S1

(IPr)CuF-Catalyzed α-Site Regiocontrolled trans-Hydrofluorination

of Ynamides

Guohao Zhu, Shineng Qiu, Yang Xi, Yao Ding, Dongming Zhang, Rong Zhang,

Guangke He∗ and

Hongjun Zhu∗

Department of Applied Chemistry, College of Chemistry and Molecular Engineering, Nanjing

Tech University, Nanjing 211816, People’ s Republic of China

*E-mails: hegk@njtech.edu.cn; zhuhj@njtech.edu.cn.

Spectra of compounds Z-2a-4o

Spectra of compound Z-2a p 2-4 Spectra of compound Z-2k p 33-35

Spectra of compound Z-3a p 5 Spectra of compound Z-3k p 36

Spectra of compound Z-2b p 6-8 Spectra of compound Z-2l p 37-39

Spectra of compound Z-2c p 9-11 Spectra of compound Z-3l p 40

Spectra of compound Z-2d p 12-14 Spectra of compound Z-2m p 41-43

Spectra of compound Z-2e p 15-17 Spectra of compound Z-2n p 44-46

Spectra of compound Z-2f p 18-20 Spectra of compound Z-2o p 47-49

Spectra of compound Z-2g p 21-23 Spectra of compound Z-2p p 50-52

Spectra of compound Z-2h p 24-26 Spectra of compound 4a p 53-55

Spectra of compound Z-2i p 27-29 Spectra of compound 4o p 56-58

Spectra of compound Z-2j p 30-32 Detailed discussions p 59-60

Electronic Supplementary Material (ESI) for Organic & Biomolecular Chemistry. This journal is © The Royal Society of Chemistry 2016

mailto:hegk@njtech.edu.cn mailto:zhuhj@njtech.edu.cn

10 9

8 7

6 5

4 3

2 1

0 pp

m

−0.0000

1.6214

3.9506 3.9539 3.9733 3.9905 3.9938 4.4338 4.4508 4.4545 4.4737

5.9154 6.0027

7.2134 7.2318 7.2502 7.2589 7.3120 7.3316 7.3502 7.4454 7.4641

2.10

2.09

1.00

1.36 2.10 2.10

z g h − 2 − 1 7 6 − H

17 0

16 0

15 0

14 0

13 0

12 0

11 0

10 0

90 80

70 60

50 40

30 20

10 0

pp m

44.0761

62.0310

76.7284 77.0459 77.3637

99.2639 99.3998

127.1742 127.1974 128.3079 128.3810 128.5405 132.1570 132.2110 144.4725 147.1063

154.1797

z g h − 2 − 1 7 6 − C

−3 0

−4 0

−5 0

−6 0

−7 0

−8 0

−9 0

−1 00

−1 10

−1 20

−1 30

−1 40

−1 50

pp m

−99.2869

z g h − 2 − 1 7 6 − F

10 9

8 7

6 5

4 3

2 1

0 pp

m

0.0000

1.6044

4.1806 4.1898 4.1997 4.2038 4.2089 4.2208 4.2300 4.4576 4.4786 4.4978

6.6948 6.7724 7.2621 7.3063 7.3209 7.3242 7.3275 7.3478 7.3678 7.3859 7.4427 7.4610 7.4648

2.06

2.06

1.00

1.01 2.03 2.03

z g h − 6 − 4 1 ( 2 ) − H

10 9

8 7

6 5

4 3

2 1

0 pp

m

−0.0000

1.6363

2.3356

3.9359 3.9394 3.9588 3.9758 3.9793 4.4257 4.4428 4.4462 4.4657

5.8625 5.9493

7.1280 7.1480 7.2584 7.3383 7.3586

3.29

2.16

2.18

1.00

2.09 2.19

z g h − 2 − 1 5 8 − H

17 0

16 0

15 0

14 0

13 0

12 0

11 0

10 0

90 80

70 60

50 40

30 20

10 0

pp m

20.1695

43.1707

61.0706

75.7839 76.1028 76.4204

98.5790 98.7232

127.1743 127.2470 128.2251 136.0400 136.0621 143.0354 145.6695

153.3398

z g h − 2 − 1 5 8 − C

−3 0

−4 0

−5 0

−6 0

−7 0

−8 0

−9 0

−1 00

−1 10

−1 20

−1 30

−1 40

−1 50

pp m

−99.8240

z g h − 2 − 1 5 8 − F

11 10

9 8

7 6

5 4

3 2

1 0

pp m

−0.0000

1.5836

3.8146 3.9400 3.9470 3.9636 3.9667 3.9793 3.9862 4.4343 4.4429 4.4557 4.4588 4.4626 4.4646 4.4741 4.4827 5.8285 5.8335 5.9142 5.9193 6.8621 6.8839 7.2631 7.3917 7.4136

3.22 2.10

2.09

1.00

2.08

2.07

z g h − 2 − 1 7 8 − H

21 0

20 0

19 0

18 0

17 0

16 0

15 0

14 0

13 0

12 0

11 0

10 0

90 80

70 60

50 40

30 20

10 0

pp m

44.3281

55.2408

62.1106

76.7795 77.0970 77.4152

100.0712 100.2221

113.9769

124.6053 124.6629 129.6482 129.7229

143.3047 145.9325

154.5499 158.7374 158.7656

z g h − 2 − 1 7 8 − C

−4 0

−5 0

−6 0

−7 0

−8 0

−9 0

−1 00

−1 10

−1 20

−1 30

−1 40

−1 50

pp m

−101.1844

z g h − 2 − 1 7 8 − F

10 9

8 7

6 5

4 3

2 1

0 pp

m

0.0000

1.5827

3.9648 3.9682 3.9847 3.9878 4.0047 4.0081 4.4496 4.4664 4.4700 4.4895

5.9064 5.9935

7.2623 7.2806 7.3021 7.3648 7.3862

2.12

2.14

1.00

2.00 2.13

z g h − 6 − 6 3 − H

19 0

18 0

17 0

16 0

15 0

14 0

13 0

12 0

11 0

10 0

90 80

70 60

50 40

30 20

10 0

pp m

43.9588

62.0486

76.7393 77.0564 77.3746

97.7155 97.8515

128.7164 129.4867 129.5608 130.7747 130.8279 132.6984 132.7330 144.8934 147.5247 153.9960

z g h − 6 − 6 3 − C

−1 80

−1 60

−1 40

−1 20

−1 00

−8 0

−6 0

−4 0

−2 0

0 pp

m

−98.9613

z g h − 6 − 6 3 − F

11 10

9 8

7 6

5 4

3 2

1 0

pp m

0.0000

1.5828

3.9658 3.9688 3.9863 3.9882 4.0056 4.0086 4.4499 4.4704 4.4898

5.8960 5.9834

7.2625 7.2989 7.3202 7.4351 7.4564

2.11

2.13

1.00

2.05 2.15

z g h − 2 − 1 6 1 − H

20 0

19 0

18 0

17 0

16 0

15 0

14 0

13 0

12 0

11 0

10 0

90 80

70 60

50 40

30 20

10 pp

m

43.9258

62.0502

76.7411 77.0585 77.3763

97.6167 97.7486

120.8242 120.8556 129.7788 129.8528 131.2374 131.2916 131.6737 144.9764 147.6081 153.9525

z g h − 2 − 1 6 1 − C

−1 80

−1 60

−1 40

−1 20

−1 00

−8 0

−6 0

−4 0

−2 0

0 pp

m

−98.6946

z g h − 2 − 1 6 1 − F

10 9

8 7

6 5

4 3

2 1

0 pp

m

0.0000

1.5768

3.9615 3.9808 4.0013 4.4495 4.4707 4.4894

5.8935 5.9797

6.9997 7.0214 7.0431 7.2622 7.4071 7.4209 7.4288 7.4425

2.10

2.15

1.00

2.05

2.20

z g h − 6 − 6 4 − H

19 0

18 0

17 0

16 0

15 0

14 0

13 0

12 0

11 0

10 0

90 80

70 60

50 40

30 20

10 pp

m

44.0833

62.0768

76.7403 77.0588 77.3755

98.4645 98.6074

115.4007 115.6148 128.2607 128.2941 128.3466 129.9232 129.9993 130.0774 144.2729 146.9043

154.2216 160.5061 160.5378 162.9642 162.9966

z g h − 6 − 6 4 − C

−1 80

−1 60

−1 40

−1 20

−1 00

−8 0

−6 0

−4 0

−2 0

0 pp

m

−114.1784

−100.4135

z g h − 6 − 6 4 − F

11 10

9 8

7 6

5 4

3 2

1 0

pp m

−0.0000

1.7066

2.5927

4.0104 4.0301 4.0483 4.0503 4.4699 4.4906 4.5098

6.0377 6.1270

7.2726 7.5052 7.5263 7.9013 7.9223

3.01

2.01

2.03

1.00

2.02

2.03 z g h − 2 − 1 8 0 − H

20 0

19 0

18 0

17 0

16 0

15 0

14 0

13 0

12 0

11 0

10 0

90 80

70 60

50 40

30 20

10 pp

m

26.5454

43.7797

62.0890

76.8038 77.1220 77.4406

96.4795 96.5977

128.1245 128.2015 128.6266 135.1678 135.1877 137.4290 137.4839 146.1508 148.7939 153.6775

197.5101

z g h − 2 − 1 8 0 − C

−1 60

−1 40

−1 20

−1 00

−8 0

−6 0

−4 0

−2 0

0 pp

m

−96.7446

z g h − 2 − 1 8 0 − F

11 10

9 8

7 6

5 4

3 2

1 0

pp m

−0.0000

1.6125

4.0464 4.0487 4.0661 4.0686 4.0861 4.0887 4.4961 4.5130 4.5166 4.5360

6.1416 6.2316

7.