Supporting Information

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1 Supporting Information An Amphiphilic Pillar[5]arene as Efficient and Substrate-Selective Phase-Transfer Catalyst Tomoki Ogoshi*, Naosuke Ueshima and Tada-aki Yamagishi Table of Contents Experimental Section Figure S1 1 H and 13 C NMR spectra of 1 Figure S2 1 H and 13 C NMR spectra of 3 Figure S3 Job plots for a mixture of 1-hexene and 1 Figure S4 1 H NMR titration of 1-hexene with 1 Figure S5 1 H NMR spectra of (a) CDCl 3 and (b) D 2 O phases after oxidation of 1-hexene by KMnO 4 with 1 for 5 h Figure S6 Job plots for a mixture of 1,4-dicyanobutane and 1 References S2-S3 S4 S5 S6 S7 S8 S9 S10 S1

2 Experimental Section Measurements. The 1 H NMR spectra were recorded at 500 MHz and 13 C NMR spectra were recorded at 125 MHz with a JEOL-ECA500 spectrometer. Determination of association constants between 1-hexene and 1. In 1-hexene 1 complex in CDCl 3, chemical exchange between free and complexed species was fast on an NMR timescale. Thus, NMR titrations were done with solutions which had a constant concentration of 1-hexene (3 mm) and varying concentrations of 1 (3 to 60 mm). By the non-linear curve-fitting methods, the association constant for 1-hexene 1 complex is 65 ± 16 M 1 for 1:1 stoichiometry. The non-linear curve-fitting was based on the equation: 1 δ obs = δ 11 [1 + K[H] 0 + K[G] 0 - {(1 + K[H] 0 + K[G] 0 ) 2-4K 2 [H] 0 [G] 0 } 1/2 ] 2K[G]0 Where δ obs is the chemical shift change of proton signal of methylene moiety of 1-hexene (Figure 2, peak H a ) at [H] 0, δ 11 is the chemical shift change of methylene moiety of 1-hexene when the axle is completely complexed, [G] 0 is the fixed initial concentration of 1-hexene, and [H] 0 is the initial concentration of the host 1. Determination of association constant between 1,4-dicyanobutane and 1. In 1H NMR spectrum of a mixture of 1,4-dicyanobutane and 1 in CDCl 3, chemical exchange between free and complexed species is slow on an NMR timescale. Thus, 1 H NMR spectra of mixtures of 1 and 1,4-dicyanobutane in different ratio showed two sets of resonances for complexed and free 1,4-dicyanobutane. The association constant for 1 1,4-dicyanobutane complex was calculated from integrations of complexed and free signals of the methylene moiety of 1,4-dicyanobutane. Amphiphilic Pillar[5]arene 1. To a solution of tributylphosphine (679 mg, 3.33 mmol) in acetonitrile (10 ml), 2 2 (550 mg, mmol) was added. The mixture was heated at 90 o C for 120 h. The resulting solution was poured into a mixture of diethyl ether and hexane (5:1) and the precipitate was collected by filtration (1, 1.10 g, mmol, Yield: 95%). 1 H NMR (CDCl 3, 500 MHz, ppm): δ 6.87 (s, 10H, phenyl), 4.17 (br, 20H, methylene), 3.74 (s, 10H, methylene bridge), (br, 20H, methylene), S2

3 (br, 80H, methylene), (m, 120H, methylene), 0.91 (t, J = 12 Hz, 90H, methyl). 13 C NMR (CDCl 3, 125 MHz, ppm): δ 149.2, 128.7, 115.3, 68.1, 29.6, 23.9, 23.8, 22.0, 18.8, 16.5, Anal. Calcd for C185H350Br10O10P10 5H 2 O C, 56.49; H, 9.22; N, Found: C, 56.40; H, 9.34; N, MALDI-TOFMS: m/z Calcd for C185H36O10P19F54 [M-PF 6 +H] + : 4348, found 4348 (We can detected the peak after counter anion exchange from Br - to PF 6 - ). Unit Model 3. To a solution of tributylphosphine (730 mg, 3.58 mmol) in acetonitrile (5 ml), bis(1-bromopropoxy)benzene 3 (420 mg, 1.19 mmol) was added. The reaction mixture was stirred at 90 o C for 24 h. The resulting solution was poured into a mixture of diethyl ether and hexane (5:1) and the precipitate was collected by filtration (3, 900 mg, 1.18 mmol, Yield: 99%). 1 H NMR (CDCl 3, 500 MHz, ppm): 6.82 (s, 4H, phenyl), 4.07 (t, J = 5.4 Hz, 4H, methylene), (m, 4H, methylene), (m, 12H, methylene), (m, 4H, methylene), (m, 24H, methylene), 0.97 (t, J = 14 Hz, 18H, methyl). 13 C NMR (CDCl 3, 125 MHz, ppm): δ 152.6, 115.6, 67.4, 53.5, 23.9, 23.8, 22.2, 19.0, 16.4, HRFABMS: m/z Calcd for C 36 H 70 O 2 P 2 [M 2Br] 2+ : , found Oxidation reaction of alkenes with PTCs by KMnO 4 in two-phase D 2 O/CDCl 3 system. To a mixture of D 2 O (4 ml) and CDCL 3 (4 ml), alkene (13 mmol), KMnO 4 (62.8 mg, 0.40 mmol) and PTC were added. The reaction mixture was stirred for 12 h at 25 o C. The CDCl 3 phase was collected. To remove KMnO 4, excess NaHSO 4 was added. The resulting solid was filtered off. The filtrate was used for 1 H NMR measurements. S3

4 1 H and 13 C NMR spectra of 1 Figure S1 1 H and 13 C NMR spectra of 1 in CDCl 3 at 25 o C. S4

5 1 H and 13 C NMR spectra of 3 Figure S2 1 H and 13 C NMR spectra of 3 in CDCl 3 at 25 o C. S5

6 Job plots for a mixture of 1-hexene and 1 Figure S3 Job plot between 1-hexene (guest) and 1 (host) was collected by plotting the δ in chemical shift of the proton signal of methylene (Figure 2, peak H a ) of 1-hexene observed by 1 H NMR spectroscopy against the change in the mole fraction of the guest (X guest ). Concentration: [1-hexene] + [1] = 10 mm. The plot indicates that stoichiometry of the host-guest complex is mainly 1:1. S6

7 1 H NMR titration of 1-hexene with 1 Figure S4. 1 H NMR titration of 1-hexene (3 mm, methylene proton peak H a in Figure 2) with 1 in CDCl 3 at 25 o C. S7

8 1 H NMR spectra of the (a) CDCl 3 and (b) D 2 O phases after oxidation of 1-hexene using 1 for 5 h Figure S5. 1 H NMR spectra of the (a) CDCl 3 and (b) D 2 O phases after the oxidation of 1-hexene using 1 for 5 h. We found the new proton peak from aldehyde moiety of 1-pentanal along with the proton peaks from remaining substance 1-hexene in CDCl 3 phase, but not in D 2 O phase, which indicates that the oxidation reaction proceeded in CDCl 3 phase, but not in D 2 O phase. S8

9 Job plots for a mixture of 1,4-dicyanobutane and 1 Figure S6. Job plots between 1,4-dicyanobutane (guest) and 1 (host). The job plot was conducted by varying the mole fractions of the guest and host. Integration ratios between complexed and free methylene proton signals of 1,4-dicyanobutane were utilized. Concentration: [1,4-dicyanobutane] + [1] = 10 mm. The plot indicates a 1:1 binding between the host and guest. S9

10 References 1) Ashton, P. R.: Ballardini, R.; Balzani, V.; Bělohradský, M.; Gandolfi, M. T.; Philp, D.; Prodi, L.; Raymo, F. M.; Reddington, M. V.; Spencer, N.; Stoddart, J. F.; Venturi, M.; Williams, D. J. J. Am. Chem. Soc. 1996, 118, ) Ogoshi, T.; Ueshima, N.; Yamagishi, T.; Toyota, Y.; Matsumi, N. Chem. Commun. 2012, 48, ) Adams, R.; Whitehill, L. N. J. Am. Chem. Soc. 1941, 63, S10