an all-purpose preparation of oxime carbonates and …benzaldehyde o-((benzyloxy)carbonyl) oxime -...
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Electronic Supplementary Information
An all-purpose preparation of oxime carbonates and resultant insightsinto the chemistry of alkoxycarbonyloxyl radicals.
Roy T. McBurney,* Andrew D. Harper, Alexandra M. Z. Slawin and John C. Walton.*
School of Chemistry, University of St. Andrews, EaStChem, St. Andrews,
Fife, KY16 9ST, UK.
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Table of Contents
General Experimental Section S3
Scheme S1. General one-pot procedure for the synthesis of oxime carbonates. S4
Scheme S2. General two-pot procedure for the synthesis of oxime carbonates. S4
Scheme S3. Chloroformate synthesis of oxime carbonates. S5
Synthesis and Experimental Section S6
Figure S1. The X-ray crystal structure of 5e. S18
Table S1. Crystal data and structure refinement for 5e. S18
Figure S2. The X-ray crystal structure of 9a. S19
Table S2. Crystal data and structure refinement for 9a. S19
UV Photolyses of Oxime Carbonates S20
EPR Spectroscopy S25
EPR spectra S26
Computational Methods S31
DFT Optimised Structures and Energies S31
References S40
1H and 13C NMR spectra of novel compounds S42
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General Experimental Section
All reagents and solvents were purchased from either Sigma Aldrich or Alfa Aesar and used
without further purification. Toluene and tetrahydrofuran were distilled over sodium and
dichloromethane was distilled over calcium hydride. Benzaldehyde oxime, acetophenone oxime, 4-
methoxyacetophenone oxime, and benzophenone oxime were prepared according to the literature
procedure,1 as was 4-(1H-indol-3-yl)butan-2-one.2 1-Phenylpent-4-en-1-ol was prepared in an
analogous fashion to the method reported by Studer;3 1H NMR and 13C NMR spectra were
consistent with literature values.4 Column chromatography was carried out using Silica 60A
(particle size 40-63 µm, Silicycle, Canada) as the stationary phase, and TLC was performed on
precoated silica gel plates (0.20 mm thick, Sil G UV254, Macherey-Nagel, Germany) and observed
under UV light. 1H and 13C NMR spectra were recorded on Bruker AV III 500, Bruker AV II 400
and Bruker AV 300 instruments. Chemical shifts are reported in parts per million (ppm) from low
to high frequency and referenced to the residual solvent resonance. Coupling constants (J) are
reported in hertz (Hz). Standard abbreviations indicating multiplicity were used as follows: s =
singlet, d = doublet, t = triplet, dd = double doublet, q = quartet, m = multiplet, b = broad. Melting
points (M.p.) were determined using a Sanyo Gallenkamp apparatus and are reported uncorrected.
Mass spectrometry was carried out at the EPSRC National Mass Spectrometry Service Centre,
Swansea, UK.
One-Pot CDI Oxime Carbonate General Procedure5
1,1-Carbonyldiimidazole (CDI) (1.0 equiv) was dissolved in THF (20 cm3) at 0 °C, alcohol (1
equiv.) in THF (10 cm3) was added dropwise and the solution stirred at 0 °C for 1 h then allowed to
warm to rt for another hour. In a second flask oxime (1 equiv.) was dissolved in THF (20 cm3) at 0
°C and sodium hydride was added (0.3 equiv.), the suspension was stirred for 5 min. The imidazole
intermediate mixture was then added slowly to the oxime/sodium hydride flask and stirred at 0 °C
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for 30 min before being allowed to warm to rt for a further 2 h. The solvent was removed under
reduced pressure and the crude residue was redissolved in EtOAc (100 cm3) and washed with
NH4Cl (3 × 100 cm3), dried over MgSO4, filtered and purified by column chromatography
(CH2Cl2/Pet Ether 40:60 (1:1) as eluent).
Scheme S1. General one-pot procedure for the synthesis of oxime carbonates. Reagents and conditions: i) R1OH, CDI,
THF, O °C to rt, 2 h; oxime, NaH, THF, O °C to rt, 2 h.
Two-Pot CDI Oxime Carbonate General Procedure6
To a 0 °C solution of 1,1-carbonyldimiidazole (3 equiv.) in THF (30 cm3) was added alcohol (1
equiv.). The reaction was stirred and allowed to warm to rt over 2 h. The solvent was removed
under reduced pressure and the crude residue was re-dissolved in EtOAc (100 cm3) and washed
with NH4Cl (3 × 100 cm3), dried over MgSO4, filtered and concentrated under reduced pressure. To
a solution of oxime (1.5 equiv.) in THF (20 cm3) at 0 °C, pre-treated with sodium hydride (0.3
equiv.), was added a THF solution (10 cm3) of the imidiazole intermediate. The reaction mixture
was stirred at 0 °C for 30 min and allowed to warm to rt and stirred for 18 h. The solvent was
removed under reduced pressure and the crude residue was re-dissolved in EtOAc (100 cm3) and
washed with NH4Cl (3 × 100 cm3), dried over MgSO4, filtered and purified by column
chromatography (CH2Cl2/Pet Ether 40:60 (1:1) as eluent). (For the cases where the imidazole
carboxylate intermediate was characterised, its spectral data immediately follows the
characterisation data for the resultant oxime carbonate.)
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Scheme S2. General two-pot procedure for the synthesis of oxime carbonates. Reagents and conditions: i) R1OH, CDI,
THF, O °C to rt, 2 h; ii) oxime, NaH, THF, O °C to rt, 18 h.
Chloroformate Synthesis of Oxime Carbonates General Procedure
To a stirred 0 °C solution of oxime (1.0 equiv.) and pyridine (1.0 equiv.) in CH2Cl2 (25 cm3) was
added dropwise chloroformate (1.0 equiv.). The solution was allowed to warm to rt over 18 h. The
reaction mixture was diluted with CH2Cl2 (75 cm3) and washed with 1 M HCl (100 cm3), sat. aq.
NHCO3 (100 cm3) and brine (100 cm3). The organic layer was dried over MgSO4, filtered,
concentrated under reduced pressure and purified by column chromatography (gradient elution Pet
Ether 40:60 to CH2Cl2).
Scheme S3. Chloroformate synthesis of oxime carbonates. Reagents and conditions: i) R1OC(O)Cl, oxime, pyridine,
CH2Cl2, O °C to rt, 18 h.
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Synthesis and Experimental Section
Benzaldehyde O-phenoxycarbonyl oxime
Prepared from phenyl chloroformate (0.68 cm3, 5.42 mmol), benzaldehyde oxime (0.547 g, 4.52
mmol) and pyridine (0.44 cm3, 5.42 mmol) to give a colourless oil (0.255 g, yield = 22%). 1H NMR
(300 MHz, CDCl3, 299 K): = 7.26‒7.31 (m, 3H, HAr), 7.39‒7.54 (m, 5H, HAr), 7.77 (dd, J = 1.6
Hz, 7.9 Hz, 2H, Ha), 8.45 (s, 1H, Hb);13C NMR (75 MHz, CDCl3, 297 K): = 121.0, 126.3, 128.5,
129.0, 129.6, 129.6, 132.0, 150.9, 152.1, 156.5; LR-ESIMS: m/z = 242 [MH]+; HR-ESIMS: m/z =
242.0813 (calcd. for C14H12NO3, 242.0812).
Benzaldehyde O-((benzyloxy)carbonyl) oxime - 5a
Prepared from benzyl chloroformate (0.63 cm3, 4.42 mmol), benzaldehyde oxime (0.446 g, 3.69
mmol) and pyridine (0.35 cm3, 4.42 mmol) to give a colourless crystalline powder, 0.648 g, yield =
69%. M.p. = 58‒61 °C; 1H NMR (400 MHz, CDCl3, 297 K): = 5.31 (s, 2H, Ha), 7.34‒7.50 (m,
8H, HAr), 7.72 (d, J = 9.6 Hz, 2H, Hc), 8.34 (s, 1H, Hb);13C NMR (75 MHz, CDCl3, 297 K): =
70.7, 128.8, 129.1 (× 2), 129.2, 129.3, 130.2, 132.2, 135.2, 154.2, 156.3; LR-ESIMS: m/z = 256
[MH]+; HR-ESIMS: m/z = 256.0970 (calcd. for C15H14NO3, 256.0968).
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Acetophenone O-((benzyloxy)carbonyl) oxime - 5b
Chloroformate Route: Prepared from benzyl chloroformate (0.45 cm3, 3.16 mmol), acetophenone
oxime (0.355 g, 2.63 mmol) and pyridine (0.25 cm3, 3.16 mmol) to give a colourless crystalline
powder, 0.648 g, yield = 87%.
CDI One-Pot Route: Prepared from benzyl alcohol (0.50 cm3, 4.83 mmol), CDI (0.783 g, 4.83
mmol), acetophenone oxime (0.652 g, 4.83 mmol) and sodium hydride (0.035 g, 1.45 mmol) to give
a colourless crystalline powder, 0.597 g, yield = 46%.
CDI Two-Pot Route: Prepared from benzyl alcohol (0.50 cm3, 4.83 mmol), CDI (2.348 g, 14.5
mmol), acetophenone oxime (0.979 g, 7.25 mmol), sodium hydride (0.035 g, 1.44 mmol) to give a
colourless crystalline powder, 0.861 g, yield = 63%.
M.p. = 53‒56 °C; 1H NMR (400 MHz, CDCl3, 294 K): = 2.39 (s, 3H, Hb), 5.31 (s, 2H, Ha), 7.36‒
7.47 (m, 8H, HAr), 7.74 (d, J = 8.3 Hz, 2H, Hc);13C NMR (100 MHz, CDCl3, 295 K): = 14.4,
70.2, 127.0, 128.6, 128.7 (× 2), 128.8, 130.6, 134.6, 134.9, 153.9, 162.7; LR-ESIMS: m/z = 270
[MH]+; HR-ESIMS: m/z = 270.1126 (calcd. for C16H16NO3, 270.1125).
Benzyl 1H-imidazole-1-carboxylate - 4b: 1H NMR (400 MHz, CDCl3, 296 K): = 5.42 (s, 2H,
Hd), 7.06 (d, J = 1.0 Hz, 1H, Hg), 7.11 (d, J = 1.0 Hz, 1H, Hf), 7.40‒7.46 (m, 5H, Ha,b,c), 8.15 (s, 1H,
He);13C NMR (100 MHz, CDCl3, 297 K): = 69.9, 117.2, 128.8, 128.9, 129.2, 130.7, 134.0, 135.1,
137.2.
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Benzaldehyde O-((1-phenylethoxy)carbonyl) oxime - 5c
CDI Two-Pot Route: Prepared from 1-phenyl ethanol (0.25 cm3, 2.05 mmol), CDI (1.000 g, 6.17
mmol), benzaldehyde oxime (0.372 g, 3.07 mmol) and sodium hydride (0.015 g, 0.62 mmol) to give
a colourless solid, 0.294 g, yield = 51%. M.p. = 74‒76 °C; 1H NMR (500 MHz, CDCl3, 295 K): =
1.68 (d, J = 6.6 Hz, 3H, Ha), 5.90 (q, J = 6.6 Hz, 1H, Hb), 7.31‒7.49 (m, 8H, HAr), 7.71 (d, J = 7.0
Hz, 2H, Hd), 8.33 (s, 1H, Hc);13C NMR (100 MHz, CDCl3, 295 K): = 22.0, 126.3, 128.4 (× 2),
128.6 (× 2), 128.9, 129.9, 131.7, 140.4, 153.1, 155.7; LR-ESIMS: m/z = 287 [MNH4]+; HR-ESIMS:
m/z = 287.1392 (calcd. for C16H19N2O3, 287.1390).
1-phenylethyl 1H-imidazole-1-carboxylate - 4c: 1H NMR (400 MHz, CDCl3, 294 K): = 1.73 (d,
J = 6.6 Hz, 3H, Ha), 6.07 (q, J = 6.6 Hz, 1H, Hb), 7.06 (d, J = 1.0 Hz, 1H, He), 7.11 (d, J = 1.0 Hz,
1H, Hd), 7.33‒7.44 (m, 5H, HAr), 8.15 (s, 1H, Hc);13C NMR (100 MHz, CDCl3, 295 K): = 21.9,
117.2, 126.2, 128.8, 128.9, 130.6, 135.1, 137.1, 139.6, 148.0; LR-ESIMS: m/z = 217 [MH]+; HR-
ESIMS: m/z = 217.0973 (calcd. for C12H13N2O2, 217.0972).
Acetophenone O-((1-phenylethoxy)carbonyl) oxime - 5d
CDI Two-Pot Route: Prepared from 1-phenyl ethanol (0.25 cm3, 2.05 mmol), CDI (1.000 g, 6.17
mmol), acetophenone oxime (0.415 g, 3.07 mmol), sodium hydride (0.015 g, 0.62 mmol) to give a
colourless solid, 0.355 g, yield = 65%. M.p. = 45‒48 °C; 1H NMR (300 MHz, CDCl3, 296 K): =
1.69 (d, J = 6.6 Hz, 3H, Ha), 2.39 (s, 3H, Hc), 5.91 (q, J = 6.6 Hz, 1H, Hb), 7.30‒7.46 (m, 8H, HAr),
7.73 (dd, J = 6.6 Hz, 2H, Hd);13C NMR (75 MHz, CDCl3, 298 K): = 14.4, 22.0, 126.3, 126.4,
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127.0, 128.3, 128.6 (× 2), 130.6, 134.7, 140.6, 153.4, 162.4; LR-ESIMS: m/z = 284 [MH]+; HR-
ESIMS: m/z = 284.1212 (calcd. for C17H18NO3, 284.1281).
1-(4-Methoxyphenyl)ethanone O-benzyloxycarbonyl oxime - 5e
Prepared from benzyl chloroformate (0.62 cm3, 4.39 mmol), 4-methoxyacetophenone oxime (0.604
g, 3.66 mmol) and pyridine (0.35 cm3, 4.39 mmol) to give a colourless solid, 1.010 g, yield = 92%.
M.p. = 92 °C; 1H NMR (400 MHz, CDCl3, 296 K): = 2.35 (s, 3H, Hd), 3.84 (s, 3H, Ha), 5.30 (s,
2H, He), 6.91 (d, J = 8.9 Hz, 2H, Hb), 7.36‒7.47 (m, 5H, Hf,g,h), 7.71 (d, J = 8.9 Hz, 2H, Hc);13C
NMR (75 MHz, CDCl3, 298 K): = 14.5, 55.8, 70.5, 114.3, 127.2, 129.0, 129.1 (× 2), 129.1, 135.4,
154.4, 162.0, 162.5; LR-ESIMS: m/z = 300 [MH]+; HR-ESIMS: m/z = 300.1232 (calcd. for
C17H18NO4, 300.1230).
Benzophenone O-benzyloxycarbonyl oxime - 5f
Prepared from benzyl chloroformate (0.29 cm3, 2.01 mmol), benzophenone oxime (0.323 g, 1.67
mmol) and pyridine (0.16 cm3, 2.01 mmol) to give colourless solid, 0.518 g, yield = 94%. M.p. = 92
°C; 1H NMR (300 MHz, CDCl3, 297 K): = 5.25 (s, 2H, Ha), 7.31‒7.47 (m, 13H, HAr), 7.57 (d, J =
8.6 Hz, 2H, Hb);13C NMR (75 MHz, CDCl3, 298 K): = 70.6, 128.7, 128.8, 129.0, 129.1, 129.1,
129.4, 129.5, 130.2, 131.3, 132.5, 135.0, 135.3, 154.5, 164.9; LR-ESIMS: m/z = 354 [MNa]+; HR-
ESIMS: m/z = 354.1106 (calcd. for C21H17NO3Na, 354.1101).
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Acetophenone O-(((1-phenylpent-4-en-1-yl)oxy)carbonyl) oxime – 5g
CDI One-Pot Route: Prepared from 1-phenylpent-4-en-1-ol3,4 (0.533 g, 3.29 mmol), CDI (0.533 g,
3.29 mmol), acetophenone oxime (0.772 g, 3.29 mmol) and sodium hydride (0.024 g, 0.99 mmol) to
give a colourless oil, 0.578 g, yield = 54%. 1H NMR (300 MHz, CDCl3, 296 K): = 1.94‒2.02 (m,
1H, Hd), 2.10‒2.26 (m, 3H, Hd’,e), 2.39 (s, 3H, Hb), 4.99‒5.09 (m, 2H, Hg), 5.73‒5.90 (m, 2H, Hc,f),
7.24‒7.43 (m, 8H, HAr), 7.73 (dd, J = 1.4 Hz, 7.9 Hz, 2H, Ha);13C NMR (100 MHz, CDCl3, 298 K):
= 9.1, 24.4, 30.0, 75.1, 110.3, 121.6, 121.8, 123.2, 123.3 (×2), 125.3, 129.4, 132.0, 134.2, 148.2,
157.2; LR-ESIMS: m/z = 324 [MH]+; HR-ESIMS: m/z = 324.1593 (calcd. for C20H22NO3,
324.1594).
Acetophenone O-(biphenyl-2-ylmethoxy)carbonyl oxime - 5h
CDI One-Pot Route: Prepared from biphenylmethanol (0.184 g, 1.0 mmol), CDI (0.162 g, 1.0
mmol), acetophenone oxime (0.235 g, 1.0 mmol) and sodium hydride (0.007 g, 0.3 mmol) to give a
colourless solid, 0.251 g, yield = 73%. M.p. = 87 °C; 1H NMR (400 MHz, CDCl3, 296 K): = 2.39
(s, 3H, Hb), 5.25 (s, 2H, Hc), 7.34‒7.46 (m, 11 H, HAr), 7.62‒7.64 (m, 1H, Hd), 7.74 (dd, J = 1.3 Hz,
7.9 Hz, 2H, Ha);13C NMR (100 MHz, CDCl3, 297 K): = 14.4, 68.2, 127.0, 127.5, 127.7, 128.3,
128.6, 128.8, 129.3, 130.1, 130.3, 130.6, 132.3, 134.6, 140.2, 142.7, 153.8, 162.6; LR-ESIMS: m/z
= 368 [MNa]+; HR-ESIMS: m/z = 368.1258 (calcd. for C22H19NO3Na, 368.1257).
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4-(1H-Indol-3-yl)butan-2-ol
To a solution of 4-(1H-indol-3-yl)butan-2-one2 (1.007 g, 5.82 mmol, 1.0 equiv.) in THF (50 cm3)
and MeOH (0.1 cm3) was added sodium borohydride (0.885 g, 23.30 mmol, 4.0 equiv.), the
resulting suspension was stirred for 18 h. The solvent was removed under reduced pressure and the
crude residue redissolved in EtOAc (100 cm3), washed with 1M HCl (100 cm3), saturated aqueous
NaHCO3 (100 cm3) and brine (100 cm3), dried over MgSO4 and concentrated under reduced
pressure to give the title compound as a colourless oil, 1.057 g, yield = 96%, which was used
without further purification. The 1H NMR spectrum was consistent with that reported in the
literature.7 1H NMR (300 MHz, CDCl3, 297 K): = 1.26 (d, J = 6.3 Hz, 3H, Ha), 1.50‒1.56 (br, 1H,
Hb), 1.85‒1.92 (m, 2H, He), 2.79‒2.96 (m, 2H, Hd), 3.85‒3.96 (m 1H, Hc), 6.98 (d, J = 2.3 Hz, 1H,
Hf), 7.09‒7.23 (m, 2H, Hi,j), 7.35 (d, J = 7.9 Hz, 1H, Hk), 7.63 (d, J = 7.8 Hz, 1H, Hh), 7.96‒8.09
(br, 1H, Hg).
Acetophenone O-(((4-(1H-indol-3-yl)butan-2-yl)oxy)carbonyl) oxime – 5i
CDI One-Pot Route: Prepared from 4-(1H-indol-3-yl)butan-2-ol (1.019 g, 5.82 mmol), CDI (0.942
g, 5.82 mmol), acetophenone oxime (1.368 g, 5.82 mmol) and sodium hydride (0.042 g, 1.75 mmol)
to give a tan coloured oil, 1.440 g, yield = 74%. 1H NMR (400 MHz, CDCl3, 296 K): = 1.42 (d, J
= 6.2 Hz, 3H, He), 1.94‒2.06 (m, 1H, Hg), 2.12‒2.25 (m, 1H, Hg’), 2.43 (s, 3H, Hd), 2.80‒2.99 (m,
2H, Hh), 5.00‒5.10 (m, 1H, Hf), 7.00 (d, J = 2.3 Hz, 1H, Hi), 7.13 (td, J = 1.3 Hz, 7.0 Hz, 1H, Hml),
7.19 (td, J = 1.3 Hz, 7.0 Hz, 1H, Hlm), 7.35 (d, J = 7.7 Hz, 1H, Hk), 7.38‒7.46 (m, 3H, Ha,b), 7.62 (d,
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J = 7.7 Hz, 1H, Hn), 7.77 (dd, J = 1.5 Hz, 7.9 Hz, 2H, Hc), 8.00‒8.10 (br, 1H, Hj);13C NMR (100
MHz, CDCl3, 297 K): = 14.9, 20.5, 21.5, 36.5, 111.6, 115.6, 119.1, 119.6, 122.0, 122.4, 127.4,
127.7, 129.0, 131.0, 135.2, 136.8, 154.2, 162.8, 203.3; LR-ESIMS: m/z = 351 [MH]+; HR-ESIMS:
m/z = 351.1701 (calcd. for C21H23N2O3, 351.1703).
Benzaldehyde O-((allyloxy)carbonyl) oxime - 6a
Prepared from benzaldehyde oxime (0.320 g, 2.64 mmol), pyridine (0.21 cm3, 2.64 mmol) and
allylchloroformate (0.28 cm3, 2.64 mmol) to give a colourless oil, 0.269 g, yield = 50%. 1H NMR
(400 MHz, CDCl3, 300 K): = 4.77 (dt, J = 1.4 Hz, 5.8 Hz, 2H, Hc), 5.33 (dd, J = 1.2 Hz, 10.4 Hz,
1H, Ha), 5.43 (dd, J = 1.4 Hz, 17.2 Hz, 1H, Ha’), 5.95‒6.04 (m, 1H, Hb), 7.40‒7.49 (m, 3H, HAr),
7.73 (d, J = 6.9 Hz, 2H, He), 8.35 (s, 1H, Hd);13C NMR (100 MHz, CDCl3, 300 K): = 69.1, 119.7,
128.4, 128.9, 129.8, 131.1, 131.8, 153.6, 155.9; LR-ESIMS: m/z = 206 [MH]+; HR-ESIMS: m/z =
206.0813 (calcd. for C11H12NO3, 206.0812).
Acetophenone O-((allyloxy)carbonyl) oxime - 6b
Prepared form acetophenone oxime (0.567 g, 4.2 mmol), pyridine (0.34 cm3, 4.2 mmol) and
allylchloroformate (0.34 cm3, 4.2 mmol) to give a colourless crystalline solid, 0.777 g, yield = 84%.
M.p. = 44‒46 °C; 1H NMR (300 MHz, CDCl3, 300 K): = 2.40 (s, 3H, Hd), 4.77 (dt, J = 1.3 Hz,
5.9 Hz, 2H, Hc), 5.32 (dd, J = 1.2 Hz, 10.3 Hz, 1H, Ha), 5.43 (dd, J = 1.4 Hz, 17.2 Hz, 1H, Ha’),
5.94‒6.07 (m, 1H, Hb), 7.37‒7.46 (m, 3H, HAr), 7.74 (dd, J = 1.5 Hz, 7.8 Hz, 2H, He);13C NMR
(100 MHz, CDCl3, 300 K): = 14.4, 69.0, 119.6, 127.0, 128.6, 130.6, 131.3, 134.6, 153.7, 162.7;
LR-ESIMS: m/z = 220 [MH]+; HR-ESIMS: m/z = 220.0969 (calcd. for C12H14NO3, 220.0968).
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Benzophenone O-allyloxycarbonyl oxime - 6c
Prepared from benzophenone oxime (0.503 g, 2.55 mmol), allyl chloroformate (0.26 cm3, 2.45
mmol) and pyridine (0.21 cm3, 2.60 mmol) to give a colourless solid, 0.667 g, yield = 97%. M.p. =
67‒69 °C; 1H NMR (400 MHz, CDCl3, 296 K): = 4.71 (d, J = 5.9 Hz, 2H, Hc), 5.27 (dd, J = 1.2
Hz, 10.4 Hz, 1H, Ha), 5.36 (dd, J = 1.4 Hz, 17.2 Hz, 1H, Ha’), 5.95 (m, 1H, Hb), 7.33‒7.39 (m, 4H,
HAr), 7.43‒7.48 (m, 4H, HAr), 7.56‒7.59 (m, 2H, Hd);13C NMR (100 MHz, CDCl3, 297 K): =
(both isomers) 69.1, 119.6, 128.3, 128.4, 129.0, 129.1, 129.8, 130.9, 131.3, 132.1, 134.6, 153.8,
164.5; LR-ESIMS: m/z = 304 [MNa]+; HR-ESIMS: m/z = 304.0942 (calcd. for C17H15NO3Na,
304.0944).
4-Methoxyacetophenone O-((allyloxy)carbonyl) oxime - 6d
Prepared from 4-methoxyacetophenone oxime (0.502 g, 3.04 mmol), allyl chloroformate (0.32 cm3,
3. 95 mmol) and pyridine (0.25 cm3, 3.11 mmol) to give a colourless solid, 0.746 g, yield = 98%.
M.p. = 53‒56 °C; 1H NMR (400 MHz, CDCl3, 296 K): = 2.36 (s, 3H, Hd), 3.83 (s, 3H, Hg), 4.75
(d, J = 5.94 Hz, 2H, Hc), 5.32 (dd, J = 1.2 Hz, 10.4 Hz, 1H, Ha), 5.42 (dd, J = 1.4 Hz, 17.3 Hz, 1H,
Ha’), 6.00 (m, 1H, Hb), 6.90 (d, J = 8.9 Hz, 2H, Hf), 7.70 (d, J = 8.9 Hz, 2H, He);13C NMR (75
MHz, CDCl3, 297 K): = 14.5, 55.8, 69.3, 114.3, 119.9, 127.2, 128.9, 131.8, 154.2, 162.0, 162.5;
LR-ESIMS: m/z = 250 [MH]+; HR-ESIMS: m/z = 250.1077 (calcd. for C13H16NO4, 250.1074).
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Acetophenone O-allyloxycarbonothioyl oxime - 7
CDI Two-Pot Route: Prepared from allyl alcohol (0.38 cm3, 5.60 mmol), 1,1’-
thiocarbonyldiimidazole (3.011 g, 16.90 mmol), acetophenone oxime (1.014 g, 7.51 mmol), sodium
hydride (0.037 g, 1.50 mmol) to give a tan coloured oil, 0.584 g, yield = 44%. 1H NMR (400 MHz,
CDCl3, 296 K): = 2.44 (s, 3H, Hd), 5.09 (dq, J = 1.3 Hz, 5.8 Hz, 2H, Hc), 5.36 (dq, J = 1.2 Hz,
10.4 Hz, 1H, Ha), 5.47 (dq, J = 1.3 Hz, 17.2 Hz, 1H, Ha’), 6.06 (qt, J = 5.8 Hz, 10.4 Hz, 17.2 Hz,
1H, Hb), 7.40‒7.49 (m, 3H, HAr), 7.76 (dd, J = 1.4 Hz, 8.0 Hz, 2H, He);13C NMR (100 MHz,
CDCl3, 297 K): = 14.8, 74.2, 119.9, 127.2, 128.7, 130.7, 130.9, 134.3, 163.4, 193.0; LR-
ASAPMS: m/z = 235 [M]+.
O-Allyl 1H-imidazole-1-carbothioate: 1H NMR (400 MHz, CDCl3, 296 K): = 5.14 (dt, J = 1.2
Hz, 6.0 Hz, 2H, Hc), 5.40 (dq, J = 1.2 Hz, 10.4 Hz, 1H, Ha), 5.48 (dq, J = 1.2 Hz, 17.2 Hz, 1H, Ha’),
6.09 (qt, J = 6.0 Hz, 10.4 Hz, 17.2 Hz, 1H, Hb), 7.02 (s, 1H, Hf), 7.63 (s, 1H, He), 8.34 (s, 1H, Hd);
13C NMR (100 MHz, CDCl3, 297 K): = 73.7, 117.9, 120.9, 130.0, 130.9, 136.9, 183.9.
Acetophenone O-(cyclohex-2-enyloxy)carbonyl oxime - 8
CDI Two-Pot Route: Prepared from 2-cyclohexanol (0.34 cm3, 3.54 mmol), CDI (1.719 g, 10.61
mmol), acetophenone oxime (0.717 g, 5.32 mmol) and sodium hydride (0.026 g, 1.06 mmol) to give
a colourless oil, 0.569 g, yield = 62%. 1H NMR (400 MHz, CDCl3, 296 K): = 1.61‒1.69 (m, 1H,
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Hb), 1.71‒1.84 (m, 1H, Hb’), 1.87‒2.05 (m, 3H, Ha,c), 2.07‒2.15 (m, 1H, Ha’), 2.37 (s, 3H, Hg),
5.26‒5.31 (m, 1H, Hf), 5.82‒5.86 (m, 1H, Hd), 5.99‒6.04 (m, 1H, He), 7.36‒7.44 (m, 3H, HAr), 7.73
(dd, J = 1.5 Hz, 7.9 Hz, 2H, Hh);13C NMR (100 MHz, CDCl3, 297 K): = 14.4, 18.6, 24.9, 28.2,
72.7, 124.8, 127.0, 128.6, 130.5, 133.8, 134.7, 153.7, 162.3; LR-ESIMS: m/z = 282 [MNa]+; HR-
ESIMS: m/z = 282.1100 (calcd. for C15H17NO3Na, 282.1101).
Cyclohex-2-enyl 1H-imidazole-1-carboxylate: 1H NMR (300 MHz, CDCl3, 296 K): = 1.62‒2.19
(m, 6H, Ha,b,c), 5.41‒5.49 (m, 1H, Hf), 5.78‒5.86 (m, 1H, Hd), 6.04‒6.12 (m, 1H, He), 7.04 (s, 1H,
Hi), 7.41 (s, 1H, Hh), 8.12 (s, 1H, Hg);13C NMR (75 MHz, CDCl3, 297 K): = 18.9, 25.2, 28.5,
73.1, 117.5, 124.3, 130.9, 135.2, 137.5, 148.8; LR-ESIMS: m/z = 193 [MH]+; HR-ESIMS: m/z =
193.0971 (calcd. for C10H13N2O2, 193.0972).
Benzaldehyde O-((prop-2-yn-1-yloxy)carbonyl) oxime - 9a
Prepared form benzaldehyde oxime (0.274 g, 2.26 mmol), pyridine (0.18 cm3, 2.26 mmol) and
propargyl chloroformate (0.24 cm3, 2.26 mmol) to give a colourless crystalline solid, 0.054 g, yield
= 12%. M.p. = 96 °C; 1H NMR (400 MHz, CDCl3, 300 K): = 2.58 (t, J = 2.5 Hz, 1H, Ha), 4.87 (d,
J = 2.5 Hz, 2H, Hb), 7.40‒7.50 (m, 3H, HAr), 7.72 (d, J = 6.9 Hz, 2H, Hd), 8.35 (s, 1H, Hc);13C
NMR (100 MHz, CDCl3, 300 K): = 55.9, 76.3, 76.6, 128.5, 129.0, 129.6, 131.9, 153.2, 156.4; LR-
ESIMS: m/z = 204 [MH]+; HR-ESIMS: m/z = 204.0655 (calcd. for C11H10NO3, 204.0655).
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Acetophenone O-(prop-2-yn-1-yloxy)carbonyl oxime - 9b
Prepared form acetophenone oxime (0.670 g, 4.96 mmol), pyridine (0.38 cm3, 4.96 mmol) and
propargyl chloroformate (0.53 cm3, 5.46 mmol) to give a colourless crystalline solid, 0.983 g, yield
= 91%. M.p. = 88 °C; 1H NMR (300 MHz, CDCl3, 300 K): = 2.41 (s, 3H, Hc), 2.58 (t, J = 2.5 Hz,
1H, Ha), 4.88 (d, J = 2.5 Hz, 2H, Hb), 7.39‒7.47 (m, 3H, HAr), 7.74 (dd, J = 1.4 Hz, 8.0 Hz, 2H, Hd);
13C NMR (100 MHz, CDCl3, 300 K): = 14.5, 55.7, 55.8, 76.2, 127.1, 128.6, 130.8, 134.4, 153.3,
163.2; LR-ESIMS: m/z = 218 [MH]+; HR-ESIMS: m/z = 218.0813 (calcd. for C12H12NO3,
218.0812).
Acetophenone O-((2-allylphenoxy)carbonyl) oxime - 10
CDI One-Pot Route: Prepared from 2-allyl phenol (0.65 cm3, 5.00 mmol), CDI (0.810 g, 5.00
mmol), acetophenone oxime (0.675 g, 5.00 mmol) and sodium hydride (0.036 g, 1.50 mmol) to give
a colourless oil, 0.392 g, yield = 26%. 1H NMR (300 MHz, CDCl3, 296 K): = 2.50 (s, 3H, Hd),
3.46 (d, J = 6.6 Hz, 2H, Hi), 5.10‒5.18 (m, 2H, Hk), 5.99 (m, J = 6.6 Hz, 10.2 Hz, 16.8 Hz, 1H, Hj),
7.23‒7.35 (m, 4H, He,f,g,h), 7.42‒7.50 (m, 3H, Ha,b), 7.81 (dd, J = 1.4 Hz, 7.8 Hz, 2H, Hc);13C NMR
(75 MHz, CDCl3, 298 K): = 14.9, 34.8, 117.0, 122.3, 127.0, 127.5, 128.0, 129.1, 130.9, 131.2,
132.4, 134.8, 136.1, 149.6, 152.5, 163.7; LR-ESIMS: m/z = 296 [MH]+; HR-ESIMS: m/z =
296.1288 (calcd. for C18H18NO3, 296.1281).
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Acetophenone O-((cinnamyloxy)carbonyl) oxime - 11
Half of the crude mixture of acetophenone O-(((1-phenylallyl)oxy)carbonyl) oxime 13 (1.343 g)
was refluxed in toluene (30 cm3) for 5 days. The solvent was removed under reduced pressure and
the crude residue was purified by column chromatography (gradient elution, Pet Ether to
CH2Cl2:Pet Ether 1:1) to give the title compound as a colourless solid, 0.505 g, yield = 45% (w.r.t.
α-vinyl benzyl alcohol). M.p. = 70 °C. 1H NMR (400 MHz, CDCl3, 300 K): = 2.32 (s, 3H, Hd),
4.85 (d, J = 6.6 Hz, 2H, Hc), 6.29 (dd, J = 6.6 Hz, 15.9 Hz, 1H, Hb), 6.68 (d, J = 15.9 Hz, 1H, Ha),
7.17‒7.38 (m, 8H, HAr), 7.66 (d, J = 8.0 Hz, 2H, He);13C NMR (100 MHz, CDCl3, 300 K): =
14.4, 69.1, 122.1, 126.8, 127.0, 128.3, 128.6, 128.7, 130.7, 134.6, 135.7, 136.0, 153.8, 162.7; LR-
ESIMS: m/z = 318 [MNa]+; HR-ESIMS: m/z = 318.1103 (calcd. for C18H17NO3, 318.1101).
Acetophenone O-(((1-phenylallyl)oxy)carbonyl) oxime - 13
Prepared from α-vinyl benzyl alcohol 23 (1.00 cm3, 7.61 mmol), CDI (3.698 g, 22.8 mmol),
acetophenone oxime (1.541 g, 11.41 mmol) and sodium hydride (0.055 g, 2.28 mmol) to give a tan
coloured oil, 2.686 g, the product was used without further purification. 1H NMR (400 MHz,
CDCl3, 297 K): = 2.30 (s, 3H, Hd), 5.33‒5.45 (m, 2H, Hc), 6.07‒6.16 (m, 1H, Hb), 6.26‒6.27 (d, J
= 6.1 Hz, 1H, Ha), 7.34‒7.46 (m, 8H, HAr), 7.63‒7.65 (m, 2H, He);13C NMR (100 MHz, CDCl3,
300 K): = 12.2, 80.7, 118.2, 126.1, 127.0, 127.4, 128.5, 128.6, 128.7, 129.2, 130.6, 135.4, 153.3,
162.6; LR-ESIMS: m/z = 318 [MNa]+; HR-ESIMS: m/z = 318.1100 (calcd. for C18H17NO3,
318.1101).
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O N
O
N
bc
a
d
e
f
1-Phenylallyl 1H-imidazole-1-carboxylate: 1H NMR (400 MHz, CDCl3, 294 K): = 5.38‒5.44
(m, 2H, Hc), 6.09‒6.17 (m, 1H, Hb), 6.42 (d, J = 6.1 Hz, 1H, Ha), 7.07 (s, 1H, Hf), 7.30‒7.45 (m,
6H, HAr,e), 8.17 (s, 1H, Hd);13C NMR (75 MHz, CDCl3, 295 K): = 80.6, 117.1, 118.9, 127.3,
128.9, 129.1, 130.7, 134.6, 137.1, 137.1, 147.9.
Figure S1. The X-ray crystal structure of 5e.
Table S1. Crystal data and structure refinement for 5e.
Identification code 5e
CCDC code 896683
Empirical Formula C17H17NO4
Formula Weight 299.33
Crystal Colour, Habit colourless, prism
Crystal Dimensions 0.120 × 0.050 × 0.030 mm
Crystal System monoclinic
Lattice Type Primitive
Lattice Parameters a = 11.892(3) Å β = 95.099(8)°
b = 7.5168(13) Å
c = 17.092(4) Å
Volume 1521.8(5) Å3
Space Group P21/n (#14)
Z value 4
Density (calculated) 1.306 g/cm3
F(000) 632.00
μ(CuKα) 7.715 cm-1
Diffractometer Saturn70
Radiation CuKα (λ = 1.54187 Å)
Voltage, Current 40 kV, 20 mA
Temperature -100.0 °C
Detector Aperture 70 × 70 mm
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ω oscillation Range 1.0 - 0.0°
Pixel Size 0.034 mm
2θmax 135.1°
No. of Reflections Measured Total: 16358, Unique: 2628 (Rint = 0.0806)
Corrections Lorentz-polarization
Structure Solution Direct Methods
Refinement Full-matrix least-squares on F2
Function Minimized Σ w (Fo2 - Fc2)2
Least Squares Weights w = 1/ [σ2(Fo2) + (0.1051 · P)2 + 2.9953 · P ]
where P = (Max(Fo2,0) + 2Fc2)/3
2θmax cutoff 135.1°
Anomalous Dispersion All non-hydrogen atoms
No. Observations (All reflections) 2628
No. Variables 199
Reflection/Parameter Ratio 13.21
Residuals: R1 (I>2.00σ(I)) 0.1086
Residuals: R (All reflections) 0.1272
Residuals: wR2 (All reflections) 0.3165
Goodness of Fit Indicator 1.465
Max Shift/Error in Final Cycle 0.004
Maximum peak in Final Diff. Map 0.32 e /Å3
Minimum peak in Final Diff. Map -0.33 e /Å3
Figure S2. The X-ray crystal structure of 9a.
Table S2. Crystal data and structure refinement for 9a.
Identification code 9a
CCDC code 896684
Empirical Formula C11H9NO3
Formula Weight 203.20
Crystal Colour, Habit colourless, prism
Crystal Dimensions 0.100 × 0.100 × 0.100 mm
Crystal System orthorhombic
Lattice Type Primitive
Lattice Parameters a = 19.168(13) Å
b = 6.189(5) Å
c = 8.461(5) Å
Volume 1003.7(12) Å3
Space Group Pnma (#62)
Z value 4
Density (calculated) 1.345 g/cm3
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F(000) 424.00
μ(MoKα) 0.992 cm-1
Diffractometer Mercury70
Radiation MoKα (λ = 0.71075 Å)
Voltage, Current 50 kV, 16 mA
Temperature -180.0 °C
Detector Aperture 70 × 70 mm
Pixel Size 0.068 mm
2θmax 50.7°
No. of Reflections Measured Total: 5804, Unique: 1006 (Rint = 0.1655)
Corrections Lorentz-polarization
Absorption (trans. factors: 0.247 - 0.990)
Secondary Extinction (coefficient: 1.38700e-001)
Structure Solution Charge Flipping (Superflip)
Refinement Full-matrix least-squares on F2
Function Minimized Σ w (Fo2 - Fc2)2
Least Squares Weights w = 1/ [σ2(Fo2) + (0.2000 · P)2 + 0.0000 · P]
where P = (Max(Fo2,0) + 2Fc2)/3
2θmax cutoff 50.7°
Anomalous Dispersion All non-hydrogen atoms
No. Observations (All reflections) 1006
No. Variables 92
Reflection/Parameter Ratio 10.93
Residuals: R1 (I>2.00σ(I)) 0.1057
Residuals: R (All reflections) 0.1145
Residuals: wR2 (All reflections) 0.2968
Goodness of Fit Indicator 1.134
Max Shift/Error in Final Cycle 0.132
Maximum peak in Final Diff. Map 0.70 e /Å3
Minimum peak in Final Diff. Map -0.41 e /Å3
UV Photolyses of Oxime Carbonates
Scheme S4. UV photolyses of oxime carbonate 5g.
A solution of oxime carbonate 5g (0.060 g, 0.19 mmol) in benzene (2 cm3) was irradiated at RT for
4 h. 1H NMR product analysis (w.r.t. MAP) revealed: 41% alcohol.
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A solution of oxime carbonate 5g (0.060 g, 0.19 mmols) and 4-methoxyacetophenone (0.060 g,
0.27 mmol) in t-BuOH (2 cm3) was irradiated at RT for 4 h. 1H NMR product analysis (w.r.t. MAP)
revealed: 52% alcohol.
A solution of oxime carbonate 5g (0.040 g, 0.12 mmols) and 4-methoxyacetophenone (0.040 g,
0.27 mmol) in PhCF3 (2 cm3) was heated at 70 °C and irradiated for 3 h. 1H NMR product analysis
(w.r.t. MAP) revealed: 30% alcohol.
A solution of oxime carbonate 5g (0.048 g, 0.15 mmol) and 4-methoxyacetophenone (0.048 g, 0.32
mmol) in t-BuOH (2 cm3) was heated at 70 °C and irradiated for 3 h. 1H NMR product analysis
(w.r.t. MAP) revealed: 39% alcohol.
Table S3. UV photolyses results for oxime carbonate 5g.
entry solvent temperature time / h yield alcohol
1 Benzene RT 4 41%
2 t-BuOH RT 4 52%
3 PhCF3 70 °C 3 30%
4 t-BuOH 70 °C 3 39%
Scheme S5. UV photolysis of oxime carbonate 5h
A solution of oxime carbonate 5h (0.038 g, 0.11 mmol) and 4-methoxyacetophenone (0.038 g, 0.25
mmol) in PhCF3 (2.5 cm3) was irradiated for 3 h. 1H NMR product analysis (w.r.t. MAP) revealed:
22% 2-biphenylmethanol; <5% unreacted oxime carbonate 5h.
A solution of oxime carbonate 5h (0.047 g, 0.14 mmol) and 4-methoxyacetophenone (0.047 g, 0.31
mmol) in PhCF3 (2 cm3) was heated at 70 °C and irradiated for 4.5 h. 1H NMR product analysis
(w.r.t. MAP and CH2Br2) revealed: 35% 2-biphenylmethanol; <5% unreacted 5h.
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A solution of oxime carbonate 5h (0.047 g, 0.14 mmol) and 4-methoxyacetophenone (0.047 g, 0.31
mmol) in toluene (2 cm3) was heated at 70 °C and irradiated for 4.5 h. 1H NMR product analysis
(w.r.t. MAP and CH2Br2) revealed: 40% 2-biphenylmethanol; <5% unreacted 5h.
Scheme S6. UV photolysis of indole oxime carbonate 5i.
A solution of oxime carbonate 5i (0.067 g, 0.20 mmol) and 4-methoxy acetophenone (0.067 g, 0.45
mmol) in toluene (2 cm3) was heated at 80 °C and irradiated for 3 h. 1H NMR product analysis
(w.r.t. MAP) revealed: 11% unreacted 5i; 42% 4-(1H-indol-3-yl)butan-2-ol.
.
Scheme S7. UV photolysis of allyl oxime carbonates 6b-d, 7. Reagents and conditions: MAP, Tol, UV.
0 °C: A solution of oxime carbonate 6b (0.053 g, 0.24 mmol) and 4-methoxy acetophenone (MAP)
(0.053 g, 0.35 mmol) in toluene (2 cm3) was irradiated for 5 h at 0 °C. 1H NMR product analysis
(w.r.t. MAP) revealed: 44% unreacted oxime carbonate 6b; 14% 4-methyl-1,3-dioxolan-2-one 30a;
6% allyl alcohol.
RT: A solution of oxime carbonate 6b (0.061 g, 0.28 mmol) and 4-methoxy acetophenone (MAP)
(0.061 g, 0.41 mmol) in toluene (2 cm3) was irradiated for 4 h at RT. 1H NMR product analysis
(w.r.t. MAP) revealed: 22% unreacted 6b; 18% 4-methyl-1,3-dioxolan-2-one 30a; 6% allyl alcohol.
4-Methyl-1,3-dioxolan-2-one was purified by column chromatography (gradient elution, Pet Ether
to CH2Cl2) to yield the 4-methyl-1,3-dioxolan-2-one 30a as a tan coloured oil, 0.005 g, yield =
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18%. 1H NMR was consistent with data reported in the literature.8 1H NMR (400 MHz, CDCl3, 296
K): = 1.50 (d, J = 6.3 Hz, 3H, Ha), 4.03 (t, J = 8.1 Hz, 1H, Hc), 4.55 (t, J = 8.1 Hz, 1H, Hc’), 4.85
(m, 1H, Hb).
RT: A solution of oxime carbonate 6c (0.058 g, 0.21 mmol) and 4-methoxy acetophenone (MAP)
(0.063 g, 0.42 mmol) in toluene (2 cm3) was irradiated for 5 h at RT. 1H NMR product analysis
(w.r.t. MAP) revealed: 24% unreacted oxime carbonate 17c; 19% 4-methyl-1,3-dioxolan-2-one 30a.
RT: A solution of oxime carbonate 6d (0.050 g, 0.21 mmol) and 4-methoxy acetophenone (MAP)
(0.050 g, 0.33 mmol) in toluene (2 cm3) was irradiated for 5 h at RT. 1H NMR product analysis
(w.r.t. MAP) revealed: 43% unreacted oxime carbonate 6d; 14% 4-methyl-1,3-dioxolan-2-one 30a.
A solution of oxime thiocarbonate 7 (0.053 g, 0.23 mmol) and 4-methoxy acetophenone (MAP)
(0.053 g, 0.35 mmol) in toluene (2 cm3) was irradiated for 4 h at RT. 1H NMR product analysis
(w.r.t. CH2Br2, 0.142 mmol) revealed: 9% unreacted 7; 5% 4-methyl-1,3-dioxolane-2-thione 30b;
25% allyl alcohol.
Scheme S8. UV photolyis of oxime carbonate 8.
A solution of acetophenone O-(cyclohex-2-enyloxy)carbonyl oxime 8 (0.050 g, 0.19 mmol) and 4-
methoxyacetophenone (0.049 g, 0.33 mmol) in toluene (3 cm3) was irradiated for 5 h. 1H NMR
product analysis (w.r.t. MAP) revealed: 13% unreacted 8; 22% hexahydrobenzo[1,3]dioxol-2-one.
A solution of acetophenone O-(cyclohex-2-enyloxy)carbonyl oxime (0.108 g, 0.42 mmol) and 4-
methoxyacetophenone (0.108 g, 0.72 mmol) in toluene (3 cm3) was irradiated for 4 h. 1H NMR
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product analysis (w.r.t. MAP) revealed: 22% hexahydrobenzo[1,3]dioxol-2-one; 7% 2-cyclohexen-
1-ol.
Scheme S9. UV photolysis of allylphenoxy oxime carbonate 10.
A solution of allylphenoxy oxime carbonate 10 (0.080 g, 0.271 mmol) and 4-methoxyacetophenone
(0.080 g, 0.533 mmol) in toluene (2 cm3) was irradiated for 3 h at RT. 1H NMR product analysis
(w.r.t. MAP) revealed: 11% unreacted 10; 55% 2-allylphenol.
Scheme S10. UV photolysis of oxime carbonate 11.
A solution of allylphenoxy oxime carbonate 11 (0.053 g, 0.179 mmol) and 4-methoxyacetophenone
(0.053 g, 0.353 mmol) in toluene (2 cm3) was irradiated for 3 h at RT. 1H NMR product analysis
(w.r.t. MAP) revealed no identifiable products or by-products.
O ON
O
UV
Scheme S11. UV photolysis of oxime carbonate 13.
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A solution of allylphenoxy oxime carbonate 13 (0.058 g, 0.179 mmol) and 4-methoxyacetophenone
(0.058 g, 0.387 mmol) in toluene (3 cm3) was irradiated for 3 h at RT. 1H NMR product analysis
(w.r.t. MAP) revealed no identifiable products or by-products.
EPR Spectroscopy
EPR spectra were obtained with a Bruker EMX 10/12 spectrometer fitted with a rectangular
ER4122 SP resonant cavity and operating at 9.5 GHz with 100 kHz modulation. Stock solutions of
each oxime carbonate (2 to 15 mg) and MAP (1 equiv. wt/wt) in tert-butylbenzene or benzene (0.5
cm3) were prepared and sonicated if necessary. An aliquot (0.2 cm3), to which any additional
reactant had been added, was placed in a 4 mm o.d. quartz tube, de-aerated by bubbling nitrogen for
15 min, and photolysed in the resonant cavity by unfiltered light from a 500 W super pressure
mercury arc lamp. Solutions in cyclopropane were prepared on a vacuum line by distilling in the
cyclopropane, degassing with three freeze-pump-thaw cycles and finally flame sealing the tubes. In
all cases where spectra were obtained, hfs were assigned with the aid of computer simulations using
the Bruker SimFonia and NIEHS Winsim2002 software packages. For kinetic measurements,
precursor samples were used mainly in 'single shot' experiments, i.e. new samples were prepared for
each temperature and each concentration to minimize sample depletion effects. EPR signals were
digitally filtered and double integrated using the Bruker WinEPR software and radical
concentrations were calculated by reference to the double integral of the signal from a known
concentration of the stable radical DPPH [1 10-3 M in PhMe], run under identical conditions, as
described previously. The majority of EPR spectra were recorded with 2.0 mW power, 0.8 Gpp
modulation intensity and gain of ca. 106.
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EPR Spectra
Scheme S12. Radicals detected upon UV photolyses of allyl oxime carbonates 6a-d, 7.
Figure S3. Top spectrum from 6b at 217 K in t-BuPh showing iminyl radical PhMeC=N• and 21 (X=O); bottom
spectrum from 6a at 230 K in t-BuPh showing iminyl radical PhHC=N• and 21 (X=O).
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Figure S4. Top: experimental EPR spectrum from allyl oxime thiocarbonate 7 in t-BuPh at 220 K showing iminyl
radical PhMeC=N• and cyclised 2-thiono-1,3-dioxolanyl-4-methyl radical 22; bottom: simulation with parameters listed
in Table 3 of main text
Scheme S13. Radicals detected upon UV photolyses of acetophenone O-((cyclohex-2-en-1-yloxy)carbonyl) oxime 19.
Figure S5. a) Experimental EPR spectrum from acetophenone O-((cyclohex-2-en-1-yloxy)carbonyl) oxime 8 in t-BuPh
at 265 K showing iminyl PhMeC=N• and bicyclic hexahydrobenzo[d][1,3]dioxol-2-one-4-yl radical 23; b) simulation
with the parameters from Table 3 in the main text.
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Scheme S14. Radicals detected upon UV photolyses of oxime carbonate 11.
Figure S6. Full black line experimental EPR spectrum from oxime carbonate 11 in t-BuPh at 220 K (NB a peroxyl
signal was digitally removed to the left and an F-centre (trapped electron in quartz EPR tube) is visible at ~3390 G).
Red line: simulation of radical 24 with parameters from Table 3.
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Table S4. Reference parameters from DPPH standard.
[DPPH] 1.00E-03
Gain DPPH 2.00E+03
D.Int DPPH 76
temp DPPH 300
Actual T 302.258
F[Spiro] 1
F[Im] 1
Table S5. Kinetic EPR data for CO2 loss from PhCHMeOC(O)ON=CHPh precursor 5c and MAP with UV in t-BuPh. Results from using [Spiro]/[Im] ratio.
Dial Actual scans Gain [Sp]/[Im] D Int D Int [Spiro] [Im] Im-Spiro kd/2kt logkd/2kt log2kt 103/T log log log2kt log kd kd s-1
Temp / K / K Spiro Im M M M n-C7 n-C7 t-BuPh t-BuPh t-BuPh
210 210.55 5 2.0E+06 9.60E-01 11.92 12 3.04E-08 3.17E-08 1.27E-09 1.32E-09 -8.879 9.292 4.750 0.17 1.06 8.402 -4.770E-01 3.33E-01
220 220.74 7 2.0E+06 9.20E-01 11.6 12.69 2.31E-08 2.51E-08 2.01E-09 2.18E-09 -8.661 9.400 4.530 0.08 0.85 8.635 -2.615E-02 9.42E-01
230 230.93 5 2.0E+06 9.20E-01 9.76 12.42 3.31E-08 3.60E-08 2.88E-09 3.13E-09 -8.505 9.498 4.330 0.00 0.66 8.834 3.286E-01 2.13E+00
240 241.12 16 2.0E+06 9.20E-01 18.68 20.7 1.80E-08 1.96E-08 1.56E-09 1.70E-09 -8.769 9.588 4.147 -0.08 0.51 9.004 2.342E-01 1.71E+00
250 251.31 5 2.0E+06 8.20E-01 6.32 10.8 2.79E-08 3.40E-08 6.12E-09 7.47E-09 -8.127 9.671 3.979 -0.15 0.37 9.150 1.024E+00 1.06E+01
260 261.50 8 2.0E+06 6.60E-01 7.2 12.72 1.72E-08 2.61E-08 8.86E-09 1.34E-08 -7.872 9.747 3.824 -0.21 0.26 9.277 1.405E+00 2.54E+01
270 271.69 8 2.0E+06 4.90E-01 6.96 10.46 1.09E-08 2.23E-08 1.14E-08 2.32E-08 -7.635 9.818 3.681 -0.27 0.16 9.388 1.753E+00 5.66E+01
280 281.88 11 2.0E+06 4.10E-01 5.68 9.84 6.48E-09 1.58E-08 9.33E-09 2.27E-08 -7.643 9.883 3.548 -0.33 0.07 9.484 1.841E+00 6.94E+01
290 292.07 10 2.0E+06 2.40E-01 4.8 10.24 4.50E-09 1.87E-08 1.42E-08 5.94E-08 -7.226 9.944 3.424 -0.38 -0.01 9.569 2.342E+00 2.20E+02
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Table S6. Kinetic EPR data for CO2 loss from BnOC(O)ON=CHPh precursor 5a and MAP with UV in t-BuPh. Results from using [Spiro]/[Im] ratio.
Dial Actual T [Im] [Spiro]/ [Spiro] Im-Spiro kd/2kt logkd/2kt log2kt 103/T log log log2kt log kd kd s-1
Temp / K / K M [Im] M M n-C7 n-C7 t-BuPh t-BuPh t-BuPh
210 210.55 7.63E-08 0.98 7.48E-08 1.53E-09 1.56E-09 -8.807 9.292 4.750 0.17 1.06 8.402 -4.050E-01 3.94E-01
220 220.74 7.08E-08 0.923 6.53E-08 5.45E-09 5.91E-09 -8.229 9.400 4.530 0.08 0.85 8.635 4.064E-01 2.55E+00
230 230.93 5.96E-08 0.65 3.87E-08 2.08E-08 3.21E-08 -7.494 9.498 4.330 0.00 0.66 8.834 1.340E+00 2.19E+01
240 241.12 3.45E-08 0.48 1.65E-08 1.79E-08 3.73E-08 -7.428 9.588 4.147 -0.08 0.51 9.004 1.576E+00 3.77E+01
240 241.12 3.03E-08 0.48 1.45E-08 1.57E-08 3.28E-08 -7.484 9.588 4.147 -0.08 0.51 9.004 1.519E+00 3.31E+01
250 251.31 4.50E-08 0.34 1.53E-08 2.97E-08 8.73E-08 -7.059 9.671 3.979 -0.15 0.37 9.150 2.091E+00 1.23E+02
260 261.50 2.92E-08 0.28 8.17E-09 2.10E-08 7.50E-08 -7.125 9.747 3.824 -0.21 0.26 9.277 2.152E+00 1.42E+02
280 281.88 2.75E-08 0.22 6.05E-09 2.15E-08 9.75E-08 -7.011 9.883 3.548 -0.33 0.07 9.484 2.473E+00 2.97E+02
290 292.07 1.63E-08 0.18 2.93E-09 1.34E-08 7.42E-08 -7.130 9.944 3.424 -0.38 -0.01 9.569 2.439E+00 2.75E+02
300 302.26 2.49E-08 0.11 2.74E-09 2.22E-08 2.02E-07 -6.696 10.001 3.308 -0.43 -0.07 9.643 2.947E+00 8.86E+02
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Computational Methods
Radical ground-state calculations were carried out using the Gaussian 03 program package.9
Becke’s three-parameter hybrid exchange potential (B3)10 was used with the LYP correlation
functional, B3LYP. This method has previously described the chemistry of iminyl radicals
accurately. The standard split-valence 6-31+G(d) basis set was initially employed.
Geometries were fully optimised for all model compounds. Optimised structures were
characterised as minima or saddle points by frequency calculations. The experimental kinetic
and spectroscopic data was all obtained in the non-polar hydrocarbon solvents tert-
butylbenzene or cyclopropane. Solvent effects, particularly differences in solvation between
the neutral reactants and neutral transition states, are therefore expected to be minimal. In
view of this, no attempt was made to computationally model the effect of the solvent.
DFT Optimised Structures and Energies
Table S7. Spiro radical 16 optimised geometry: UB3LYP/6-311+G(2d,p) E = -534.8507054 H.
CentreNumber
AtomicNumber
AtomicType
Coordinates (Angstroms)X Y Z
1 6 0 -2.295664 1.227332 -0.1648612 6 0 -0.944819 1.251142 0.0489003 6 0 -0.945707 -1.251442 0.0472004 6 0 -2.296534 -1.226366 -0.1665415 6 0 -3.000103 0.000807 -0.2736336 1 0 -2.839570 2.164257 -0.2559307 1 0 -0.403467 2.191879 0.1167798 1 0 -0.405021 -2.192653 0.1137549 1 0 -2.841106 -2.162778 -0.25890010 1 0 -4.071536 0.001304 -0.44849711 6 0 -0.130049 -0.000534 0.17576012 6 0 0.778799 -0.001697 1.45324713 1 0 0.625047 -0.895675 2.06362514 1 0 0.623988 0.890458 2.06599615 8 0 2.125259 -0.000238 0.97090416 6 0 2.152564 0.000360 -0.39046917 8 0 3.155067 0.001103 -1.04698718 8 0 0.894767 -0.000165 -0.895723
Table S8. Formate radical HOC(O)O UB3LYP/6-31+G(d), E = -264.338117801 AU.
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CentreNumber
AtomicNumber
AtomicType
Coordinates (Angstroms)X Y Z
1 6 0 -0.054666 -0.000501 0.0000802 8 0 -0.899010 -0.939414 -0.0000123 8 0 1.243704 -0.287237 -0.0000384 1 0 1.757043 0.543099 0.0001185 8 0 -0.523325 1.159140 -0.000026
Table S9. Transition State (TS) for CO2 loss from formate radical, UB3LYP/6-31+G(d), E = -264.305299191.
CentreNumber
AtomicNumber
AtomicType
Coordinates (Angstroms)X Y Z
1 6 0 0.364846 0.135899 0.0030122 8 0 -0.208296 1.212615 -0.0113743 8 0 -1.178588 -0.703318 -0.1024734 1 0 -1.673760 -0.520111 0.7250165 8 0 1.322469 -0.546207 0.020961
Table S10. EtOC(O)O radical UB3LYP/6-311+G(2d,p), E = -343.067582235.
CentreNumber
AtomicNumber
AtomicType
Coordinates (Angstroms)X Y Z
1 6 0 1.213554 0.488541 0.0001512 1 0 1.097009 1.111970 0.8869793 1 0 1.096878 1.112353 -0.8863904 6 0 -1.091098 -0.057660 0.0001145 8 0 -2.054983 -0.871394 -0.0000236 8 0 -1.420654 1.143830 -0.0001197 8 0 0.143805 -0.510903 0.0000158 6 0 2.524517 -0.262042 -0.0001089 1 0 2.614646 -0.891339 -0.88654310 1 0 3.349501 0.453435 -0.00001311 1 0 2.614776 -0.891723 0.886042
Table S11. TS for CO2 loss from EtOC(O)O UB3LYP/6-311+G(2d,p), E = -343.047081623.
CentreNumber
AtomicNumber
AtomicType
Coordinates (Angstroms)X Y Z
1 6 0 -1.182615 -0.639242 -0.2662772 1 0 -1.482932 -1.673483 -0.0336463 1 0 -0.802705 -0.626469 -1.2916664 6 0 1.303105 0.145697 0.0007685 8 0 0.996152 1.317523 -0.0545616 8 0 2.103601 -0.699475 -0.1801537 8 0 -0.142475 -0.390947 0.6560948 6 0 -2.358161 0.305112 -0.0651269 1 0 -2.053414 1.329600 -0.28205410 1 0 -3.169916 0.027835 -0.74114611 1 0 -2.723228 0.256304 0.961280
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Table S12. t-BuOC(O)O radical UB3LYP/6-31+G(d), E = -421.601173354.
CentreNumber
AtomicNumber
AtomicType
Coordinates (Angstroms)X Y Z
1 6 0 -1.103701 0.823024 1.2756992 1 0 -0.947496 0.198141 2.1616383 1 0 -0.377487 1.640004 1.2880954 1 0 -2.108467 1.255953 1.3385285 6 0 -0.996675 -0.014687 -0.0000026 6 0 -2.011279 -1.157590 -0.0004847 1 0 -1.888765 -1.785193 -0.8889048 1 0 -1.889129 -1.785619 0.8876869 1 0 -3.027411 -0.748929 -0.00059410 6 0 -1.103164 0.823634 -1.27534411 1 0 -0.376911 1.640593 -1.28705912 1 0 -0.946631 0.199169 -2.16151913 1 0 -2.107887 1.256634 -1.33836414 8 0 0.307877 -0.750360 0.00006715 6 0 1.472044 -0.136573 0.00018916 8 0 1.676150 1.100426 -0.00003217 8 0 2.531828 -0.837266 -0.000017
Table S13. TS for CO2 loss from t-BuOC(O)O radical UB3LYP/6-31+G(d), E = -421.581836272.
CentreNumber
AtomicNumber
AtomicType
Coordinates (Angstroms)X Y Z
1 6 0 0.668857 -0.349850 1.4980342 1 0 0.021930 0.413972 1.9422033 1 0 0.180210 -1.324699 1.5935004 1 0 1.600268 -0.374839 2.0736385 6 0 0.978176 -0.025925 0.0344196 6 0 1.617763 1.364527 -0.1321727 1 0 1.805426 1.579029 -1.1885168 1 0 0.950341 2.133797 0.2675829 1 0 2.568680 1.398360 0.41123810 6 0 1.875810 -1.114938 -0.60691111 1 0 1.409634 -2.100699 -0.52099012 1 0 2.056022 0.896761 -1.66326413 1 0 2.835438 -1.128637 -0.07778214 6 0 -1.718179 0.010920 -0.14324015 8 0 -2.257591 -1.042953 -0.02254616 8 0 -1.794434 1.225345 -0.02420317 8 0 -0.193289 -0.058383 -0.795550
Table S14. AllylOC(O)O radical 19, UB3LYP/6-31+G(d), E = -381.042619081.
CentreNumber
AtomicNumber
AtomicType
Coordinates (Angstroms)X Y Z
1 6 0 0.668857 -0.349850 1.4980342 8 0 0.021930 0.413972 1.9422033 8 0 0.180210 -1.324699 1.593500
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4 8 0 1.600268 -0.374839 2.0736385 6 0 0.978176 -0.025925 0.0344196 1 0 1.617763 1.364527 -0.1321727 1 0 1.805426 1.579029 -1.1885168 6 0 0.950341 2.133797 0.2675829 1 0 2.568680 1.398360 0.41123810 6 0 1.875810 -1.114938 -0.60691111 1 0 1.409634 -2.100699 -0.52099012 1 0 -0.193289 -0.058383 -0.795550
Table S15. TS for CO2 loss from allylOC(O)O radical 19, UB3LYP/6-31+G(d), E = -381.020982285.
CentreNumber
AtomicNumber
AtomicType
Coordinates (Angstroms)X Y Z
1 6 0 1.689265 0.176429 -0.0648442 8 0 2.233366 -0.911423 0.0390183 8 0 0.203282 -0.391112 -0.5766894 8 0 1.767160 1.359426 0.0361455 6 0 -0.748907 -0.639792 0.4577426 1 0 -1.146670 -1.651131 0.3275627 1 0 -0.279119 -0.541570 1.4433698 6 0 -1.819864 0.405530 0.2438269 1 0 -1.525502 1.430523 0.45843810 6 0 -3.044216 0.112510 -0.20850611 1 0 -3.336218 -0.904943 -0.45960912 1 0 -3.800630 0.883931 -0.326848
Table S16. Radical PhCHMeOC(O)O 15c, UB3LYP/6-31+G(d), E = -574.025742529.
CentreNumber
AtomicNumber
AtomicType
Coordinates (Angstroms)X Y Z
1 6 0 -2.680173 -0.726364 -0.9878892 6 0 -1.413096 -0.188939 -1.2324113 6 0 -0.658923 0.358763 -0.1879374 6 0 -1.184750 0.350009 1.1124825 6 0 -2.445491 -0.195245 1.3595126 6 0 -3.198255 -0.730791 0.3089727 1 0 -3.254360 -1.149911 -1.8077068 1 0 -1.005403 -0.204462 -2.2408799 1 0 -0.601088 0.755997 1.93471710 1 0 -2.840181 -0.203942 2.37220911 1 0 -4.180159 -1.154531 0.50298512 6 0 0.690820 0.980018 -0.47810913 1 0 1.000795 0.727681 -1.49584914 8 0 1.710795 0.427778 0.44269715 6 0 2.296845 -0.706771 0.10665016 8 0 3.136036 -1.233193 0.89843217 8 0 2.117844 -1.337975 -0.96091618 6 0 0.744227 2.489082 -0.27274019 1 0 0.492121 2.752294 0.759421
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20 1 0 1.743667 2.873757 -0.50049021 1 0 0.019985 2.971665 -0.937288
Table S17. TS for CO2 loss from radical PhCHMeOC(O)O 15c, UB3LYP/6-31+G(d), E = -574.006040808.
CentreNumber
AtomicNumber
AtomicType
Coordinates (Angstroms)X Y Z
1 6 0 2.369930 -1.538783 0.2833932 6 0 1.079250 -1.056185 0.4926393 6 0 0.772930 0.292972 0.2331464 6 0 1.767793 1.136781 -0.2848755 6 0 3.059130 0.651744 -0.4905906 6 0 3.363376 -0.685237 -0.2075227 1 0 2.598572 -2.579572 0.4955128 1 0 0.297092 -1.721192 0.8493419 1 0 1.545004 2.174488 -0.51015910 1 0 3.829486 1.316251 -0.87262711 1 0 4.369526 -1.060253 -0.37564512 6 0 -0.655762 0.764482 0.49035713 1 0 -1.023679 0.301901 1.41468114 8 0 -1.344079 0.190320 -0.62885515 6 0 -2.651188 -0.753635 -0.23199016 8 0 -3.530579 0.078700 -0.38205117 8 0 -2.378347 -1.876299 0.07078218 6 0 -0.891416 2.270982 0.52988119 1 0 -0.620314 2.742644 -0.41898920 1 0 -1.951976 2.464435 0.71382921 1 0 -0.303925 2.720813 1.338414
Table S18. Radical BnOC(O)O 15a, UB3LYP/6-31+G(d), E = -534.706276187.
CentreNumber
AtomicNumber
AtomicType
Coordinates (Angstroms)X Y Z
1 6 0 -2.780182 -1.236783 0.1235372 6 0 -1.443381 -1.187008 -0.2757393 6 0 -0.786475 0.044220 -0.4069404 6 0 -1.488837 1.226262 -0.1371385 6 0 -2.826560 1.179396 0.2612046 6 0 -3.473503 -0.052705 0.3925407 1 0 -3.280534 -2.196531 0.2213358 1 0 -0.905507 -2.108987 -0.4856249 1 0 -0.986718 2.185940 -0.23834910 1 0 -3.362727 2.102132 0.46647211 1 0 -4.515218 -0.090081 0.70043212 6 0 0.654870 0.094542 -0.82384313 1 0 0.919653 -0.731501 -1.48882514 1 0 0.908661 1.040463 -1.30888515 8 0 1.481710 -0.024480 0.39210416 6 0 2.790877 -0.018122 0.22295717 8 0 3.552518 -0.119381 1.233178
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18 8 0 3.383465 0.081330 -0.876034
Table S19. TS for CO2 loss from radical BnOC(O)O 15a, UB3LYP/6-31+G(d), E = -534.686689163.
CentreNumber
AtomicNumber
AtomicType
Coordinates (Angstroms)X Y Z
1 6 0 -2.232691 1.451185 0.0392522 6 0 -0.956429 0.967035 0.3246413 6 0 -0.716162 -0.418155 0.3311414 6 0 -1.751026 -1.306879 0.0043535 6 0 -3.027039 -0.819165 -0.2767996 6 0 -3.268869 0.560016 -0.2597397 1 0 -2.417707 2.521804 0.0431828 1 0 -0.140967 1.653636 0.5362899 1 0 -1.559280 -2.376888 -0.01322010 1 0 -3.831917 -1.511180 -0.50930411 1 0 -4.262396 0.938371 -0.48547812 6 0 0.672989 -0.930593 0.65640413 1 0 1.087237 -0.457767 1.55362814 1 0 0.675782 -2.019814 0.77046015 8 0 1.438843 -0.590228 -0.49571816 6 0 2.807118 0.312764 -0.17740017 8 0 3.621857 -0.592720 -0.20327118 8 0 2.599538 1.477271 -0.019345
Figure S7. Plot of Activation Energies (E‡a - experimental and E‡ - DFT computed) vs. DFT computed
reaction enthalpies H298 for CO2 loss from ROC(O)O radicals. Red squares: experimental data. Blue circles:DFT computed data.
Table S20. 2-Oxo-1,3-dioxolan-4-yl-methyl radical 21, UB3LYP/6-311+G(2d,p), E = -381.170257965.
CentreNumber
AtomicNumber
AtomicType
Coordinates (Angstroms)X Y Z
1 6 0 -1.120665 -0.163631 -0.0273252 8 0 -2.221982 -0.566897 -0.2163293 8 0 -0.691935 1.089444 -0.3309394 8 0 -0.113352 -0.887563 0.5265645 6 0 0.640482 1.284595 0.1552406 1 0 1.222748 1.782880 -0.6174987 1 0 0.600065 1.905610 1.0519898 6 0 1.128771 -0.150425 0.452267
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9 1 0 1.578234 -0.203704 1.45165010 6 0 2.022214 -0.738262 -0.57175611 1 0 2.885453 -0.183569 -0.91562612 1 0 1.906838 -1.774751 -0.855431
Table S21. TS for ring closure to 2-oxo-1,3-dioxolan-4-yl-methyl radical 21, UB3LYP/6-311+G(2d,p), E = -381.144538739.
CentreNumber
AtomicNumber
AtomicType
Coordinates (Angstroms)X Y Z
1 6 0 -1.150100 -0.132783 -0.0044412 8 0 -2.314504 -0.341124 -0.2727233 8 0 -0.524115 1.008089 -0.3831354 8 0 -0.444270 -0.988881 0.6713005 6 0 0.744051 1.225238 0.2569306 1 0 1.261102 1.954482 -0.3671957 1 0 0.567749 1.667478 1.2389868 6 0 1.534034 -0.053657 0.3895279 1 0 1.886945 -0.311112 1.38097010 6 0 1.935953 -0.790501 -0.66911811 1 0 1.645494 -0.533082 -1.68139612 1 0 2.518187 -1.692230 -0.532286
Table S22. 2-Thio-1,3-dioxolan-4-yl-methyl radical 22, UB3LYP/6-311+G(2d,p), E = -704.117593880.
CentreNumber
AtomicNumber
AtomicType
Coordinates (Angstroms)X Y Z
1 6 0 0.761608 0.027335 -0.0264592 8 0 0.268369 1.280806 -0.0041343 8 0 -0.227366 -0.872195 -0.1444624 6 0 -1.166365 1.230107 0.0881885 1 0 -1.455739 1.386581 1.1299036 1 0 -1.580055 2.018334 -0.5365977 6 0 -1.508571 -0.179842 -0.4013298 1 0 -1.649726 -0.200864 -1.4836449 6 0 -2.612853 -0.851795 0.30145810 1 0 -3.366779 -1.401912 -0.24227511 1 0 -2.619389 -0.883100 1.38337612 16 0 2.343797 -0.346422 0.072928
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Figure S8. DFT computed rotational potential functions for radicals 21, 26 and 27.
0
5
10
15
20
25
30
35
40
45
-90 -70 -50 -30 -10 10 30 50 70 90
a(H
-Be
ta)/
G
Theta/deg.
Figure S9. DFT computed a(H) values [UB3LYP/6-311+G(2d,p)] as a function of the dihedral angle theta ()
between the SOMO and the CH bond.
Table S23. Cyclopentylmethyl radical 26, UB3LYP/6-311+G(2d,p), E = -235.271710952.
CentreNumber
AtomicNumber
AtomicType
Coordinates (Angstroms)X Y Z
1 6 0 -0.004178 -1.197215 0.1747202 1 0 0.209128 -1.322217 1.241272
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3 1 0 0.252878 -2.136467 -0.3183924 6 0 0.826119 -0.001282 -0.3608495 1 0 0.768092 -0.014912 -1.4557386 6 0 2.248820 0.004540 0.0538677 1 0 2.507135 0.062501 1.1055068 1 0 3.058052 -0.071159 -0.6596709 6 0 -1.472549 -0.780783 -0.03941410 1 0 -2.127072 -1.202889 0.72542511 1 0 -1.834233 -1.152597 -1.00090912 6 0 -1.477953 0.775472 -0.02675813 1 0 -2.109314 1.177757 0.76763814 1 0 -1.875951 1.161732 -0.96771815 6 0 -0.005478 1.201306 0.15198816 1 0 0.239690 2.128056 -0.36994017 1 0 0.222909 1.357962 1.211211
Table S24. Tetrahydrofuranylmethyl radical 27, UB3LYP/6-311+G(2d,p), E = -271.182610301.
CentreNumber
AtomicNumber
AtomicType
Coordinates (Angstroms)X Y Z
1 8 0 -0.052687 -1.144240 -0.1089442 6 0 0.064742 1.197832 0.1879933 1 0 -0.121767 1.299847 1.2600714 1 0 -0.150030 2.153895 -0.2904815 6 0 -0.802932 0.052859 -0.3839826 1 0 -0.866117 0.182931 -1.4762827 6 0 -2.165635 -0.063322 0.1749298 1 0 -2.338866 -0.682711 1.0443629 1 0 -2.984009 0.503977 -0.24738010 6 0 1.480311 0.677484 -0.07567711 1 0 2.233311 1.125294 0.57447312 1 0 1.769895 0.873331 -1.11119413 6 0 1.320602 -0.827444 0.16367314 1 0 1.539044 -1.095066 1.20313715 1 0 1.957501 -1.432039 -0.486771
Table S25. 2-Phenylpyrrolomethyl radical 28, UB3LYP/6-31+G(d), E = -481.097360008.
CentreNumber
AtomicNumber
AtomicType
Coordinates (Angstroms)X Y Z
1 6 0 -1.645993 1.162228 0.2090682 6 0 -0.858119 0.029552 -0.0541453 6 0 -1.497707 -1.210986 -0.2354334 6 0 -2.884418 -1.310965 -0.1559565 6 0 -3.660654 -0.175418 0.1089396 6 0 -3.037370 1.060335 0.2925817 1 0 -1.175945 2.130652 0.3547128 1 0 -0.886814 -2.084733 -0.4382899 1 0 -3.364535 -2.275673 -0.30042010 1 0 -4.743074 -0.255691 0.170754
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11 1 0 -3.631490 1.946866 0.49951612 6 0 0.616786 0.128056 -0.13880513 6 0 1.371022 1.447703 -0.01071814 6 0 2.779109 -0.516494 -0.30064515 6 0 2.801532 1.043493 -0.41496116 1 0 1.311688 1.814393 1.02363117 1 0 0.953503 2.232223 -0.65173718 1 0 3.243041 -0.963231 -1.19830919 1 0 3.569393 1.498468 0.21758120 1 0 3.002246 1.340156 -1.45051921 7 0 1.357793 -0.907583 -0.30070922 6 0 3.466213 -1.057019 0.91219323 1 0 3.032951 -1.885625 1.46260224 1 0 4.482080 -0.747640 1.142736
Table S26. 1-Methyl-pyrrolidin-2-on-5-methyl radical (model for 29), E = -364.603412866.
CentreNumber
AtomicNumber
AtomicType
Coordinates (Angstroms)X Y Z
1 6 0 -0.239854 -1.698600 0.1557752 6 0 1.084644 -1.322695 -0.5242163 6 0 1.177817 0.235534 -0.3603994 1 0 -0.775910 -2.515379 -0.3350875 1 0 -0.107104 -1.981190 1.2078916 1 0 1.045799 -1.563108 -1.5928637 1 0 1.956420 -1.825196 -0.0971988 1 0 1.579948 0.676079 -1.2843489 7 0 -0.231435 0.614753 -0.21799810 6 0 -1.072096 -0.418656 0.10745711 8 0 -2.272583 -0.318436 0.33396912 6 0 2.014752 0.683073 0.79532813 1 0 3.078774 0.861062 0.66864414 1 0 1.602988 0.700650 1.80075915 6 0 -0.667992 1.995780 -0.27851916 1 0 -1.752146 2.011199 -0.14815817 1 0 -0.200365 2.596250 0.51213718 1 0 -0.411314 2.437238 -1.250098
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