Supporting Information for. Photocatalytic Decarboxylative Hydroxylation of Carboxylic Acids. Driven by Visible Light and Using Molecular Oxygen

Transcription

1 Supporting Information for Photocatalytic Decarboxylative Hydroxylation of Carboxylic Acids Driven by Visible Light and Using Molecular Oxygen Hai-Tao Song, Wei Ding, Quan-Quan Zhou, Jing Liu, Liang-Qiu Lu* and Wen-Jing Xiao Key Laboratory of Pesticide & Chemical Biology, Ministry of Education, College of Chemistry, Central China Normal University, 152 Luoyu Road, Wuhan, Hubei , China * Table of Contents 1. Details for Condition Optimization S2 2. Copies of 1 H NMR and 13 C NMR Spectra of Products S3 3. References for Known Compounds S23 4. Mechanism Study S24 S1

2 1. Details for Condition Optimization a Table S1. Base effects for the photocatalytic decarboxylative hydroxylation. entry variation from the standard conditions yield/% b 1 none 78 (80 c ) 2 K3PO4, instead of K2HPO K2CO3, instead of K2HPO4 0 4 Cs2CO3, instead of K2HPO Na2CO3, instead of K2HPO DBU, instead of K2HPO ,6-lutidine, instead of K2HPO eq. K2HPO4 was used eq. K2HPO4 was used eq. K2HPO4 was used 76 a Standard conditions: 1a (0.5 mmol), PC-I (0.01 mmol, 2 mol%), K2HPO4 (0.75 mmol, 1.5 equiv.), O2 balloon and CHCl3 (5.0 ml) at r.t. under the irradiation of 7 W blue LEDs for 36 h; then NaBH4 (1.0 mmol, 2.0 eq.) and MeOH (2 ml) were added and stirred for 0.5 h. b Determined by 1 H NMR using 1, 3, 5-trimethoxybenzene as an internal standard. c Isolated yield. Mes-AcrClO4: 9-mesityl-10-methylacridinium perchlorate. DCE: 1, 2-dichloroethane. DBU: 1, 8-diazabicyclo[5.4.0]undec-7-ene. S2

3 2. Copies of 1 H NMR and 13 C NMR Spectra of Products 1 H NMR spectrum (600 MHz, CDCl3) of product 2a 13 C NMR spectrum (100 MHz, CDCl3) of product 2a S3

4 1 H NMR spectrum (600 MHz, CDCl3) of product 2b 13 C NMR spectrum (100 MHz, CDCl3) of product 2b S4

5 1 H NMR spectrum (600 MHz, CDCl3) of product 2c 13 C NMR spectrum (100 MHz, CDCl3) of product 2c S5

6 1 H NMR spectrum (600 MHz, CDCl3) of product 2d 13 C NMR spectrum (100 MHz, CDCl3) of product 2d S6

7 1 H NMR spectrum (600 MHz, CDCl3) of product 2e 13 C NMR spectrum (100 MHz, CDCl3) of product 2e S7

8 1 H NMR spectrum (400 MHz, CDCl3) of product 2f 13 C NMR spectrum (100 MHz, CDCl3) of product 2f S8

9 1 H NMR spectrum (600 MHz, CDCl3) of product 2h 13 C NMR spectrum (100 MHz, CDCl3) of product 2h S9

10 1 H NMR spectrum (600 MHz, CDCl3) of product 2i 13 C NMR spectrum (100 MHz, CDCl3) of product 2i S10

11 1 H NMR spectrum (400 MHz, CDCl3) of product 2j 13 C NMR spectrum (100 MHz, CDCl3) of product 2j S11

12 1 H NMR spectrum (600 MHz, CDCl3) of product 2k 13 C NMR spectrum (100 MHz, CDCl3) of product 2k S12

13 1 H NMR spectrum (600 MHz, CDCl3) of product 2l 13 C NMR spectrum (100 MHz, CDCl3) of product 2l S13

14 1 H NMR spectrum (600 MHz, CDCl3) of product 2m 13 C NMR spectrum (100 MHz, CDCl3) of product 2m S14

15 1 H NMR spectrum (600 MHz, CDCl3) of product 2n 13 CNMR spectrum (100 MHz, CDCl3) of product 2n S15

16 1 H NMR spectrum (600 MHz, CDCl3) of product 2o 13 C NMR spectrum (100 MHz, CDCl3) of product 2o S16

17 1 H NMR spectrum (600 MHz, CDCl3) of product 2p 13 C NMR spectrum (100 MHz, CDCl3) of product 2p S17

18 1 H NMR spectrum (400 MHz, CDCl3) of product 2q 13 C NMR spectrum (100 MHz, CDCl3) of product 2q S18

19 1 H NMR spectrum (600 MHz, CDCl3) of product 2r 13 C NMR spectrum (100 MHz, CDCl3) of product 2r S19

20 1 H NMR spectrum (600 MHz, d 6 -DMSO) of product 2s 13 C NMR spectrum (100 MHz, d 6 -DMSO) of product 2s S20

21 1 H NMR spectrum (600 MHz, CDCl3) of product 2t 13 C NMR spectrum (100 MHz, CDCl3) of product 2t S21

22 1 H NMR spectrum (400 MHz, CDCl3) of product 2u 13 C NMR spectrum (100 MHz, CDCl3) of product 2u S22

23 3. References for Known Compounds No. reference Compd. 1 Zhang, W.-X.; Dai, Y.-S.; Zhu, H.-Z.; Zhang, W. Tetrahedron Lett. 2013, 54, a, 2j 2 Battilocchio, C.; Hawkins, J. M.; Ley, S. V. Org. Lett. 2013, 15, b, 2c, 2h 3 Liao, Y.-X.; Hu, Q.-S. J. Org. Chem. 2011, 76, d 4 Kwon, M. S.; Park, I. S.; Jang, J. S.; Lee, J. S.; Park, J. Org. Lett. 2007, 9, e, 2t 5 Stefan, E.; Nalin, A. P..; Taylor, R. E. Tetrahedron 2013, 69, f 6 (f) Wang, J.; Wan, W.; Jiang, H.-Z.; Gao, Y.; Jiang, X.-Y.; Lin, H.-P.; Zhao, W.-M.; Hao, J. Org. Lett. 2010, 12, i 7 Li, J.; Wang, H,-N.; Liu, L.; Sun, J.-T. RSC Adv. 2014, 4, k 8 Li, J.; Wang, C.; Xue, D.; Wei, Y.-W.; Xiao, J.-L. Green Chemistry 2013, 15, Waals, D. V. D.; Pettmanb, A.; Williams, J. M. J. RSC Adv. 2014, 4, Mori, S.; Takubo, M.; Makida, K.; Yanase, T.; Aoyagi, S.; Maegawaz, T.; Monguchi, Y.; Sajiki, H. Chem. Commun. 2009, Aramini, A.; Cesta, M. C.; Coniglio, S.; Bijani, C.; Colagioia, S.; Elia, V. D.; Allegretti, M. J. Org. Chem. 2003, 68, Noji, M.; Ohno, T.; Fuji, K.; Futaba, N.; Tajima, H.; Ishii, K. J. Org. Chem. 2003, 68, Manchand, P. S.; Coffen, D. L.; Belica, P. S.; Wong, F.; Wong, H. S.; Berger, L. Heterocyclic Chemistry 1994, 39, Fernandes, T. A.; Santos, C. I. M.; Andre, V.; Kłak, J.; Kirillova, M. V.; Kirillov, A. M. Inorg. Chem. 2016, 55, l, 2m, 2n 2o 2p 2q 2r 2s 2u S23

24 4. Mechanism Study O Labeling Experiments The HRMS data of 2a for the reaction in the presence of 18 O2 S24

25 The HRMS data of 2a for the reaction in the presence of H2 18 O S25

26 The MS data of the reaction before the reduction operation with NaBH4 S26

27 The MS data of the reaction after the reduction operation with NaBH4 S27