Supporting Information For. metal-free methods for preparation of 2-acylbenzothiazoles and. dialkyl benzothiazole-2-yl phosphonates

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1 Supporting Information For Peroxide as switch of dialkyl H-phosphonate: two mild and metal-free methods for preparation of 2-acylbenzothiazoles and dialkyl benzothiazole-2-yl phosphonates Xiao-Lan Chen,*, Xu Li, Ling-Bo Qu,*,, Yu-Chun Tang, Wen-Peng Mai, Dong-hui Wei, Wen-Zhu Bi, Li-Kun Duan, Kai Sun, Jian-Yu Chen, Dian-Dian Ke, and Yu-Fen Zhao, College of Chemistry and Molecular Engineering, Zhengzhou University, Henan Province, Zhengzhou, , (P. R. China); Chemistry and Chemical Engineering School, Henan University of Technology, Henan Province, Zhengzhou, , (P. R. China); Department of Chemistry, Xiamen University, Xiamen, , (P. R. China) Table of Contents 1. Computational details by density functional theory (DFT).S2-S H NMR, 13 C NMR, and 31 P NMR copies of products...s10-s67 S1

2 1. Computational details by density functional theory (DFT) All DFT calculations were performed using the Gaussian 09 program 1. The structures of the reactants, transition states, and products in all reaction channels were optimized at the B3LYP 2 /6-31G(d, p) level in CH 3 CN solvent, using the integral equation formalism polarizable continuum model (IEF-PCM) 3. The corresponding vibrational frequencies were calculated and to identify the transition states have one and only one imaginary frequency. And we also confirmed that all the reactants, intermediates, and products have no imaginary frequencies. The same level of intrinsic reaction coordinate (IRC) 4 calculations were performed to ensure that the transition states lead to the expected reactants and products. References: 1. Frisch, M.J.; Trucks, G.. W.; Schlegel, H. B.; Scuseria, G. E.; Robb, M. A.; Cheeseman, J. R.; Scalmani, G.; Barone, V.; Mennucci, B.; Petersson, G. A.; Nakatsuji, H.; Caricato, M.; Li, X.; Hratchian, H. P.; Izmaylov, A. F.; Bloino, J.; Zheng, G.; Sonnenberg, J. L.; Hada, M.; Ehara, M.; Toyota, K.; Fukuda, R.; Hasegawa, J.; Ishida, M.; Nakajima, T.; Honda, Y.; Kitao, O.; Nakai, H.; Vreven, T.; Montgomery, J. A.; Jr, J.E.; Peralta, F.; Ogliaro, M.; Bearpark, J. J.; Heyd, E.; Brothers, K. N.; Kudin, V. N.; Staroverov, T.; Keith, R.; Kobayashi, J.; Normand, K.; Raghavachari, A.; Rendell, J. C.; Burant, S. S.; Iyengar, J.; Tomasi, M.; Cossi, N.; Rega, J. M.; Millam, M.; Klene, J. E.; Knox, J. B.; Cross, V.; Bakken, C.; Adamo, J.; Jaramillo, R.; Gomperts, R. E.; Stratmann, O.; Yazyev, A. J.; Austin, R.; Cammi, C.; Pomelli, J. W.; Ochterski, R. L.; Martin, K.; Morokuma, V. G.; Zakrzewski, G. A.; Voth, P.; Salvador, J. J.; Dannenberg, S.; Dapprich, A. D.; Daniels, O.; Farkas, J. B.; Foresman, J. V.; Ortiz, J.; Cioslowski, D.J. Fox, Revision C.01;, GAUSSIAN 09,Gaussian, Inc.: Wallingford, CT., GAUSSIAN 09(2010) (a) Becke, A. D.; Density-Functional Thermochemistry.3. The Role of Exact Exchange. J. Chem. Phys. 1993, 98 (7), ; (b) Lee, C. T.; Yang, W. T.; Parr, R. G., Development of the Colle-Salvetti Correlation-Energy Formula into a Functional of the Electron-Density. Phys. Rev. B. 1988, 37 (2), ; (c) Miehlich, B.; Savin, A.; Stoll, H.; Preuss, H. Results Obtained with the Correlation-Energy Density Functionals of Becke and Lee, Yang and Parr. Chem. Phys. Lett. 1989, 157 (3), (a) Barone, V.; Cossi, M., Quantum calculation of molecular energies and energy gradients in solution by a conductor solvent model. J. Phys. Chem. A. 1998, 102 (11), ; (b) Mennucci, B.; Tomasi, J., Continuum solvation models: A new approach to the problem of solute's charge distribution and cavity boundaries. J. Chem. Phys. 1997, 106 (12), (a) Gonzalez, C.; Schlegel, H. B., Reaction-Path Following in Mass-Weighted Internal Coordinates. J. Phys. Chem. 1990, 94 (14), ; (b) Gonzalez, C.; Schlegel, H. B., An Improved Algorithm for Reaction-Path Following. J. Chem. Phys. 1989, 90 (4), SUPPORTING INFORMATION The cartesian coordinates of reactants, transition states, products. R1 Center Atomic Atomic Coordinates (Angstroms) S2

3 Number Number Type X Y Z a Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z S3

4 3 a Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z R2 Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z TS1 Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z S4

5 TS2 Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z S5

6 TS3 Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z S6

7 TS4 Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z P1 Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z S7

8 a Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z a S8

9 Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z P2 Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z H NMR, 13 C NMR, and 31 P NMR copies of products S9

10 Fig.1 1 H NMR spectrum of compound 3a Fig.2 13 C NMR spectrum of compound 3a S10

11 Fig.3 1 H NMR spectrum of compound 3b Fig.4 13 C NMR spectrum of compound 3b S11

12 Fig.5 1 H NMR spectrum of compound 3c Fig.6 13 C NMR spectrum of compound 3c S12

13 Fig.7 1 H NMR spectrum of compound 3d Fig.8 13 C NMR spectrum of compound 3d S13

14 Fig.9 1 H NMR spectrum of compound 3e Fig C NMR spectrum of compound 3e S14

15 Fig.11 1 H NMR spectrum of compound 3f Fig C NMR spectrum of compound 3f S15

16 Fig.13 1 H NMR spectrum of compound 3g Fig C NMR spectrum of compound 3g S16

17 Fig.15 1 H NMR spectrum of compound 3h Fig C NMR spectrum of compound 3h S17

18 Fig.17 1 H NMR spectrum of compound 3i Br S O 2 N Fig C NMR spectrum of compound 3i S18

19 Fig.19 1 H NMR spectrum of compound 3j Fig.20 1 H NMR spectrum of compound 3j S19

20 Fig.21 1 H NMR spectrum of compound 3k Fig C NMR spectrum of compound 3k S20

21 Br S O 2 N Fig.23 1 H NMR spectrum of compound 3l Fig C NMR spectrum of compound 3l S21

22 Fig H NMR spectrum of compound 3m Fig C NMR spectrum of compound 3m S22

23 Fig H NMR spectrum of compound 3n Fig C NMR spectrum of compound 3n S23

24 Fig H NMR spectrum of compound 3o Fig C NMR spectrum of compound 3o S24

25 Fig.31 1 H NMR spectrum of compound 3p Fig C NMR spectrum of compound 3p S25

26 Fig.33 1 H NMR spectrum of compound 3q Fig C NMR spectrum of compound 3q S26

27 Fig.35 1 H NMR spectrum of compound 3r Fig C NMR spectrum of compound 3r S27

28 Fig H NMR spectrum of compound 3s Fig C NMR spectrum of compound 3s S28

29 Fig H NMR spectrum of compound 3t Fig C NMR spectrum of compound 3t S29

30 Fig.41 1 H NMR spectrum of compound 3u Fig C NMR spectrum of compound 3u S30

31 Fig H NMR spectrum of compound 3v Fig C NMR spectrum of compound 3v S31

32 Fig H NMR spectrum of compound 3w Fig C NMR spectrum of compound 3w S32

33 Fig.47 1 H NMR spectrum of compound 3x Fig C NMR spectrum of compound 3x S33

34 Fig.49 HRMS (ESI) spectrum of compound 3y Fig.50 HRMS (ESI) spectrum of compound 3z S34

35 Fig.51 1 H NMR spectrum of compound 8a Fig C NMR spectrum of compound 8a S35

36 Fig P NMR spectrum of compound 8a Fig.54 1 H NMR spectrum of compound 8b S36

37 Fig C NMR spectrum of compound 8b Fig P NMR spectrum of compound 8b S37

38 Fig H NMR spectrum of compound 8c Fig C NMR spectrum of compound 8c S38

39 Fig P NMR spectrum of compound 8c Fig H NMR spectrum of compound 8d S39

40 Fig C NMR spectrum of compound 8d Fig P NMR spectrum of compound 8d S40

41 O S 2 p N O 3 12 O 11 Fig H NMR spectrum of compound 8e O S 2 p N O 3 12 O 11 Fig C NMR spectrum of compound 8e S41

42 O S 2 p N O 3 12 O 11 Fig P NMR spectrum of compound 8e Fig H NMR spectrum of compound 8f S42

43 Fig C NMR spectrum of compound 8f Fig P NMR spectrum of compound 8f S43

44 Fig H NMR spectrum of compound 8g Fig C NMR spectrum of compound 8g S44

45 Fig P NMR spectrum of compound 8g Br S O 2 p 10 N O 3 11 O Fig H NMR spectrum of compound 8h S45

46 Fig C NMR spectrum of compound 8h Fig P NMR spectrum of compound 8h S46

47 Fig H NMR spectrum of compound 8i Fig C NMR spectrum of compound 8i S47

48 Fig P NMR spectrum of compound 8i Fig H NMR spectrum of compound 8j S48

49 Fig C NMR spectrum of compound 8j Fig P NMR spectrum of compound 8j S49

50 Fig H NMR spectrum of compound 8k Fig C NMR spectrum of compound 8k S50

51 Fig P NMR spectrum of compound 8k Fig H NMR spectrum of compound 8l S51

52 Fig C NMR spectrum of compound 8l Fig P NMR spectrum of compound 8l S52

53 Fig H NMR spectrum of compound 8m Fig C NMR spectrum of compound 8m S53

54 Fig P NMR spectrum of compound 8m Fig.90 1 H NMR spectrum of compound 8n S54

55 Fig C NMR spectrum of compound 8n Fig P NMR spectrum of compound 8n S55

56 Fig H NMR spectrum of compound 8o Fig C NMR spectrum of compound 8o S56

57 Fig P NMR spectrum of compound 8o Fig.96 1 H NMR spectrum of compound 8p S57

58 Fig C NMR spectrum of compound 8p Fig P NMR spectrum of compound 8p S58

59 H 3 CO S N 3 O 2 P O O Fig.99 1 H NMR spectrum of compound 8q H CO O S 2 P N O O Fig C NMR spectrum of compound 8q S59

60 H CO S N 3 O 2 P O O Fig P NMR spectrum of compound 8q Fig H NMR spectrum of compound 8r S60

61 Fig C NMR spectrum of compound 8r Fig P NMR spectrum of compound 8r S61

62 Fig H NMR spectrum of compound 8s Fig C NMR spectrum of compound 8s S62

63 Fig P NMR spectrum of compound 8s Fig H NMR spectrum of compound 8t S63

64 Fig C NMR spectrum of compound 8t Fig P NMR spectrum of compound 8t S64

65 Fig H NMR spectrum of compound 8u Fig C NMR spectrum of compound 8u S65

66 Fig P NMR spectrum of compound 8u Fig.114 HRMS (ESI) spectrum of compound 8v S66

67 Fig H NMR spectrum of compound 7d S O N Fig C NMR spectrum of compound 7d S67