86 3.13

ppm (t1)

6.50 7.00

-50 0 50 100 150 200

7.310 7.287 7.251 7.223 7.200 7.141 7.112 7.030 7.007 6.881 6.852 6.750 6.722 6.654 6.616 6.587 6.539

0.93

3.93

2.01

2.08

3.04

7.86

300 MHz, CDCl₃ H

OMe CH₂Ph Me

OMe

9a

(33)

SI-33

ppm (t1)

0 50

100 150

200

0 5000 10000 15000

158.368 157.241 140.977 138.912 138.613 137.643 131.411 130.450 128.903 128.194 128.089 127.964 127.274 126.182 125.675 113.318 112.785 77.000 55.234 55.139 49.969 42.998 42.840 23.311

ppm (t1)

126.0 127.0

128.0 129.0

130.0 131.0

-1000 0 1000 2000 3000 4000 5000 6000

131.411 130.450 128.903 128.194 128.089 127.964 127.274 126.182 125.675

75 MHz, CDCl₃ H

OMe CH₂Ph Me

OMe

9a

(34)

SI-34

ppm (t1)

0.0 5.0

10.0 15.0

0 100 200 300 400 500 600

7.082 7.070 7.066 7.054 7.029 7.004 6.986 6.848 6.819 6.780 6.774 6.753 6.740 6.723 6.693 6.657 6.628 6.148 3.779 3.752 3.081 3.045 3.037 3.002 2.874 2.829 2.801 2.757 1.118 0.000

1.001.012.00

6.01

0.94 3.00

8.11 2.15 1.855.84 ppm (t1)

6.60 6.70 6.80 6.90 7.00 7.10

-50 0 50 100 150 200 250

7.082 7.070 7.066 7.054 7.029 7.004 6.986 6.848 6.819 6.780 6.774 6.753 6.740 6.723 6.693 6.6576.628

8.11 2.15 1.85

5.84

ppm (t1) 2.80 2.90 3.00 3.10

0 50 100 150

3.081 3.045 3.037 3.002 2.874 2.829 2.8012.757

1.00

1.01

2.00

300 MHz, CDCl3 H

OMe CH₂Ph Me

OMe

9b

(35)

SI-35

ppm (t1)

0 50

100 150

200

-5000 0 5000 10000 15000 20000 25000 30000

158.123 157.338 139.636 138.562 138.368 137.675 134.324 130.504 130.010 128.881 128.160 127.658 127.348 125.860 125.771 113.527 112.862 77.000 55.171 55.091 53.589 50.367 42.850 23.307

ppm (t1)

126.0 127.0

128.0 129.0

130.0

0 5000 10000 15000

130.504 130.010 128.881 128.160 127.658 127.348 125.860 125.771

75 MHz, CDCl3 H

OMe CH₂Ph Me

OMe

9b

(36)

SI-36

ppm (t1)

0.0 5.0

10.0 15.0

0 100 200 300 400

8.338 8.332 8.311 8.306 7.723 7.717 7.699 7.694 7.689 7.671 7.665 7.475 7.449 7.390 7.386 7.363 7.340 7.336 0.000

2.00 2.10 2.052.00

300 MHz, CDCl₃ O O

11a

(37)

SI-37

ppm (t1)

0.0 5.0

10.0 15.0

0 50 100 150 200 250 300

7.174 7.150 7.129 7.108 7.016 6.993 6.974 6.949 4.045 0.000

2.00

3.743.96

ppm (t1)

6.90 7.00 7.10 7.20 7.30 7.40

-50 0 50 100 150

7.174 7.150 7.129 7.108 7.016 6.993 6.974 6.949

3.74

3.96

O

11b

300 MHz, CDCl3

(38)

SI-38

ppm (t1)

0.0 5.0

10.0 15.0

0 50 100 150 200 250

7.493 7.487 7.464 7.343 7.337 7.316 7.291 7.286 7.139 7.121 7.112 7.098 5.744 2.859 0.000

1.00 3.00

2.19 4.161.97 ppm (t1)

7.00 7.50

0 50 100

7.493 7.487 7.464 7.343 7.337 7.316 7.291 7.286 7.139 7.121 7.112 7.098

2.19 4.16

1.97

O OMe

300 MHz, CDCl3

11c

(39)

SI-39

ppm (t1)

0 50

100 150

200

0 500 1000 1500 2000 2500

152.501 130.023 129.605 123.197 119.608 116.573 77.000 70.803 51.534

75 MHz, CDCl3 O OMe

11c