benzoyl radicals from (hetero)aromatic aldehydes ... · benzoyl radicals from (hetero)aromatic...

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.

[email protected]

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.


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.


S4

2) 1H-NMR and 13C-NMR spectra of compounds 3-9, 11-15

Compound 3.

O

MeO

COOMe

COOMe

1H-NMR


S5

Compound 3.

O

MeO

COOMe

COOMe

13C-NMR


S6

Compound 4. O

MeO

O

1H-NMR


S7

Compound 4. O

MeO

O

13C-NMR


S8

Compound 5.

O

MeO O

1H-NMR (CDCl3)


S9

Compound 5.

O

MeO O

13C-NMR


S10

Compound 5.

O

MeO O

1H-NMR (C6D6)


S11

Compound 5.

O

MeO O

1H-NMR (C6D6, enlarged portion)


S12

Compound 5.

O

MeO O

Long-range COSY


S13

Compound 5.

O

MeO O

Long-range COSY (enlarged portion)


S14

Compound 5.

O

MeO O

NOESY


S15

Compound 5.

O

MeO O

NOESY (enlarged portion)


S16

Compound 6. O

COOMe

1H-NMR


S17

Compound 6. O

COOMe

13C-NMR


S18

Compound 7. O

ClO

1H-NMR


S19

Compound 7. O

ClO

13C-NMR


S20

Compound 8. OCl

COOMe

1H-NMR


S21

Compound 8. OCl

COOMe

13C-NMR


S22

Compound 9. O

COOMe

1H-NMR


S23

Compound 9. O

COOMe

13C-NMR


S24

Compound 11. O

t-BuMe2SiOO

1H-NMR


S25

Compound 11. O

t-BuMe2SiOO

13C-NMR


S26

Compound 12.

O

O

OHC

1H-NMR


S27

Compound 12.

O

O

OHC

13C-NMR


S28

Compound 13.

SO

COOMe

1H-NMR


S29

Compound 13.

SO

COOMe

13C-NMR


S30

Compound 14.

N

CN

O

1H-NMR


S31

Compound 14.

N

CN

O

13C-NMR


S32

Compound 15.

N

COOMe

O

1H-NMR


S33

Compound 15.

N

COOMe

O

13C-NMR


benzoyl radicals from (hetero)aromatic aldehydes ... · benzoyl radicals from (hetero)aromatic...

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