Supporting Information

Unique Synthetic Approach toward a Phosphaalkene: Synthesisof a Selenium-substituted Phosphaalkene with Bulky Substituents

Koh Sugamata, Takahiro Sasamori,* and Norihiro Tokitoh*

Institute for Chemical Research, Kyoto University, Gokasho Uji, Kyoto 611-0011

(Received September 18, 2013; CL-130862; E-mail: sasamori@boc.kuicr.kyoto-u.ac.jp)

Copyright © The Chemical Society of Japan

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Supporting Information

Experimental Procedures

General Procedures

All experiments were performed under an argon atmosphere unless otherwise noted. Solvents used for the

reactions were purified by an Ultimate Solvent System (Glass Contour Company).S1 The 1H and 13C NMR

spectra were measured in C6D6 or CD2Cl2 with a JEOL JNM AL-300 spectrometer or a Bruker

Avance-600 spectrometer. Signals due to C6D5H (7.15 ppm) and CHDCl2 (5.32 ppm) in 1H NMR spectra

and those due to C6D6 (128 ppm) and in 13C NMR spectra were used as internal references. The 31P NMR

spectra were measured in C6D6 or CD2Cl2 with a JEOL AL-300 spectrometer or a Bruker Avance-600

spectrometer using 85% H3PO4 in water (0 ppm) as an external standard. The 77Se NMR spectra were

measured in C6D6 with a JEOL AL-300 spectrometer using Ph2Se2 (460 ppm) as an external standard. All

melting points were determined on a Yanaco micro melting point apparatus and are uncorrected.

Elemental analyses were carried out at the Microanalytical Laboratory of the Institute for Chemical

Research, Kyoto University. 9-Tryptycylselenol (TrpSeH),S2 tris(trimethylsilyl)methyldichlorophosphine

(TsiPCl2),S3 bis(trimethylsilyl)methyldichlorophosphine (DisPCl2),S4 and chlorophosphaalkene 3

((Me3Si)2C=PCl)S5 were prepared according to the reported procedures.

Synthesis of TrpSeP(Cl)Dis (2): To a THF solution (2 mL) of TrpSeH (238 mg, 0.714 mmol) was added

n-BuLi (1.58 M hexane solution, 542 µL, 0.857 mmol) under vigorous stirring at 0 ºC. The mixture was

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stirred for 1 h at room temperature. The resulting white suspension was slowly added to the solution of

DisPCl2 (189 mg, 0.567 mmol) in THF (10 mL) at 0 ºC, and then it was stirred for 1 h at room

temperature. The reaction mixture was washed by saturated NH4Cl aq. and extracted with CH2Cl2 (10

mL). The organic layer was dried with MgSO4. After filtration, removal of the solvents under vacuum

to give TrpSeP(Cl)Dsi as colorless solid (2, 177 mg, 0.369 mmol, 52%). 2: colorless crystals, mp > 300

ºC, 1H NMR (300 MHz, C6D6) δ 0.116 (brs, 9H), 0.53 (s, 9H), 1.50 (s, 1H), 5.17 (s, 1H), 6.80-7.00 (m,

6H), 7.10-7.20 (m, 3H), 7.50-7.90 (m, 3H); 13C{1H} NMR (75 MHz, C6D6) δ 0.91 (d, 3JPC = 8.2 Hz), 3.60

(d, 3JPC = 1.5 Hz), 26.8 (d, 1JPC = 72.6 Hz), 54.8, 66.0 (d, 2JP-C = 16.2 Hz), 123.8, 125.3, 125.4, 126.1,

145.9, 146.0; 31P NMR (121 MHz, C6D6) δ 187 (satellite, 1JSeP = 320 Hz); 77Se{1H} NMR (57 MHz,

C6D6) δ 355 (d, 1JPSe = 320 Hz). Anal. Calcd for C, 58.11; H, 5.78; found: C, 59.27; H, 5.89; HRMS

(DART) Found: m/z 558.0631 ([M]+). Calcd for C27H3135ClP77SeSi2 558.0633 ([M]+)

Synthesis of TrpSeP(Cl)Tsi (4): To a THF solution (10 mL) of TrpSeH (189 mg, 0.567 mmol) was

added n-BuLi (1.58 M hexane solution, 0.395 mL, 0.624 mmol) under vigorous stirring at 0 ºC. The

mixture was stirred for 1 h at room temperature. The resulting white suspension was slowly added to the

solution of TsiPCl2 (189 mg, 0.567 mmol) in THF (10 mL) at 0 ºC, and then it was stirred for 1 h at room

temperature. The reaction mixture was washed by saturated NH4Cl aq. and extracted with CH2Cl2 (10

mL). The organic layer was dried with MgSO4. After filtration, removal of the solvents under vacuum

to give TrpSeP(Cl)Tsi as colorless solid (4, 287 mg, 0.455 mmol, 80%). 4: colorless crystals, mp >300 ºC, 1H NMR (300 MHz, C6D6) δ 0.56 (s, 27H), 5.14 (s, 1H), 6.80-6.95 (m, 6H), 7.10-7.15 (m, 3H), 8.30-8.33

(m, 3H); 13C{1H} NMR (75 MHz, C6D6) δ 5.73 (d, 3JPC = 5.1 Hz), 23.1 (d, 1JPC = 97.3 Hz), 54.9, 65.9 (d, 2JPC = 4.9 Hz), 123.4, 124.9, 125.9 (d, 3JPC = 11.0 Hz), 126.0, 145.7, 146.3, 31P NMR (243 MHz, C6D6) δ

198 (satellite, 1JSeP = 320 Hz); 77Se{1H} NMR (57 MHz, C6D6) δ 341 (d, 1JSeP = 320 Hz). Anal. Calcd for

C, 57.17; H, 6.40; found: C, 58.13; H, 6.61; HRMS (EI) Found: m/z 630.1028 ([M]+). Calcd for

C30H4035ClP77SeSi3 630.1029 ([M]+)

Synthesis of TrpSeP=C(SiMe3)2 (1): (a) To a mixture of compound 4 (31.5 mg, 50.0 µmol) and 0.5 eq.

of AlCl3 (3.3 mg, 25.0 µmol) in a 5φ NMR tube was added CH2Cl2 (0.7 mL), and then the tube was

degassed and sealed. The mixture was warm up to room temperature and then stirred for 1 h. The all

volatiles were removed under pressure. The residues were filtered with hexane. The solvent of the filtrate

was removed in vacuo to give 1 (24.1 mg, 46.2 µmol, 92%) as colorless powder. (b) n-BuLi (1.58 M in

hexane, 140 µL, 0.22 mmol) was added to the solution of TripSeH (66.7 mg, 0.20 mmol) in THF (3 mL)

at room temperature. After stirring for 2 h, the reaction mixture was slowly added to the solution of

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chlorophosphaalkene 3 in THF (1 mL) at 0 ºC, and then it was stirred for 1 h at this temperature. The

solvent was removed in vacuo. Insoluble inorganic salts were removed by filtration through Celite®.

After the solvent was removed, recrystallization of the residue from hexane to afford 1 (57.2 mg, 0.11

mmol, 55%) as colorless crystals. 1: colorless crystals, mp 222.8 – 223.8 ºC. 1H NMR (600 MHz, C6D6) δ

0.13 (d, 2JPH = 1.8 Hz, 9H), 0.67 (s, 9H), 5.16 (s, 1H), 6.75-6.85 (m, 6H), 7.10-7.20 (m 3H), 7.90- 8.00 (m,

3H); 13C{1H} NMR (151 MHz, C6D6) δ 1.67 (d, 3JPC = 14.3 Hz), 1.85 (d, 3JPC = 1.6 Hz), 54.7, 63.3 (d, 2JPC

= 8.1 Hz), 123.7, 125.2, 125.5 (d, 3JPC = 5.0 Hz), 126.0, 145.9, 146.0, 190.7 (1JPC = 93.8 Hz), 31P NMR

(243 MHz, C6D6) δ 378 (satellite, 1JSeP = 300 Hz); 77Se{1H} NMR (57 MHz, C6D6) δ 398 (d, 1JPSe =

300Hz). Anal. Calcd for C, 62.19; H, 5.99; found: C, 62.61; H, 6.09; HRMS (DART) Found: m/z

523.0941 ([M+H]+). Calcd for C27H32P77SeSi2 523.0966 ([M+H]+)

X-Ray crystallographic analysis of 1, 2, and 4

Single crystals of 1, 2, and 4 were grown by slow recrystallization of their toluene (1), CHCl3/benzene (2),

and hexane (4) solutions at room temperature, respectively. The intensity data were collected on a Rigaku

Saturn 70 CCD diffractometer with a VariMax Mo Optic using Mo Kα radiation(λ = 0.71075 Å). The

reflection data were integrated, scaled, ad averaged by using the HKL-2000 program package.S6 The

structures were solved by a direct method (SIR2004)S7 and refined by full-matrix least square method on

F2 for all reflections (SHELXL-97).S8 All hydrogen atoms were placed using AFIX instructions, while the

other atoms were refined anisotropically. In the analysis of compound 2, it was found to contain benzene

and CHCl3 molecules in the unit cell in 8:2 ratio, which were solved as disordered molecules. In the

analysis of compound 4, Se and Cl moieties were disordered in 91:9 ratio. Data of 1 (C27H31PSeSi2): M =

521.63, T = –160 ºC, triclinic, P–1 (no.2), a = 9.3762(2) Å, b = 16.3881(6) Å, c = 17.0058(5) Å, α =

90.102(3)º, β = 93.9826(12)º, γ = 89.937(2)º, V = 2606.76(13) Å3, Z = 4, Dcalc = 1.329 g cm–3, µ = 1.607

mm–1, 2θmax = 52.0º, measured/independent reflections = 32059/10198 (Rint = 0.0599), 571 refined

parameters, GOF = 1.021, R1 = 0.0482 [I>2s(I)], wR2 = 0.1229 [for all data], largest diff. peak and hole

1.621 and -0.899 e.Å–3; 2 (C27H32ClPSeSi2,0.8(C6H6),0.2(CHCl3)): M = 644.45, T = –170 ºC, monoclinic,

P21/a (no.14), a = 8.7105(3) Å, b = 30.2167(9) Å, c = 12.0465(4) Å, β = 92.384(2)º, V = 3167.93(18) Å3,

Z = 4, Dcalc = 1.351 g cm–3, µ = 1.467 mm–1, 2θmax = 52.0º, measured/independent reflections =

33676/6153 (Rint = 0.0512), 373 refined parameters, GOF = 1.082, R1 = 0.0342 [I>2s(I)], wR2 = 0.1110

[for all data], largest diff. peak and hole 0.646 and -0.400 e.Å–3; 4 (C30H40ClPSeSi3): M = 630.27, T = –

170 ºC, orthorhombic, P212121 (no.19), a = 8.6038(3) Å, b = 18.6862(7) Å, c = 19.3474(7) Å, V =

3110.53(19) Å3, Z = 4, Dcalc = 1.346 g cm–3, µ = 1.479 mm–1, 2θmax = 51.0º, measured/independent

reflections = 26502/5771 (Rint = 0.0461), 354 refined parameters, GOF = 1.132, R1 = 0.0303 [I>2s(I)],

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wR2 = 0.643 [for all data], largest diff. peak and hole 0.353 and -0.334e.Å–3;CCDC-961394 (1), CCDC–

961395 (2), and CCDC–961396 (4) were contained the supplementary crystallographic data for this

paper. These data can be obtained free of charge from The Cambridge Crystallographic Data Centre via

www.ccdc.cam.ac.uk/data_request/cif.

Figure S1. Molecular structures of 1 with thermal ellipsoids plots at 50% probability.

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Figure S2. Molecular structure of 2 with thermal ellipsoids plots at 50% probability. Disordered benzene

and chloroform molecules were omitted for clarity.

Figure S3. Molecular structure of 4 with thermal ellipsoids plots at 50% probability. Only a major part

(91%) of the disordered moieties was shown here.

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