Supporting Information

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1 Supporting Information Substituted 5,6,11,12-tetradehydrodibenzo[a,e]cyclooctenes: Syntheses, Properties and DFT Studies of Substituted Sondheimer-Wong Diynes Feng Xu, 1 Lifen Peng, 1 Kenta Shinohara, 1 Takamoto Morita, 2 Suguru Yoshida, 2 Takamitsu Hosoya, 2 Akihiro Orita, 1 * and Junzo Otera 1 orita@dac.ous.ac.jp 1 Department of Applied Chemistry, Okayama University of Science, 1-1 Ridai-cho, Kita-ku,Okayama , Japan 2 Laboratory of Chemical Bioscience, Institute of Biomaterials and Bioengineering, Tokyo Medical and Dental University, Kanda-Surugadai, Chiyoda-ku, Tokyo , Japan Table of contents Cyclic voltammetry Theoretical Calculations Calculations of strain energies Kinetic studies on double-click reaction References NMR charts of products S2 S4 S30 S32 S34 S35 S1

2 Cyclic voltammetry The reduction and oxidation potentials (vs Fc/Fc + ) were measured under the following conditions: in CH 2 Cl 2 (1.0 x 10-4 M, 100 mv/s scan rate, 0.1 M Bu 4 NPF 6 ), a glassy carbon as the working electrode, a Pt counter electrode, and an Ag/Ag + reference electrode (0.01M AgNO 3 and 0.1M tetrabutylammonium perchlorate in acetonitrile) in 0.1 M LiClO 4 /acetonitrile. Figure S1. Oxidation potentials of 2. Figure S2. Reduction potentials of 2. S2

3 Semi-differential cyclic voltammetry of 2a indicated that 2a underwent two-electron oxidation to provide 14 system (Figures S3 and S4). (Electron number transferred in oxidation of 2a) = 5.62/2.44 = 2.30 Figure S3. Semi-differential cyclic voltammetry of 2a. Figure S4. Semi-differential cyclic voltammetry of ferrocene (Fc). S3

4 Theoretical Calculations Calculations were performed by using Gaussian09 program package. S1 Cartesian coordinates for optimized structures 2 at the B3LYP/6-31G(d) level and calculated transition states (S 0 =>S n ) of 2. 2a (B3LYP/6-31G(d)) C C C C H C C H H H C C C C C C H C C H H H C C TD-DFT (B3LYP/6-31G(d)// B3LYP/6-31G(d)) Excited State 1: Singlet-A ev nm f= <S**2>= > Excited State 2: Singlet-A ev nm f= <S**2>= > > Excited State 3: Singlet-A ev nm f= <S**2>= > S4

5 Excited State 4: Singlet-A ev nm f= <S**2>= > > Excited State 5: Singlet-A ev nm f= <S**2>= > > > > Excited State 6: Singlet-A ev nm f= <S**2>= > > > Excited State 7: Singlet-A ev nm f= <S**2>= > > > > Excited State 8: Singlet-A ev nm f= <S**2>= > > Excited State 9: Singlet-A ev nm f= <S**2>= > > Excited State 10: Singlet-A ev nm f= <S**2>= > > b (B3LYP/6-31G(d)) C C C C H C C H S5

6 C C C C C C H C C H C C O O O O C H H H C H H H C H H H C H H H TD-DFT (B3LYP/6-31G(d)// B3LYP/6-31G(d)) Excited State 1: Singlet-A ev nm f= <S**2>= > Excited State 2: Singlet-A ev nm f= <S**2>= > > Excited State 3: Singlet-A ev nm f= <S**2>= > S6

7 Excited State 4: Singlet-A ev nm f= <S**2>= > Excited State 5: Singlet-A ev nm f= <S**2>= > > Excited State 6: Singlet-A ev nm f= <S**2>= > > > > Excited State 7: Singlet-A ev nm f= <S**2>= > > > Excited State 8: Singlet-A ev nm f= <S**2>= > > Excited State 9: Singlet-A ev nm f= <S**2>= > > > Excited State 10: Singlet-A ev nm f= <S**2>= > > > c (B3LYP/6-31G(d)) C C C C H C C H C C S7

8 C C C C H C C H C C O O O O C H H C H H C H H C H H C H H C H H C H H C H H C H H H C H S8

9 H C H H C H H C H H C H H H C H H C H H C H H C H H C H H H C H H C H H C H H C H H C H S9

10 H H TD-DFT (B3LYP/6-31G(d)// B3LYP/6-31G(d)) Excited State 1: Singlet-A ev nm f= <S**2>= > Excited State 2: Singlet-A ev nm f= <S**2>= > > Excited State 3: Singlet-A ev nm f= <S**2>= > Excited State 4: Singlet-A ev nm f= <S**2>= > > Excited State 5: Singlet-A ev nm f= <S**2>= > > Excited State 6: Singlet-A ev nm f= <S**2>= > > > > > Excited State 7: Singlet-A ev nm f= <S**2>= > > > > > > > Excited State 8: Singlet-A ev nm f= <S**2>= > > > > > S10

11 Excited State 9: Singlet-A ev nm f= <S**2>= > > > > Excited State 10: Singlet-A ev nm f= <S**2>= > > > > > d (B3LYP/6-31G(d)) C C C C C C C C C C C C C C C C C C H C C H H H C H C H S11

12 C H C H O O O O C H H H C H H H C H H H C H H H e (B3LYP/6-31G(d)) C C C C H C C H H C C C C C C H C S12

13 C H H C C F F f (B3LYP/6-31G(d)) C C C C H C C H H C C C C C C H C C H H C C Br Br j (B3LYP/6-31G(d)) C C C C H C C S13

14 H H C C C C C C H C C H H C C C C C C C C C C H C H C H H C C C C H C H C H H C H H C H S14

15 H C H H C H H C H H C H H C H H H C H H C H H C H H C H H C H H H TD-DFT (B3LYP/6-31G(d)// B3LYP/6-31G(d)) Excited State 1: Singlet-A ev nm f= <S**2>= > > Excited State 2: Singlet-A ev nm f= <S**2>= > > Excited State 3: Singlet-A ev nm f= <S**2>=0.000 S15

16 149 -> > > Excited State 4: Singlet-A ev nm f= <S**2>= > > > Excited State 5: Singlet-A ev nm f= <S**2>= > Excited State 6: Singlet-A ev nm f= <S**2>= > > > Excited State 7: Singlet-A ev nm f= <S**2>= > > Excited State 8: Singlet-A ev nm f= <S**2>= > > > > Excited State 9: Singlet-A ev nm f= <S**2>= > > Excited State 10: Singlet-A ev nm f= <S**2>= > > > > k (B3LYP/6-31G(d)) C C C C H S16

17 C C H H C C C C C C H C C H H C C C C C C H C H C H H C C C C H C H C H H C H H C H H C S17

18 H H C H H C H H C H H C H H H C H H C H H C H H C H H C H H H TD-DFT (B3LYP/6-31G(d)// B3LYP/6-31G(d)) Excited State 1: Singlet-A ev nm f= <S**2>= > Excited State 2: Singlet-A ev nm f= <S**2>= > > > Excited State 3: Singlet-A ev nm f= <S**2>= > S18

19 Excited State 4: Singlet-A ev nm f= <S**2>= > > > Excited State 5: Singlet-A ev nm f= <S**2>= > > Excited State 6: Singlet-A ev nm f= <S**2>= > > > Excited State 7: Singlet-A ev nm f= <S**2>= > > Excited State 8: Singlet-A ev nm f= <S**2>= > > Excited State 9: Singlet-A ev nm f= <S**2>= > > > > > Excited State 10: Singlet-A ev nm f= <S**2>= > > > > m (B3LYP/6-31G(d)) C C C C H C C S19

20 H C C C C C C H C C H C C O O C H H H C H H H H C C C C H C H C O O O C H H H C H H H C S20

21 H H H TD-DFT (B3LYP/6-31G(d)// B3LYP/6-31G(d)) Excited State 1: Singlet-A ev nm f= <S**2>= > > Excited State 2: Singlet-A ev nm f= <S**2>= > > > Excited State 3: Singlet-A ev nm f= <S**2>= > Excited State 4: Singlet-A ev nm f= <S**2>= > > > Excited State 5: Singlet-A ev nm f= <S**2>= > Excited State 6: Singlet-A ev nm f= <S**2>= > > > > > Excited State 7: Singlet-A ev nm f= <S**2>= > > Excited State 8: Singlet-A ev nm f= <S**2>= > > > > Excited State 9: Singlet-A ev nm f= <S**2>= > S21

22 106 -> > > > > > Excited State 10: Singlet-A ev nm f= <S**2>= > > > > > > > > > ab (B3LYP/6-31G(d)) C C C C H C C H C C C C C C H C C H C C O O C H S22

23 H H C H H H H H TD-DFT (B3LYP/6-31G(d)// B3LYP/6-31G(d)) Excited State 1: Triplet-B ev nm f= <S**2>= > > Excited State 2: Singlet-B ev nm f= <S**2>= > Excited State 3: Triplet-A ev nm f= <S**2>= > > > Excited State 4: Triplet-A ev nm f= <S**2>= > > Excited State 5: Singlet-A ev nm f= <S**2>= > > Excited State 6: Singlet-B ev nm f= <S**2>= > be (B3LYP/6-31G(d)) C C C C H C C H C S23

24 C C C C C H C C H H C C F O O C H H H C H H H TD-DFT (B3LYP/6-31G(d)// B3LYP/6-31G(d)) Excited State 1: Singlet-A ev nm f= <S**2>= > Excited State 2: Singlet-A ev nm f= <S**2>= > > Excited State 3: Singlet-A ev nm f= <S**2>= > Excited State 4: Singlet-A ev nm f= <S**2>= > Excited State 5: Singlet-A ev nm f= <S**2>= > > > Excited State 6: Singlet-A ev nm f= <S**2>=0.000 S24

25 68 -> > > > > Excited State 7: Singlet-A ev nm f= <S**2>= > > > > > > > > Excited State 8: Singlet-A ev nm f= <S**2>= > > > > > > Excited State 9: Singlet-A ev nm f= <S**2>= > > > > > > Excited State 10: Singlet-A ev nm f= <S**2>= > > > > ai (B3LYP/6-31G(d)) C C C C S25

26 C H C H H H C C C C C C C C H C C C H C H C C H H H TD-DFT (B3LYP/6-31G(d)// B3LYP/6-31G(d)) Excited State 1: Triplet-B ev nm f= <S**2>= > > > > Excited State 2: Triplet-A ev nm f= <S**2>= > > Excited State 3: Singlet-B ev nm f= <S**2>= > Excited State 4: Triplet-B ev nm f= <S**2>= > > S26

27 64 -> > > > Excited State 5: Singlet-A ev nm f= <S**2>= > > Excited State 6: Singlet-B ev nm f= <S**2>= > ci (B3LYP/6-31G(d)) C C C C C H C H C C C C C C C C H C C C H C H C C H H H O O S27

28 C H H C H H C H H C H H C H H C H H H C H H C H H C H H C H H C H H C H H H TD-DFT (B3LYP/6-31G(d)// B3LYP/6-31G(d)) Excited State 1: Singlet-A ev nm f= <S**2>= > Excited State 2: Singlet-A ev nm f= <S**2>=0.000 S28

29 120 -> > Excited State 3: Singlet-A ev nm f= <S**2>= > > Excited State 4: Singlet-A ev nm f= <S**2>= > > Excited State 5: Singlet-A ev nm f= <S**2>= > Excited State 6: Singlet-A ev nm f= <S**2>= > > > Excited State 7: Singlet-A ev nm f= <S**2>= > > > Excited State 8: Singlet-A ev nm f= <S**2>= > > > > Excited State 9: Singlet-A ev nm f= <S**2>= > > > > Excited State 10: Singlet-A ev nm f= <S**2>= > > > S29

30 Calculations of strain energies Strain energy (PM3) of symmetrically substituted cyclic diyne 2 was calculated by the following equation: E strain = (E 1 )-(2/3E 2 ) E 1 : single point energy of 2 (cyclic dimer of phenyleneethynylene) E 2 : single point energy of 2 trimer (cyclic trimer of phenyleneethynylene) representative structures 2a 2a trimer Table S1. Summary of strain energies of symmetrically substituted cyclic diynes 2 2a 2b 2c b 2d b 2e 2f 2j c 2k c E [kcal/mol] a E [kcal/mol] a E strain [kcal/mol] a a) Structures of the cyclic diynes 2 and triynes 2 trimer were optimized, and their strain energies were calculated at the PM3 level. b) Calculations were performed on methoxy derivatives. c) Calculations were performed on methyl derivatives. S30

31 Strain energy (PM3) of unsymmetrically substituted cyclic diyne 2 was calculated by the following equation: E strain = (E 1 )-(2/3) x(1/2)x(e 2A + E 2B ) E 1 : single point energy of 2 (cyclic dimer of phenyleneethynylene) E 2A : single point energy of 2 trimera (cyclic trimer of phenyleneethynylenea) E 2B : single point energy of 2 trimerb (cyclic trimer of phenyleneethynyleneb) Table S2. Summary of strain energies of unsymmetrically substituted cyclic diynes 2 2m 2ab 2be 2ai 2ci b E [kcal/mol] a E2A [kcal/mol] a E2B [kcal/mol] a E strain [kcal/mol] a a) Structures of the cyclic diynes 2 and triynes 2 trimer were optimized, and their strain energies were calculated at the PM3 level. b) Calculations were performed on methoxy derivatives. S31

32 Kinetic studies on double-click reaction of diyne 2 with benzyl azide (representative) S2 The rate measurement of the first cycloaddition in the double-click reaction was performed by monitoring the absorbance of diyne 2 in the presence of an excess amount of benzyl azide. To 1.5 ml of 2.0 mm (final concentration at 1.0 mm) solution of diyne 2 in MeOH placed in a quartz cuvette (10 mm light path, temperature kept at 25 C) was added 1.5 ml of MeOH solution of benzyl azide in three different concentrations (20, 100, or 200 mm; final concentration at 10, 50 and 100 mm, respectively). The consumption of diyne 2 was monitored by UV spectroscopy focusing at characteristic absorbances observed for each diyne with a wavelength of nm for 2b (log : 2.66) or nm for 2ab (log : 3.05), which are the wavelengths that almost no significant absorption was observed for benzyl azide and bis-cycloadducts. The monitoring was continued for s for 100 mm (2b), s for 50 mm (2b), s (2b), s for 100 mm (2ab), s for 50 mm (2ab), or s (2ab), and the experiments were repeated in duplicate or triplicate for each concentration of benzyl azide. The observed absorbance data at nm for 2b or nm for 2ab, which contains absorbance of diyne 2 and benzyl azide, were plotted versus time and fitted to a first order exponential decay curve. The pseudo-first order rate constants (k ) were determined by least-squares fitting of the data to the following exponential equation using KaleidaGraph ver y = a*exp( k *(t + t 0 )) + y 0 a: absorption of diyne 2 (1.0 mm) t: time (s) from the starting point of the observation t 0 : time (s) between the starting point of the reaction and the observation The pseudo-first order rate constants (k ) were plotted versus concentrations of benzyl azide and fitted to a straight line by linear regression method using KaleidaGraph ver The slope of the straight line indicates the second order rate constant (k) for the first cycloaddition in the double-click reaction of diyne 2 and benzyl azide, which is the rate-determining step of the reaction. S32

33 Figure S5. Left graph: Time-dependent absorbance of diyne 2b (initial concentration of 1.0 mm) at nm of wavelength monitored in duplicate or triplicate during the reaction with benzyl azide in three different concentrations (10, 50, or 100 mm). Right graph: A plot of pseudo-first order rate constants (k ) versus the concentration of benzyl azide. Figure S6. Left graph: Time-dependent absorbance of diyne 2ab (initial concentration of 1.0 mm) at nm of wavelength monitored in duplicate during the reaction with benzyl azide in three different concentrations (10, 50, or 100 mm). Right graph: A plot of pseudo-first order rate constants (k ) versus the concentration of benzyl azide. S33

34 Table S3. Summary of reaction rates (k) in double-click reaction of 2 with benzyl azide diyne max [nm] max [M -1 ] k [M -1 s -1 ] x a x MeO MeO 2b a) See reference S2. OMe OMe x References S1) Gaussian09; M. J. Frisch, G. W. Trucks, H. B. Schlegel, G. E. Scuseria, M. A. Robb, J. R. Cheeseman, G. Scalmani, V. Barone, B. Mennucci, G. A. Petersson, H. Nakatsuji, M. Caricato, X. Li, H. P. Hratchian, A. F. Izmaylov, J. Bloino, G. Zheng, J. L. Sonnenberg, M. Hada, M. Ehara, K. Toyota, R. Fukuda, J. Hasegawa, M. Ishida, T. Nakajima, Y. Honda, O. Kitao, H. Nakai, T. Vreven, J. A. Montgomery, Jr., J. E. Peralta, F. Ogliaro, M. Bearpark, J. J. Heyd, E. Brothers, K. N. Kudin, V. N. Staroverov, 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, Gaussian 09, Revision A.02, Gaussian, Inc., Wallingford CT, S2) Kii, I.; Shiraishi, A.; Hiramatsu, T.; Matsushita, T.; Uekusa, H.; Yoshida, S.; Yamamoto, M.; Kudo, A.; Hagiwara, M.; Hosoya. T. Org. Biomol. Chem. 2010, 8, S34

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