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Supporting Information For:

Formal Aryne/Carbon Monoxide Copolymerization to

Form Aromatic Polyketones/Polyketals

Shingo Ito,*,† Wenhan Wang,† Katsuyuki Nishimura,‡ and Kyoko Nozaki*,†

† Department of Chemistry and Biotechnology, Graduate School of Engineering The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-8656, Japan

‡ Institute for Molecular Science, 38 Nishigo-Naka, Myodaiji, Okazaki, Aichi 444-8585, Japan

Experimental Section

General: All manipulations were carried out using glove boxes and standard Schlenk techniques under

argon purified by passing through a hot column packed with BASF catalyst R3-11. All polymerizations

were carried out using a 50-mL autoclave.

Instrumentation: Nuclear magnetic resonance (NMR) spectra in solution were recorded on JEOL

JNM-ECP500 (1H: 500 MHz, 13C: 126 MHz with digital resolution of 0.239, 0.960 Hz, respectively) or

JEOL JNM-ECS400 (1H: 400 MHz, 13C: 101 MHz with digital resolution of 0.0913, 0.767 Hz,

respectively) NMR spectrometers. Solid-state NMR spectra were recorded on a Bruker Avance 600

spectrometer at 1H resonant frequency of 600 MHz, equipped with a 2.5mm O.D. 1H-13C-15N triple

resonance MAS probe. Temperatures were controlled to 293 K using VT controller. MAS frequency

was actively controlled to 20 kHz using Bruker MAS controller. Typical rf fields of 1H and 13C pulses

were 100 and 93 kHz, respectively. 1H heteronuclear dipolar decoupling was achieved by TPPM[1] at

rf fields of 100 kHz. Repetition time was 2 seconds. The number of scans was 20000. Non- and Proton

attached 13C signals were differentiated from the comparison of the spectra from CPMAS[2,3] and 1H

homonuclear dipolar decoupled cross polarization scheme LGCPMAS[4,5,6] (data not shown) at

contact time of 3 ms and 40 µs, respectively. Infrared (IR) spectra were recorded on a Shimadzu FTIR-

8400 spectrometer equipped with an attenuated total reflection (ATR) system. Size-exclusion

chromatography (SEC) analyses were carried out on GL Science GPC apparatus or a Viscotek

TDAmax using two columns (Shodex KF-804L) with tetrahydrofuran (THF) as an eluent. Molecular

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weights were calibrated against standard polystyrene samples. Mass spectra (MS) are taken with a

MALDI (matrix-assisted laser desorption/ionization) method on a Bruker Autoflex III mass

spectrometer. Differential scanning calorimetry (DSC) measurements of polymers were performed on a

Seiko DSC 7020 analyzer at a heating and cooling rate of 10 °C/min. Thermogravimetric (TG)

analyses were performed on a Seiko EXSTAR 6000 TG/DTA 6200 analyzer at a heating rate of

10 °C/min. X-ray diffraction (XRD) analyses were performed on a Rigaku MiniFlex II instrument.

Elemental analysis was performed by the Microanalytical Laboratory, Department of Chemistry,

Graduate School of Science, The University of Tokyo.

Materials: Anhydrous dichloromethane was purchased from Kanto Chemical Co. Inc (Kanto) and

purified by the method of Pangborn et al.[7] Carbon Monoxide was purchased from Takachiho

Chemical Industrial Co. and used as received. The following compounds were purchased from

commercial suppliers and used as received: 1,4-dihydro-1,4-epoxynaphthalene (1a) (Wako Pure

Chemical Industries, Ltd. (Wako)), silver hexafluoroantimonate (Tokyo Chemical Industry, Co., Ltd.

(TCI)), 1,2-bis(diphenylphophino)ethane (Kanto), 1,3-bis(diphenylphophino)propane (Kanto), 1,4-

bis(diphenylphophino)butane (Kanto), 2,2'-bipyridine (TCI), 1,10-phenanthroline (Sigma-Aldrich

Corporation), hydrogen chloride in 1,4-dioxane (Sigma-Aldrich), 1,2-dichloroethane (TCI), and dry

methanol (Wako). The following compounds were prepared according to literature procedures:

PdMeCl(cod) [ 8 ], Pd2(dba)3⋅CHCl3 [9 ], 2-{di(2-methoxyphenyl)phosphonio}benzene-sulfonate (4)

[10], palladium complex 5 [11], 6,7-difluoro-1,4-dihydro-1,4-epoxynaphthalene (1b) [12], and 1,4-

dihydro-6,7-dioctyl-1,4-epoxynaphthalene (1c) [13].

Preparation of 1,4-Dihydro-6,7-dioctyloxy-1,4-epoxynaphthalene (1d)

BuLi (1.6 M solution in hexane, 13.4 mL, 21.4 mmol) was slowly added at −50°C to a solution of 1,2-

dibromo-4,5-dioctyloxybenzene (10.4 g, 21.2 mmol) in anhydrous THF (200 mL) and furan (45 mL)

under argon atmosphere, and the solution was stirred for 2.5 h at –50 °C. After adding distillated water

(30 mL) at −50 °C, the mixture was warmed to room temperature. The reaction mixture was extracted

with diethyl ether, dried over Na2SO4, filtrated, and evaporated. Purification by flash chromatography

(20% ethyl acetate in hexanes) gave a white solid (5.04 g, 59.4%); Rf = 0.42 on silica gel (20% ethyl

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acetate in hexane); mp 66.8 ºC; IR (neat, cm−1) ν 2954, 2920, 2850, 1600 (C=C), 1461, 1292, 1207,

1076, 833, 702, 644. 1H NMR (400 MHz, CDCl3) δ 7.00 (t, J = 1.0 Hz, 2H, H(2) and H(3)), 6.92 (s, 2H,

H(5) and H(8)), 5.63 (t, J = 1.0 Hz, 2H, H(1) and H(4)), 3.92 (m, 4H, OCH2), 1.74–1.69 (m, 4H, CH2),

1.47–1.36 (m, 4H, CH2), 1.36–1.20 (m, 16H, CH2), 0.86 (t, J = 6.9 Hz, 6H, CH3); 13C NMR (101 MHz,

CDCl3) δ 146.2 (2C, C(6) and C(7)), 143.3 (2C, C(2) and C(3)), 141.9 (2C, C(9) and C(10)), 109.9 (2C,

C(5) and C(8)), 82.6 (2C, C(1) and C(4)), 70.3 (2C, OCH2), 31.9 (2C, CH2), 29.6 (2C, CH2), 29.5 (2C,

CH2), 29.4 (2C, CH2), 26.1 (2C, CH2), 22.8 (2C, CH2), 14.2 (2C, CH3); ESI–MS (m/z): [M+H]+ calcd

for C26H41O3, 401.30; found 401.28. C26H40O3: calcd. C 77.95, H 10.06; found C 77.78, H 10.28.

Copolymerization of [2.2.1]Oxabicyclic Alkenes 1 with Carbon Monoxide (Table 2): To a mixture

of palladium complex 5 (20.4 mg, 0.030 mmol) and silver hexafluoroantimonate (10.2 mg, 0.030

mmol) was added dichloromethane (9.0 mL) at room temperature. After stirring for 10 min at room

temperature, the resulting suspension was filtrated through a membrane filter (pore size: 0.25 µm) and

added to a solution of monomer 1 (3.0 mmol) in dichloromethane (9.0 mL) in a 50-mL stainless

autoclave. After charged with carbon monoxide (5.0 MPa), the resulting mixture was stirred for 24 h at

70 °C (100 °C only for entry 5). After cooling to room temperature, the mixture was added to methanol

(ca. 100 mL). The polymer was isolated by filtration, washed with methanol, and dried under vacuum

at 70 °C. The obtained copolymers 2 were analyzed by 1H and 13C NMR, SEC, DSC, TG analyses

without further purification.

Dehydration of Polymer 2: To a suspension of polymer 2 (600 mg) in 1,1,2,2-tetrachloroethane (3.0

mL) was added hydrogen chloride in 1,4-dioxane (4.0 M, 1.5 mL, 6.0 mmol) at room temperature. The

mixture was stirred for 24 h at 110 °C (for entry 1), 48 h at 80 °C (for entries 3 and 4), and 24 h at

80 °C (for entry 5). After cooling to room temperature, the suspension was evaporated and the residue

was washed with methanol using an ultrasound bath. The obtained polymers 3 were analyzed by 1H

and 13C NMR, SEC, DSC, and TG analyses.

Control Experiment: Polymerization of 1a in the Absence of Carbon Monoxide: To a mixture of

palladium complex 5 (6.9 mg, 0.010 mmol) and silver hexafluoroantimonate (3.4 mg, 0.010 mmol) was

added dichloromethane (3.0 mL) at room temperature. After stirring for 10 min at room temperature,

the resulting suspension was filtrated through a membrane filter (pore size 0.25 µm) and added to a

solution of monomer 1a (1.0 mmol) in dichloromethane (3.0 mL) in a 10-mL Schlenk tube. The

resulting mixture was stirred for 24 h at 70 °C. After cooling to room temperature, the mixture was

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analyzed by 1H NMR and GC analyses with internal standards. 1H NMR yields: 1a: 69%, 1-naphthol

(6a): 13%. GC analysis indicated no formation of oligo-1a, including dimer and trimer.

Elemental Analysis: Elemental analyses were performed for polymers 2c, 3c, 2d, and 3d obtained in

Table 2:

2c: calcd. C 81.77, H 10.17; found C 79.41, H 10.21.

3c: calcd. C 85.66, H 10.12; found C 84.04, H 10.70.

2d: calcd. C 75.66, H 9.41; found C 73.59, H 9.36.

3d: calcd. C 78.98, H 9.33; found C 78.04, H 9.95.

Although these values are outside the acceptable ranges, they are provided to illustrate the best values

obtained to date.

References

(1) Bennett, A. E.; Rienstra, C. M.; Auger, M.; Lakshmi, K. V.; Griffin, R. G. J. Chem. Phys. 1995, 103, 6951–6958.

(2) Hartmann, S. R.; Hahn, E. L. Phys. Rev. 1962, 128, 2042–2053. (3) Stejskal, E. O.; Shaefer, J.; Waugh, J. S. J. Magn. Reson. 1977, 28, 105–112. (4) Lee, M.; Goldburg, W. I. Phys. Rev. 1965, 140, A1261–A1271. (5) Hester, R. K.; Ackerman, J. L.; Cross, V. R.; Waugh, J. S. Phys. Rev. Lett. 1975, 34, 993–995. (6) van Rossum, B.-J.; de Groot, C. P.; Ladizhansky, V.; Vega, S.; de Groot, H. J. M. J. Am. Chem. Soc.

2000, 122, 3465–3472. (7) Pangborn, A. B.; Giardello, M. A.; Grubbs, R. H.; Rosen, R. K.; Timmers, F. J. Organometallics

1996, 15, 1518–1520. (8) Rülke, R. E.; Ernsting, J. M.; Spek, A. L.; Elsevier, C. J.; van Leeuwen, P. W. N. M.; Vrieze, K.

Inorg. Chem. 1993, 32, 5769–5778. (9) Ukai, T.; Kawazura, H.; Ishii, Y.; Bonnet, J. J.; Ibers, J. A. J. Organomet. Chem. 1974. 253–266. (10) Drent, E.; van Dijk, R.; van Ginkel, R.; van Oort, B.; Pugh, R. I. Chem. Commun. 2002, 964–965. (11) Kochi, T.; Yoshimura, K.; Nozaki, K. Dalton Trnas. 2006, 25–27. (12) Caster, K. C.; Keck, C. G.; Walls, R. D. J. Org. Chem. 2001, 66, 2932–2936. (13) Ito, S.; Takahashi, K.; Nozaki, K. 2014, 136, 7547–7550.

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Polymer 2a (entry 1 in Table 2)

500100015002000250030003500ν / cm–1

Figure S1. IR spectrum of polymer 2a.

Figure S2. 13C-CPMAS solid-state NMR spectrum of polymer 2a.

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Figure S3. DSC chart of polymer 2a.

Figure S4. TG chart of polymer 2a.

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Polymer 3a (entry 1 in Table 2)

500100015002000250030003500ν / cm–1

Figure S5. IR spectrum of polymer 3a.

Figure S6. 13C-CPMAS solid-state NMR spectrum of polymer 3a.

O

n

O

na

aaromatic, a

a

S8

Figure S7. DSC chart of polymer 3a.

Figure S8. TG chart of polymer 3a.

S9

Polymer 2b (entry 2 in Table 2)

Figure S9. SEC chart of polymer 2b.

500100015002000250030003500ν / cm–1

Figure S10. IR spectrum of polymer 2b (KBr).

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Figure S11. 1H NMR spectrum of polymer 2b (500 MHz, CD2Cl2).

Figure S12. 13C NMR spectrum of polymer 2b (101 MHz, CD2Cl2).

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Figure S13. DSC chart of polymer 2b.

Figure S14. TG chart of polymer 2b.

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Polymer 2c (entry 3 in Table 2)

Figure S15. SEC chart of polymer 2c.

500100015002000250030003500�

/ cm–1

Figure S16. IR spectrum of polymer 2c.

S13

Figure S17. 1H NMR spectrum of polymer 2c (500 MHz, CDCl3).

Figure S18. 13C NMR spectrum of polymer 2c (101 MHz, CDCl3).

solvent

ArCH2

C8H17

e cb

O

O

C8H17 C8H17

nO

C8H17 C8H17

O

n

e

b c b c

e

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2000 3000 4000 5000 6000 7000 8000m/z

Figure S19. MALDI-TOF-MS spectrum of polymer 2c.

O

O

C8H17 C8H17

nO

C8H17 C8H17

O

n

mass of repeating unit: 396.3

396 interval

S15

Figure S20. DSC chart of polymer 2c.

Figure S21. TG chart of polymer 2c.

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Polymer 3c (entry 3 in Table 2)

Figure S22. SEC chart of polymer 3c.

Figure S23. IR spectrum of polymer 3c.

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Figure S24. 1H NMR spectrum of polymer 3c (500 MHz, CDCl3).

Figure S25. 13C NMR spectrum of polymer 3c (101 MHz, CDCl3).

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1000 2000 3000 4000 5000 6000m/z

Figure S26. MALDI-TOF-MS spectrum of polymer 3c.

S19

Figure S27. DSC chart of polymer 3c.

Figure S28. TG chart of polymer 3c.

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Polymer 2d (entry 4 in Table 2)

Figure S29. SEC chart of polymer 2d.

500100015002000250030003500�

/ cm–1

Figure S30. IR spectrum of polymer 2d.

O

O

C8H17O OC8H17

nO

C8H17O OC8H17

O

n2922

2854

1470

1086

980835

667

1305

1214

17141591

S21

Figure S31. 1H NMR spectrum of polymer 2d (500 MHz, CDCl3).

Figure S32. 13C NMR spectrum of polymer 2d (101 MHz, CDCl3).

O

O

C8H17O OC8H17

nO

C8H17O OC8H17

O

na

a

de

f

b c b cd

ef

solvent OCH2C7H15

a

de

f

cb

OCH2C7H15

a

solvent

OCH2

OCH2C7H15

H2O TMS

e c b

O

O

C8H17O OC8H17

nO

C8H17O OC8H17

O

n

e

b c b c

e

S22

Figure S33. DSC chart of polymer 2d.

Figure S34. TG chart of polymer 2d.

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Polymer 3d (entry 4 in Table 2)

Figure S35. SEC chart of polymer 3d.

Figure S36. IR spectrum of polymer 3d.

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Figure S37. 1H NMR spectrum of polymer 3d (500 MHz, CDCl3).

Figure S38. 13C NMR spectrum of polymer 3d (101 MHz, CDCl3).

O

C8H17O OC8H17

n

C8H17O OC8H17

O

n

solvent OCH2C7H15

OCH2C7H15

otheraromaticsignals

f'

f' f'e' e'

e'

S25

Figure S39. DSC chart of polymer 3d.

Figure S40. TG chart of polymer 3d.

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Polymer 2e (entry 5 in Table 2)

Figure S41. IR spectrum of polymer 2e.

Figure S42. 13C-CPMAS solid-state NMR spectrum of polymer 2e.

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Figure S43. DSC chart of polymer 2e.

Figure S44. TG chart of polymer 2e.

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2000 3000 4000 5000 6000 7000 8000m/z

Figure S45. MALDI-TOF-MS spectrum of polymer 2e.

O

n

O

n

222 interval

mass of repeating unit: 222.1

O O

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Polymer 3e (entry 4 in Table 2)

Figure S46. IR spectrum of polymer 3e.

Figure S47. 13C-CPMAS solid-state NMR spectrum of polymer 3e.

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Figure S48. DSC chart of polymer 3e.

Figure S49. TG chart of polymer 3e.

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1000 2000 3000 4000m/z

Figure S50. MALDI-TOF-MS spectrum of polymer 3e.