Palladium porphyrin catalyzed hydrogenation of alkynes: Stereoselective synthesis of cis -alkenes

Article abstract of DOI:10.1055/s-0033-1341240

(Tetraphenylporphyrin)palladium was developed as a catalyst for the chemoselective and stereoselective hydrogenation of alkynes to cis-alkenes by the syn-addition of hydrogen. Alkynes containing various functional groups were tolerated in the reaction, which gave the corresponding cis-alkenes in good to excellent yields. Georg Thieme Verlag Stuttgart New York.

Full text of DOI:10.1055/s-0033-1341240

Accounts and
Rapid Communications in
Synthetic Organic Chemistry
SYNLETT
SUPPORTING INFORMATION
Supporting Information
for DOI: 10.1055/s-0033-1341240
© Georg Thieme Verlag KG Stuttgart · New York 2014
Thieme

Supporting Information for:
Palladium Porphyrin Catalyzed Hydrogenation of Alkynesꢀꢁ
6WHUHRVHOHFWLYHꢁ6\QWKHVLVꢁRIꢁFLVꢂ$ONHQHV
Ryo Nishibayashi, Takuya Kurahashi*, and Seijiro Matsubara*
Department of Material Chemistry, Graduate School of Engineering, Kyoto University,
Kyoto-daigaku Katsura, Nishikyo-ku, Kyoto 615-8510, Japan
Contents
Instrumentation and Chemicals
S2
S3
S8
S9
Experimental Procedure and Characterization Data for Products
References
Details of Gas Chromatography Conditions
1H NMR and 13C NMR Spectra of [Pd(TPP)]
S10
1H NMR and 13C NMR Spectra of Products
S12
S1

Instrumentation and Chemicals
Nuclear magnetic resonance spectra were taken on Varian UNITY INOVA 500 (1H, 500
MHz; 13C, 125.7 MHz) spectrometer using tetramethylsilane (1H) as an internal standard.
1H NMR data are reported as follows: chemical shift, multiplicity (s = singlet, d =
doublet, t = triplet, q = quartet, quint = quintet, sext = sextet, sept = septet, br = broad, m
= multiplet), coupling constants (Hz), integration, and identification. High-resolution
mass spectra was obtained with a Thermo Scientific Exactive spectrometer by chemical
ionization. Preparative recycling gel permeation chromatography (GPC) was performed
with JAI LC-908 equipped with JAIGEL-1H and -2H columns (toluene as an eluent).
Elemental analyses were carried out with a YANAKO MT2 CHN CORDER machine
at Kyoto University Elemental Analysis Center. Infrared spectra (IR) spectra were
determined on a SHIMADZU FTIR-8200PC spectrometer. In-situ IR spectra were
obtained with Mettler Toledo ReactIR 45M equipped with AgX Fiber (9.5 mm). Gas
chromatography spectra (GC) were determined on a SHIMADZU GC-2014. Melting
points were determined using a YANAKO MP-500D. TLC analyses were performed by
means of Merck Kieselgel 60 F254 (0.25 mm) Plates. Visualization was accomplished
with UV light (254 nm) and/or an aqueous alkaline KMnO4 solution followed by
heating. Flash column chromatography was carried out using Kanto Chemical silica gel
(spherical, 40–50 μm). Unless otherwise noted, commerciallyavailable reagents were
used without purification. Pd(OAc)2ꢀ and Dry solvent were purchased from Wako
Pure Chemical Co..ꢀmeso-Tetraphenylporphine were purchased from Strem chemicals.
S2
ꢀ

Experimental Procedure
Preparation of TPP.
To a solution of benzaldehyde (20 mmol, 2 mL) in propionic acid (74 mL) refluxed at
170 ꢁ under air were added drop wise pyrrole (20 mmol, 1.4 mL). After refluxed for
0.5 h, the reaction mixture washed MeOH (78 ml). The residue was recrystallized with
CHCl3 and MeOH to give TPP.
Preparation of [Pd(TPP)]
TPP (1.5 mmol 0.921 g) and Palladium(II) acetate (6.0 mmol 1.34 mg) was dissolve in
CHCl3 (123 mL) and refluxed at 90 ꢁ for 12 h under Ar in darkness. H2O was added
to the reaction mixture and aqueous phase was extracted with CHCl3. The combined
organic solution was washed with saturated aqueous NaCl solution, dried over
anhydrous MgSO4, concentrated in vacuo. The residue was purified by flash silica gel
column chromatography. The residue was recrystallized with CHCl3 and MeOH to give
[Pd(TPP)].
purple solid; 1H NMR (CDCl3) δ 8.82 (s, 8H), 8.18-8.17(m, 8H), 7.79-7.72(m, 12H); 13C
NMR (CDCl3) δ 141.70, 141.49, 134.07, 130.98, 127.73, 126.68, 127.1.
General procedure for the hydrogenation of alkynes.
The reaction was performed in a 20 mL reactor equipped with a Teflon-coated magnetic
stirrer bar. To the reactor added [Pd(TPP)](0.005 mmol , 3.6 mg), 4-DMAP (0.01 mmol,
1.2 mg) and pyridine (1 mL) was stirred at 25 ꢁ for 0.5 h under hydrogen (1 atm).
After stirred, the alkynes (0.5 mmol) was added with pyridine (4 mL). After stirred for
indicated time, H2O was added to the reaction mixture and aqueous phase was extracted
with ethyl acetate. The combined organic phase solution was dreid over anhydrous
Na2SO4, concentrated in vacuo. The residue was purified by flash silica gel column
chromatography.
Preparation of various Porphyrin.
To the reaction mixture of various aldehyde (10 mmol) in CH3Cl (1 L) under Ar were
added BF3ꢂEt2O (3.3 mmol, 0.414 mL) and dropwise pyrrol (10 mmol, 0.694 mL).After
stirring for 1h at room temperature, open air. To the reaction mixture were added DDQ
(7.5 mmol, 1.84 mg). The reaction mixture was concentrated in vacuo, washed with
MeOH.
S3
ꢀ

Characterization Data
ꢀꢀ
cis-Stilbene (2a).1 CAS registry Number: 645-49-8.
1
Yield: 98%, colorless oil. TLC: Rf = 0.40 (hexane). H NMR (CDCl3) δ
13
7.27–7.18 (m, 10H), 6.60 (s, 2H); C NMR (CDCl3) δ 137.2, 130.2,
128.8, 128.1, 127.1; IR (neat): 3024, 1600 cm-1; HRMS (APCI) found
180.0931, Calcd for C14H12: [M–H] (180.0934).
ꢀ
(Z)-4-Bromo-stilbene (2b).2 CAS registry Number: 4714-24-3.
1
Yield: 99%, colorless oil. TLC: Rf= 0.45 (hexane). H NMR
(CDCl3) δ 7.37 (d, J =8.5 Hz, 2H), 7.32-7.22 (m, 5H), 7.13(d, J =
8.5 Hz, 2H), 6.66 (d, J = 12.5 Hz, 1H), 6.53 (d, J = 12,5 Hz, 1H);
13C NMR (CDCl3) δ 136.2, 131.4, 131.1, 130.5, 129.0, 128.8, 128.3,
127.3, 120.1; IR (neat): 3022, 1484, 1010, 697 cm-1; HRMS
(APCI) found 258.0034, Calcd for C14H11Br: [M–H] (258.0039).
(Z)-4-Formylstilbene (2c).3 CAS registry Number: 71093-80-6.
Yield: 99%, white solid. Mp. 116 °C (hexane/ethyl acetate).
1
TLC: Rf = 0.35 (hexane/ethyl acetate = 10/1). H NMR (CDCl3)
δ 10.0(s, 1H), 7.88-7.86 (m, 2H), 7.67-7.65 (m, 2H), 7.41-7.38
(m, 2H), 7.33-7.30 (m, 1H), 7.27 (d, J = 16.5 Hz, 1H), 7.15 (d, J
=16.5 Hz, 1H) ; 13C NMR (CDCl3) δ 191.5, 143.5, 136.3, 135.4,
132.3, 130.2, 128.8, 128.5, 127.4, 126.9, ; IR (KBr): 3028, 1701,
1599 cm-1; HRMS (APCI) found 209.0960, Calcd for C15H12O: [M–H] (209.0961).
ꢀ
Ethyl (Z)-cinnamate (2d).6 CAS registry Number: 4610-69-9.
1
Yield: 99%, red oil. TLC: Rf= 0.50 (hexane/ethyl acetate = 10/1). H
NMR (CDCl3) δ 7.59-7.57 (m, 2H), 7.37-7.325 (m, 3H), 6.96 (d, J =
12.5 Hz, 1H), 5.95 (d, J = 12.5 Hz, 1H), 4.17 (q, J = 7.2 Hz, 2H), 1.25
13
(t, J = 7.0 Hz, 3H); C NMR (CDCl3) δ 166.2, 143.1, 129.6, 129.0,
1278.0, 119.8, 60.3, 14.1; IR (neat): 2982, 1702, 1630, 1180 cm-1;
HRMS (APCI) found 177.0970, Calcd for C11H12O2: [M–H]
(177.0910).
ꢀ
ꢀ
ꢀ
ꢀ
S4
ꢀ

(Z)-1-Cyclopropyl-2-phenyl ethylene (2e).5 CAS registry Number: 16958-34-2.
1
Yield: 82%, colorless oil. TLC: Rf = 0.50 (hexane). H NMR (CDCl3) δ
7.43 (d, J = 7 Hz; 2H), 7.34 (t, 2H), 7.22 (t, 1H), 6.35 (d, J = 11.5 Hz,
1H), 5.06 (dd, J = 11.5, 10 Hz, 1H), 1.94-1.87 (m, 1H), 0.85-0.81 (m,
13
2H), 0.49-0.46 (m, 2H); C NMR (CDCl3) δ 137.9, 136.8, 128.6, 128.1,
127.2, 126.3, 11,1, 8.0; IR (neat): 3382, 2363, 1632 cm-1; HRMS (APCI)
found 145.1010, Calcd for C11H12: [M–H] (145.1012).
(Z)-Hept-1-en-1-ylbenzene (2f).4 CAS registry Number: 1021-59-9.
1
Yield: 85%, colorless oil. TLC: Rf = 0.63 (hexane). H NMR (CDCl3) δ
7.35-7.32 (m, 2H), 7.29-7.27 (m, 2H), 7.24-7.21 (m, 1H), 6.41 (d, J =
12.0 Hz; 1H), 5.67 (dt, J = 12.0, 7.0 Hz, 1H), 2.33 (dt, J = 8.0, 7.5 Hz,
1H), 2.32(dt, J = 8.0, 7.5 Hz, 1H), 1.46-1.44 (m, 2H), 1.32-1.29(m, 4H),
0.88 (t, J = 7.0 Hz, 3H); 13C NMR (CDCl3) δ 137.7, 133.3, 1278.7, 128.5,
128.0, 126.4, 31.6, 29.7, 28.6, 22.6, 14.1; IR (neat): 3000, 2957, 2926,
1600 cm-1; HRMS (APCI) found 175.1480, Calcd for C13H18: [M–H] (175.1481).
ꢀ
Tetradec-7-ene (2g).7 CAS registry Number: 41446-63-3.
Yield: 89%, colorless oil. TLC: Rf = 0.68 (hexane). 1H NMR (CDCl3) δ 5.35
Hex
Hex
(dq, J = 4.5, 1.0 Hz, 2H), 2.02 (dt, J = 12.5, 5.5 Hz, 4H), 1.35-1.26 (m, 16H),
13
0.89 (t, J = 6.8 Hz, 6H); C NMR (CDCl3) δ 129.9, 31.8, 29.8, 29.0, 27.2, 22.7, 14.1;
IR (neat): 2925, 2360, 1465 cm-1; EI (CR) found 169, Calcd for C14H18: [M–H]
(196.2191).
ꢀ
(Z)-3-Octenyl acetate (2h).
Yield: 99%, red oil. TLC: Rf = 0.48 (hexane/ethyl acetate = 10/1).
1H NMR (CDCl3) δ 5.51 (ddd, J = 18.0, 7.5, 1.5 Hz; 1H), 5.35 (dd,
J = 18.0, 7.0, 1.5 Hz, 1H), 4.06 (t, J = 7.0 Hz, 2H), 2.38 (ddt, J =
14.0, 7.0, 0.8 Hz, 1H), 2.05 (s, 3H), 2.02 (dt, J = 7.5 ,0.8, 2H), 1.37
13
(tq, J = 7.3, 7.3 Hz, 2H), 0.90 (t, J = 15.0 Hz, 3H); C NMR (CDCl3) δ 132.8, 124.4,
64.0, 29.3, 26.8, 22.7, 21.0, 13.8; IR (neat): 2960, 2360, 1743, 1037 cm-1; HRMS
(APCI) found 157.1221, Calcd for C9H16O2: [M–H] (157.1223).
ꢀ
(Z)-Oct-3-en-1-ol (2i).8 CAS registry Number: 18185-81-4.
Yield: 99%, black oil. TLC: Rf = 0.13 (hexane/ethyl acetate = 10/1).
1H NMR (CDCl3) δ 5.56 (ddd, J = 18.5, 7.5, 1.5 Hz, 1H), 5.35 (ddd,
S5
ꢀ

J = 18.5, 7.5, 1.5 Hz, 1H), 3.64 (t, J = 6.5 Hz, 2H), 2.33 (ddt, J = 14, 6.5, 0.8 Hz, 2H),
13
2.08-2.04 (m, 2H), 1.63 (br, 1H), 1.33-1.30(m, 4H), 0.89 (t, J = 7.0 Hz, 3H); C NMR
(CDCl3) δ 133.6, 124.9, 62.3, 31.8, 30.7, 27.0, 22.3, 14.0; IR (neat): 3351, , 2957, 2360
cm-1; HRMS (APCI) found 129.1274, Calcd for C8H16O: [M–H] (129.1274).
ꢀ
(Z)-Oct-3-enyl-4-methylbenzenesulfonate(2j).9 CAS registry Number: 111789-39-0.
Yield: 81%, red oil. TLC: Rf = 0.43 (hexane/ethyl acetate = 10/1).
1H NMR (CDCl3) δ 7.80-7.78 (m, 2H), 7.35-7.33 (m, 2H), 5.48
(ddd, J = 18.0, 7.5, 1.5 Hz, 1H), 5.23 (ddd, J = 18.0, 7.0, 2.0 Hz,
1H), 4.01 (t, J = 7.0 Hz, 2H), 2.45 (s,3H), 2.40 (ddt, J = 14, 7.0, 0.8
Hz, 2H), 1.94 (q, J = 7.8 Hz, 2H), 1.34 (tq, J = 7.5, 7.5 Hz, 2H), 0.87 (t, J = 14.5 Hz,
13
3H); C NMR (CDCl3) δ 144.6, 133.7, 133.5, 129.8, 127.9, 122.9, 109.8, 69.8, 29.3,
27.2, 22.6, 21.6, 13.7; IR (neat): 2959, 2872, 2361, 1599, 1361, 1176 cm-1; HRMS
(APCI) found 300.1623, Calcd for C15H22O3S: [M–H] (300.1628).
(Z)-5-Decenal (2k).10 CAS registry Number: 21662-08-8.
Yield: 83%, colorless oil. TLC: Rf = 0.30 (hexane/ethyl acetate =
1
10/1). H NMR (CDCl3) δ 9.77 (s, 1H), 5.42 (ddd, J = 18.5, 7.5,
1.0 Hz, 1H), 5.31 (ddd, J = 18.5, 7.5, 1.5 Hz, 1H), 2.44 (dt, J =
7.5, 2.0 Hz, 2H), 2.08 (dt, J = 7.3, 7.0 Hz, 2H), 2.02-1.98 (m,
2H), 1.69 (tt, J = 7.5, 7.5 Hz, 2H), 1.33-1.30 (m, 4H), 0.89 (t, J = 7.3 Hz, 3H); 13C NMR
(CDCl3) δ 131.3, 128.2, 43.3, 31.8, 26.9, 26.4, 26.4, 22.3, 22.0, 14.0; IR (neat): 2930,
1728, 1457 cm-1; HRMS (APCI) found155.1428, Calcd for C10H18O: [M–H] (155.1430).
ꢀ
(Z)-1(Benzyloxy)-3-octene (2l).
Yield: 99%, red oil. TLC: Rf = 0.55 (hexane/ethyl acetate = 10/1).
1H NMR (CDCl3) δ 7.35-7,33 (m, 4H), 7.29-7.28 (m, 1H), 5.47
(ddd, J = 17.5, 7.0, 1.0 Hz, 1H), 5.39 (ddd, J = 17.5, 7.5, 1.0 Hz,
1H), 4.52 (s, 2H), 3.48 (t, J = 7.0 Hz, 2H), 2.37 (ddt, J = 13.5, 7.0,
13
0.5 Hz, 2H), 2.07-2.03 (m, 2H), 1.35-1.30 (m, 4H), 0.90 (t, J = 7.0 Hz, 3H); C NMR
(CDCl3) δ 132.0, 128.3, 127.6, 127.5, 125.4, 72.9, 70.1, 31.8, 28.0, 27.1, 22.3, 13.9; IR
(neat): 3329, 2928, 2360, 1454, 1101 cm-1; HRMS (APCI) found 219.1740, Calcd for
C15H22O: [M–H] (219.1743).
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S6
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Benzyl (Z)-oct-3-enyl carbonate (2m). CAS registry Number:
Yield: 93%, red oil. TLC: Rf = 0.51 (hexane/ethyl acetate = 10/1).
1H NMR (CDCl3) δ 7.40-7.33 (m, 4H), 5.51 (ddd, J = 18.5, 7.0,
1.5 Hz, 1H), 5.34 (ddd, J = 18.5, 7.0, 1.5 Hz, 1H), 5,16 (s, 2H),
4.14 (t, J = 7.0 Hz, 2H), 2,43 (ddt, J = 14, 7.0, 1.0 Hz, 2H),
13
2.06–2.01 (m, 2H), 1.34-1.30 (m, 4H), 0.89 (t, J = 7.0 Hz, 3H) ; C NMR (CDCl3) δ
133.4, 128.6, 128.5, 128.3, 123.6, 109.8, 66.5, 67.6, 31.7, 27.0, 26.9, 22.3, 13.9; IR
(neat): 2957, 2360, 1746, 1457, 1260 cm-1; HRMS (APCI) found 236.1638, Calcd for
C16H22O3: [M–H] (263.1642).
ꢀ
(Z)-4-Nitrostilbene (2n).1 CAS registry Number:
Yield: 88%, orange solid. Mp. 57 °C (hexane/ethyl acetate).
1
TLC: Rf = 0.40 (hexane/ethyl acetate = 20/1). H NMR (CDCl3)
δ 8.09-8.07 (m, 2H), 7.39–7.36 (m, 2H), 7.27-7.26 (m, 2H),
7.25-7.20 (m, 2H) 6.82 (d, J = 12.5 Hz, 1H), 6.62 (d, J = 12.5 Hz,
1H); 13C NMR (CDCl3) δ 146.4, 144.1, 133.9, 129.6, 128.8,
128.5, 128.0, 127.9, 123.5,; IR (KBr): 3023, 1593, 1510, 1346,
1106 cm-1; HRMS (APCI) found 226.0860, Calcd for C14H11NO2: [M–H] (226.0863).
S7
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References
(1) Zhang, J.; Hao, J.; Wei, Y.; Xiao, F.; Yin, P.; Wang, L. Journal of the American
Chemical Society, 2010, 132, 5018.
(2) Ilies, L.; Yoshida, T.; Nakamura, E. Journal of the American Chemical Society,
2012 , 134, 16951.
(3) Xu, H.-J.; Zhao, Y.-Q.; Zhou, X.-F.; Journal of Organic Chemistry, 2011, 76, 8036.
(4) Denmark, S. E.; Wehrli, D. Organic Letters, 2000 , 2, 565.
(5) Wang, S. C.; Troast, D. M.; Conda-Sheridan, M.; Zuo, G.; LaGarde, D.; Louie, J.;
Tantillo, D. J. Journal of Organic Chemistry, 2009 , 74, 7822.
(6) Broggi, J.; Jurcik, V.; Songis, O.; Poater, A.; Cavallo, L.; Slawin, A. M. Z.; Cazin, C.
S. J. Journal of the American Chemical Society, 2013 , 135, 4588.
(7) Keitz, B. K.; Endo, K.; Herbert, M. B.; Grubbs, R. H. Journal of the American
Chemical Society, 2011, 133, 9686.
(8) Bable, J. H.; White, N. A.; Kowalski, E.; Jast, J. R. Tetrahedron Letters, 2011, 52,
745.
(9) Madelaine, C.; Ouhamou, N.; Chiaroni, A.; Vedrenne, E.; Grimaud, L.; Six, Y.
Tetrahedron, 2008, 64, 8878.
(10) Alexander, M. M.; Boris, A. C.; Natalya, M. I.; Oleg, M. N. J. Chem. Soc., Perkin
Trans. 1, 1991, 2639.
S8
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Details of Gas Chromatography Conditions
Conversion of 1a and yields of 2a, 3a, and 4a were determined on gas chromatography
spectra SHIMADZU GC-2014 using following conditions and decane as an internal
standard.
Column: GL Sciences INERTCAP 5MS/SIL 0.25um x 0.25 mm x 30 m
Rate (°C / min)
Temperature (°C)
Retention time (min)
—
2.5
70 (initial)
83
2
0
0
0
2
2
100
0.01
2.5
136
136
136
100
300 (final)
Substance
Retention time (min)
1a
2a
25.9
17.3
30.0
17.1
5.7
3a
4a
decane
S9
ꢀ

1H NMR and 13C NMR Spectra of [Pd(TPP)]
S10
ꢀ

S11
ꢀ

1H NMR and 13C NMR Spectra of Products.
2a
S12
ꢀ

2a
S13
ꢀ

Br
2b
S14
ꢀ

Br
2b
S15
ꢀ

CHO
2c
S16
ꢀ

CHO
2c
S17
ꢀ

Pen
2d
S18
ꢀ

Pen
2d
S19
ꢀ

2e
S20
ꢀ

2e
S21
ꢀ

CO2Et
2f
S22
ꢀ

CO2Et
2f
S23
ꢀ

Hex
Hex
2g
S24
ꢀ

Hex
Hex
2g
S25
ꢀ

OAc
Pr
2h
S26
ꢀ

OAc
Pr
2h
S27
ꢀ

OH
Bu
2i
S28
ꢀ

OH
Bu
2i
S29
ꢀ