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Electronic Supplementary Information

Nickel-catalyzed cross-coupling of β-carbonyl alkenyl pivalates with

arylzinc chlorides

Wen-Jing Pan† and Zhong-Xia Wang*,†,‡

† CAS Key Laboratory of Soft Matter Chemistry, Hefei National Laboratory for Physical

Sciences at Microscale and Department of Chemistry, University of Science and Technology

of China, Hefei, Anhui 230026, P. R. China.

‡ Collaborative Innovation Center of Chemical Science and Engineering (Tianjin), Tianjin

300072, P. R. China.

Contents

1. Stability study of (E)-4-oxopent-2-en-2-yl pivalate, and (Z)- and (E)-4-o-tolylpent-3-en-2-one

and monitoring of reaction of (E)-4-oxopent-2-en-2-yl pivalate with o-MeC6H4ZnCl

3

(1) 1H NMR spectra of (E)-4-oxopent-2-en-2-yl pivalate, and (Z)- and (E)-4-o-tolylpent-

3- en-2-one

3

(2) GC monitoring of the reaction of (E)-4-oxopent-2-en-2-yl pivalate with o-

MeC6H4ZnCl

5

(i) GC of the pure samples for comparison 5

(ii) GC monitoring of the reaction of (E)-4-oxopent-2-en-2-yl pivalate with o-

MeC6H4ZnCl

6

(iii) GC-MS of the reaction mixture (reaction time: 1 h) 8

2. Copies of NMR spectra of the β-carbonyl alkenyl pivalates 13

(1) (E)-4-oxopent-2-en-2-yl pivalate (1a) 13

(2) (E)-4-oxo-4-phenylbut-2-en-2-yl pivalate (1b) 14

(3) 3-oxocyclopent-1-en-1-yl pivalate (1c) 15

(4) ethyl (E)-3-(pivaloyloxy)but-2-enoate (1d) 16

(5) (E)-4-(dimethylamino)-4-oxobut-2-en-2-yl pivalate (1g) 17

3. Copies of NMR spectra of the cross-coupling products 18

(1) (E)-4-(p-tolyl)pent-3-en-2-one 18

(2) (E)-4-(4-(dimethylamino)phenyl)pent-3-en-2-one 19

Electronic Supplementary Material (ESI) for Organic & Biomolecular Chemistry.This journal is © The Royal Society of Chemistry 2018

2

(3) (E)-4-(4-methoxyphenyl)pent-3-en-2-one 20

(4) (E)-4-(4-(trifluoromethyl)phenyl)pent-3-en-2-one 21

(5) (E)-4-(o-tolyl) pent-3-en-2-one 22

(6) (Z)-4-(o-tolyl) pent-3-en-2-one 23

(7) (E)-4-(thiophen-2-yl)pent-3-en-2-one 24

(8) (E)-3-(4-(dimethylamino)phenyl)-1-phenylbut-2-en-1-one 25

(9) (E)-(4-methoxyphenyl)-1-phenylbut-2-en-1-one 26

(10) (E)-1-phenyl-3-(p-tolyl)but-2-en-1-one 27

(11) (E)-1-phenyl-3-(4-(trifluoromethyl)phenyl)but-2-en-1-one 28

(12) 3-(4-(dimethylamino)phenyl)cyclopent-2-en-1-one 29

(13) 3-(4-methoxyphenyl)cyclopent-2-en-1-one 30

(14) 3-(p-tolyl)cyclopent-2-en-1-one 31

(15) 3-(4-(trifluoromethyl)phenyl)cyclopent-2-en-1-one 32

(16) 3-(furan-2-yl)cyclopent-2-en-1-one 33

(17) 3-(thiophen-2-yl)cyclopent-2-en-1-one 34

(18) ethyl (E)-3-(4-(dimethylamino)phenyl)but-2-enoate 35

(19) ethyl (E)-(4-methoxyphenyl)but-2-enoate 36

(20) ethyl (E)-3-(p-tolyl)but-2-enoate 37

(21) ethyl (E)-3-(4-(trifluoromethyl)phenyl)but-2-enoate 38

(22) ethyl (E)-3-(o-tolyl) but-2-enoate 39

(23) ethyl-(E)-3-(furan-2-yl)but-2-enoate 40

(24) ethyl-(E)-3-(thiophen-2-yl)but-2-enoate 41

(25) ethyl 4'-methoxy-3,4,5,6-tetrahydro-[1,1'-biphenyl]-2-carboxylate 42

(26) ethyl 4'-methyl-3,4,5,6-tetrahydro-[1,1'-biphenyl]-2-carboxylate 43

(27) ethyl 4'-(dimethylamino)-3,4,5,6-tetrahydro-[1,1'-biphenyl]-2-carboxylate 44

(28) 4-(4-(dimethylamino)phenyl)-2H-chromen-2-one 45

(29) 4-(4-methoxyphenyl)-2H-chromen-2-one 46

(30) 4-(p-tolyl)-2H-chromen-2-one 47

(31) 4-(4-(trifluoromethyl)phenyl)-2H-chromen-2-one 48

(32) 4-(furan-2-yl)-2H-chromen-2-one 49

(33) 4-(thiophen-2-yl)-2H-chromen-2-one 50

(34) 3-(4-(dimethylamino)phenyl)-N,N-dimethylbut-2-enamide 51

(35) 3-(4-methoxyphenyl)-N,N-dimethylbut-2-enamide 52

(36) N,N-dimethyl-3-(p-tolyl)but-2-enamide 53

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1. Stability study of (E)-4-oxopent-2-en-2-yl pivalate, and (Z)- and (E)-4-o-tolylpent-3- en-

2-one and monitoring of reaction of (E)-4-oxopent-2-en-2-yl pivalate with o-MeC6H4ZnCl

NMR spectra were recorded by a Bruker av 400 instrument at room temperature. The GC were

recorded by Agilent Technologies 7820A GC System, and GC-MS was determined by Thermo

Trace-1300 ISQ-Mass spectrometer.

(1) 1H NMR spectra of (E)-4-oxopent-2-en-2-yl pivalate, and (Z)- and (E)-4-o-tolylpent-3-en-

2-one

Figure S1. (a) 1H NMR spectrum of (E)-4-oxopent-2-en-2-yl pivalate in CDCl3; (b) 1H NMR

spectrum of the same sample recorded after 42 h.

4

Figure S2. (a) 1H NMR spectrum of (Z)-4-o-tolylpent-3-en-2-one in CDCl3; (b) 1H NMR spectrum of the same sample recorded after 37 h.

Figure S3. (a) 1H NMR spectrum of (E)-4-o-tolylpent-3-en-2-one in CDCl3; (b) 1H NMR spectrum of the same sample recorded after 37 h.

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(2) GC monitoring of the reaction of (E)-4-oxopent-2-en-2-yl pivalate with o-MeC6H4ZnCl

(i) GC of the pure samples for comparison

Figure S4. GC of (E)-4-oxopent-2-en-2-yl pivalate

Figure S5. GC of (Z)-4-o-tolylpent-3-en-2-one

dode

cane

6

Figure S6. GC of (E)-4-o-tolylpent-3-en-2-one

(ii) GC monitoring of the reaction of (E)-4-oxopent-2-en-2-yl pivalate with o-MeC6H4ZnCl

Figure S7. GC monitoring of the reaction (1 h; Z:E = 1:1.91)

dode

cane

Z-i

som

er

E-i

som

er

2,2'

-dim

ethy

lbip

heny

l

NM

P

E-4

-oxo

pent

-2-e

n-2-

yl p

ival

ate

impu

rity

7

Figure S8. GC monitoring of the reaction (3 h; Z:E = 1:2.28)

Figure S9. GC monitoring of the reaction (6 h; Z:E = 1:2.17)

8

Figure S10. GC monitoring of the reaction (10 h; Z:E = 1:1.90)

(iii) GC-MS of the reaction mixture (reaction time: 1 h)

Figure S11. GC-MS of the reaction mixture (component 1: NMP)

9

Figure S12. GC-MS of the reaction mixture (component 2: (E)-4-oxopent-2-en-2-yl pivalate)

Figure S13. GC-MS of the reaction mixture (component 3: impurity)

10

Figure S14. GC-MS of the reaction mixture (component 4: (Z)-4-o-tolylpent-3-en-2-one)

Figure S15. GC-MS of the reaction mixture (component 5: (E)-4-o-tolylpent-3-en-2-one)

11

Figure S16. GC-MS of the reaction mixture (component 6: 2,2'-dimethylbiphenyl)

Figure S17. GC-MS of the reaction mixture (component 7: impurity)

12

Figure S18. GC-MS of the reaction mixture (component 8: maybe Cy3P=O)

13

2. Copies of NMR spectra of the β-carbonyl alkenyl pivalates (1) (E)-4-oxopent-2-en-2-yl pivalate (1a)

14

(2) (E)-4-oxo-4-phenylbut-2-en-2-yl pivalate (1b)

- 1 . 0- 0 . 50 . 00 . 51 . 01 . 52 . 02 . 53 . 03 . 54 . 04 . 55 . 05 . 56 . 06 . 57 . 07 . 58 . 08 . 59 . 0

f 1 ( p p m )

9.2

4

3.0

0

0.9

8

2.0

51

.01

1.9

9

1.3

1

2.3

9

6.7

5

7.4

47

.46

7.4

87

.53

7.5

57

.57

7.9

17

.92

7.9

4

1H N M R (CDC l 3)

15

(3) 3-oxocyclopent-1-en-1-yl pivalate (1c)

16

(4) Ethyl (E)-3-(pivaloyloxy)but-2-enoate (1d)

17

(5) (E)-4-(dimethylamino)-4-oxobut-2-en-2-yl pivalate (1g)

18

3. NMR spectral copies of the cross-coupling products

(1) (E)-4-(p-tolyl)pent-3-en-2-one

19

(2) (E)-4-(4-(dimethylamino)phenyl)pent-3-en-2-one

20

(3) (E)-4-(4-methoxyphenyl)pent-3-en-2-one

21

(4) (E)-4-(4-(trifluoromethyl)phenyl)pent-3-en-2-one

22

(5) (E)-4-(o-tolyl)pent-3-en-2-one

23

(6) (Z)-4-(o-tolyl)pent-3-en-2-one

24

(7) (E)-4-(thiophen-2-yl)pent-3-en-2-one

25

(8) (E)-3-(4-(dimethylamino)phenyl)-1-phenylbut-2-en-1-one

26

(9) (E)-(4-methoxyphenyl)-1-phenylbut-2-en-1-one

27

(10) (E)-1-phenyl-3-(p-tolyl)but-2-en-1-one

28

(11) (E)-1-phenyl-3-(4-(trifluoromethyl)phenyl)but-2-en-1-one

29

(12) 3-(4-(dimethylamino)phenyl)cyclopent-2-en-1-one

30

(13) 3-(4-methoxyphenyl)cyclopent-2-en-1-one

31

(14) 3-(p-tolyl)cyclopent-2-en-1-one

32

(15) 3-(4-(trifluoromethyl)phenyl)cyclopent-2-en-1-one

33

(16) 3-(furan-2-yl)cyclopent-2-en-1-one

34

(17) 3-(thiophen-2-yl)cyclopent-2-en-1-one

35

(18) ethyl (E)-3-(4-(dimethylamino)phenyl)but-2-enoate

36

(19) ethyl (E)-(4-methoxyphenyl)but-2-enoate

37

(20) ethyl (E)-3-(p-tolyl)but-2-enoate

38

(21) ethyl-(E)-3-(4-(trifluoromethyl)phenyl)but-2-enoate

39

(22) ethyl (E)-3-(o-tolyl) but-2-enoate

40

(23) ethyl-(E)-3-(furan-2-yl)but-2-enoate

41

(24) ethyl-(E)-3-(thiophen-2-yl)but-2-enoate

42

(25) ethyl 4'-methoxy-3,4,5,6-tetrahydro-[1,1'-biphenyl]-2-carboxylate

43

(26) ethyl 4'-methyl-3,4,5,6-tetrahydro-[1,1'-biphenyl]-2-carboxylate

44

(27) ethyl 4'-(dimethylamino)-3,4,5,6-tetrahydro-[1,1'-biphenyl]-2-carboxylate

45

(28) 4-(4-(dimethylamino)phenyl)-2H-chromen-2-one

46

(29) 4-(4-methoxyphenyl)-2H-chromen-2-one

47

(30) 4-(p-tolyl)-2H-chromen-2-one

48

(31) 4-(4-(trifluoromethyl)phenyl)-2H-chromen-2-one

49

(32) 4-(furan-2-yl)-2H-chromen-2-one

50

(33) 4-(thiophen-2-yl)-2H-chromen-2-one

51

(34) 3-(4-(dimethylamino)phenyl)-N,N-dimethylbut-2-enamide

52

(35) 3-(4-methoxyphenyl)-N,N-dimethylbut-2-enamide

53

(36) N,N-dimethyl-3-(p-tolyl)but-2-enamide