One-Pot Synthesis of Benzo[4,5]imidazo[2,1-a]isoquinolines and Isoquinolino[3,4-b]quinoxalines via Tandem Cyclization Strategies

Transcription

1 Supporting information to accompany: One-Pot Synthesis of Benzo[4,5]imidazo[2,1-a]isoquinolines and Isoquinolino[3,4-b]quinoxalines via Tandem Cyclization Strategies Alex L. Bagdasarian, [a] Huy H. Nguyen, [a] Teresa A. Palazzo, [a] James C. Fettinger, [a] Makhluf J. Haddadin, [b] and Mark J. Kurth* [a] SI pgs 2-19: 1 H- and 13 C-NMR spectra for 1a, 2a, 4a, 4b, 4c, 4d, 4e, 7a, and 7b SI pg 20: X-ray crystal structure information for 1a SI pg 21: X-ray crystal structure information for 4a SI pgs 22-27: UV-Vis and fluorescence data for 7a, and 7b [a] Department of Chemistry, University of California, One Shields Avenue, Davis, California, 95616, USA [b] Department of Chemistry, American University of Beirut, Beirut, Lebanon Corresponding author mjkurth@ucdavis.edu SI pg 1

2 SI pg 2

3 SI pg 3

4 SI pg 4

5 SI pg 5

6 4a SI pg 6

7 4a SI pg 7

8 4b SI pg 8

9 4b SI pg 9

10 4c SI pg 10

11 4c SI pg 11

12 4d SI pg 12

13 4d SI pg 13

14 4e SI pg 14

15 4e SI pg 15

16 7a (prepared by two-step protocol) SI pg 16

17 7a (prepared by two-step protocol) SI pg 17

18 7b (prepared by one-pot protocol) SI pg 18

19 7b (prepared by one-pot protocol) SI pg 19

20 Crystal data and structure refinement for 1a. Identification code TP17TW41 (2Comp Twin) Empirical formula C14 H11 N3 Formula weight Temperature 90(2) K Wavelength Å Crystal system Orthorhombic Space group P Unit cell dimensions a = (5) Å = 90. b = (11) Å = 90. c = (12) Å = 90. Volume (16) Å 3 Z 4 Density (calculated) Mg/m 3 Absorption coefficient mm -1 F(000) 464 Crystal size x x mm 3 Crystal color and habit Orange Irregular Block Diffractometer Bruker APEX-II CCD Theta range for data collection to Index ranges -7<=h<=7, -15<=k<=15, -16<=l<=17 Reflections collected 2081 Independent reflections 2081 [R(int) = 0.000] Observed reflections (I > 2sigma(I)) 2078 Completeness to theta = % Absorption correction Semi-empirical from equivalents Max. and min. transmission and Solution method SHELXT (Sheldrick, 2014) Refinement method SHELXL-2014/7 (Sheldrick, 2014) Full-matrix least-squares on F 2 Data / restraints / parameters 2081 / 0 / 198 Goodness-of-fit on F Final R indices [I>2sigma(I)] R1 = , wr2 = R indices (all data) R1 = , wr2 = Absolute structure parameter -0.1(2) Largest diff. peak and hole and e.å -3 Thermal ellipsoids presented at 50% probability. 1a: CCDC SI pg 20

21 Crystal data and structure refinement for 4a. Identification code JF2411DFMI_SQ Empirical formula C18 H15 N3 O2 Formula weight Temperature 90(2) K Wavelength Å Crystal system Monoclinic Space group P2 1 /c Unit cell dimensions a = (9) Å = 90. b = (17) Å = (12). c = (6) Å = 90. Volume (2) Å 3 Z 4 Density (calculated) Mg/m 3 Absorption coefficient mm -1 F(000) 640 Crystal size x x mm 3 Crystal color and habit Canary Yellow Plate Diffractometer Bruker APEX-II CCD Theta range for data collection to Index ranges -14<=h<=14, -27<=k<=27, -9<=l<=9 Reflections collected Independent reflections 3854 [R(int) = ] Observed reflections (I > 2sigma(I)) 3473 Completeness to theta = % Absorption correction Numerical Max. and min. transmission and Solution method SHELXT (Sheldrick, 2014) Refinement method SHELXL-2014/7 (Sheldrick, 2014) Full-matrix least-squares on F 2 Data / restraints / parameters 3854 / 14 / 273 Goodness-of-fit on F Final R indices [I>2sigma(I)] R1 = , wr2 = R indices (all data) R1 = , wr2 = Largest diff. peak and hole and e.å -3 Thermal ellipsoids presented at 50% probability. 4a: CCDC SI pg 21

22 UV-Vis and Fluorescence Data a and 7b UV- Vis (λ exctiation profile) λ excitation (nm) 7a (chloroform) 7a (acetonitrile) 7a (acetone) 7a (ethanol) 7b (chloroform) 7b (acetonitrile) 7b (acetone) 7b (ethanol) UV-Vis profile for 7a and 7b taken in chloroform, acetonitrile, acetone, and ethanol. λ max excitation bands of 292, 392, and 414 nm were chosen for fluorescence studies (data follows). 7a emission solvent excitation chloroform acetonitrile acetone ethanol n/a n/a n/a 448 n/a 456 7b emission solvent excitation chloroform acetonitrile acetone ethanol n/a SI pg 22

23 7a and 7b Fluorescence in acetone (292 excitajon) A.U λ emission (nm) blank acetone 7a acetone 7b acetone A.U. 7a and 7b fluorescence in acetone (392 nm excitajon) λ emission (nm) blank acetone 7a acetone 7b acetone SI pg 23

24 7a and 7b fluorescnece in acetone (414nm excitajon) A.U λ emission (nm) blank acetone 7a acetone 7b acetone 7a and 7b fluorescence in chloroform (292 nm excitajon) 10 8 A.U λ emission (nm) blank chloroform 7a chloroform 7b chloroform a and 7b fluorescence in chloroform (392 nm excitajon) A.U λ emission (nm) blank chloroform 7a chloroform 7b chloroform SI pg 24

25 7a and 7b fluorescence in chloroform (414 nm excitajon) A.U λ emission (nm) blank chloroform 7a chloroform 7b chloroform A.U a and 7b fluorescence in acetonitrile (292 nm excitajon) λ emission (nm) blank acetonitrile 7a acetonitrile 7b acetonitrile 15 7a and 7b fluorescence in acetonitrile (392 nm excitajon) 10 A.U λ emission (nm) blank acetonitrile 7a acetonitrile 7b acetonitrile SI pg 25

26 7a and 7b fluorescence in acetonitrile (414 nm excitajon) A.U λ emission (nm) blank acetonitrile 7a acetonitrile 7b acetonitrile 7a and 7b fluorescence in ethanol (292 nm excitajon) A.U λ emission (nm) blank ethanol 7a ethanol 7b ethanol 7a and 7b fluorescence in ethanol (392 nm excitajon) A.U λ emission (nm) blank ethanol 7a ethanol 7b ethanol SI pg 26

27 7a and 7b fluorescence in ethanol (414 nm excitajon) A.U λ emission (nm) blank ethanol 7a ethanol 7b ethanol SI pg 27