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S1
Supplementary Material (ESI) for OBC
Benzoyl Radicals from (Hetero)aromatic Aldehydes.
Decatungstate Photocatalyzed Synthesis
of Substituted Aromatic Ketones.
Davide Ravelli,§ Michele Zema,† Mariella Mella,§ Maurizio Fagnoni, *,§ and Angelo Albini§
§Department of Organic Chemistry, University of Pavia, Viale Taramelli 10, 27100 Pavia, Italy
†Department of Earth Sciences, University of Pavia, Via Ferrata 1, 27100 Pavia, Italy.
fagnoni@unipv.it
1) Selected absorption spectra of starting aldehydes, TBADT and reaction
mixture. S2-S3
2) 1H-NMR and 13C-NMR spectra of compounds 3-9, 11-15 S4-S33
Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is (c) The Royal Society of Chemistry 2010
S2
1) Selected absorption spectra of starting aldehydes, TBADT and reaction
mixture.
Figure S1 Absorption spectra of selected aldehydes (0.1 M) and of TBADT (0.002 M, these are the
concentration used in preparative experiments).
As it is apparent from Figure S1, when the competitive absorption of the aldehyde is not
overwhelming (as for aldehydes 1a-c) the reaction occurred whereas where the absorption is
comparable with TBADT (e.g. for napthaldehyde and 4-aminobenzaldehyde) no acylation took
place.
Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is (c) The Royal Society of Chemistry 2010
S3
Figure S2 Selected absorption spectra concerning the TBADT photocatalyzed reaction between
dimethyl maleate (2a) and anisaldehyde (1a) in MeCN.
Figure S2 ruled out both a possible competitive absorption of the olefin (e.g. dimethyl maleate)
used as radical traps and the formation of ground state complexes. In fact the absorption spectra of
TBADT is virtually superimposable to that of the overall reaction mixture containing aldehyde 1a
and olefin 2a confirming again that the photocatalyst is by far the main absorbing species in
solution.
Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is (c) The Royal Society of Chemistry 2010
S4
2) 1H-NMR and 13C-NMR spectra of compounds 3-9, 11-15
Compound 3.
O
MeO
COOMe
COOMe
1H-NMR
Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is (c) The Royal Society of Chemistry 2010
S5
Compound 3.
O
MeO
COOMe
COOMe
13C-NMR
Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is (c) The Royal Society of Chemistry 2010
S6
Compound 4. O
MeO
O
1H-NMR
Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is (c) The Royal Society of Chemistry 2010
S7
Compound 4. O
MeO
O
13C-NMR
Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is (c) The Royal Society of Chemistry 2010
S8
Compound 5.
O
MeO O
1H-NMR (CDCl3)
Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is (c) The Royal Society of Chemistry 2010
S9
Compound 5.
O
MeO O
13C-NMR
Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is (c) The Royal Society of Chemistry 2010
S10
Compound 5.
O
MeO O
1H-NMR (C6D6)
Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is (c) The Royal Society of Chemistry 2010
S11
Compound 5.
O
MeO O
1H-NMR (C6D6, enlarged portion)
Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is (c) The Royal Society of Chemistry 2010
S12
Compound 5.
O
MeO O
Long-range COSY
Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is (c) The Royal Society of Chemistry 2010
S13
Compound 5.
O
MeO O
Long-range COSY (enlarged portion)
Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is (c) The Royal Society of Chemistry 2010
S14
Compound 5.
O
MeO O
NOESY
Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is (c) The Royal Society of Chemistry 2010
S15
Compound 5.
O
MeO O
NOESY (enlarged portion)
Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is (c) The Royal Society of Chemistry 2010
S16
Compound 6. O
COOMe
1H-NMR
Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is (c) The Royal Society of Chemistry 2010
S17
Compound 6. O
COOMe
13C-NMR
Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is (c) The Royal Society of Chemistry 2010
S18
Compound 7. O
ClO
1H-NMR
Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is (c) The Royal Society of Chemistry 2010
S19
Compound 7. O
ClO
13C-NMR
Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is (c) The Royal Society of Chemistry 2010
S20
Compound 8. OCl
COOMe
1H-NMR
Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is (c) The Royal Society of Chemistry 2010
S21
Compound 8. OCl
COOMe
13C-NMR
Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is (c) The Royal Society of Chemistry 2010
S22
Compound 9. O
COOMe
1H-NMR
Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is (c) The Royal Society of Chemistry 2010
S23
Compound 9. O
COOMe
13C-NMR
Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is (c) The Royal Society of Chemistry 2010
S24
Compound 11. O
t-BuMe2SiOO
1H-NMR
Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is (c) The Royal Society of Chemistry 2010
S25
Compound 11. O
t-BuMe2SiOO
13C-NMR
Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is (c) The Royal Society of Chemistry 2010
S26
Compound 12.
O
O
OHC
1H-NMR
Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is (c) The Royal Society of Chemistry 2010
S27
Compound 12.
O
O
OHC
13C-NMR
Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is (c) The Royal Society of Chemistry 2010
S28
Compound 13.
SO
COOMe
1H-NMR
Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is (c) The Royal Society of Chemistry 2010
S29
Compound 13.
SO
COOMe
13C-NMR
Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is (c) The Royal Society of Chemistry 2010
S30
Compound 14.
N
CN
O
1H-NMR
Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is (c) The Royal Society of Chemistry 2010
S31
Compound 14.
N
CN
O
13C-NMR
Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is (c) The Royal Society of Chemistry 2010
S32
Compound 15.
N
COOMe
O
1H-NMR
Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is (c) The Royal Society of Chemistry 2010