Table 1. Optimization of the Reaction Conditionsa
Scheme 1. Transition Metal-Catalyzed Heck-Type Reactions
yield(%)b
3a 4a
25 22
entry catalyst
ligand
solvent
1
2
3
4
5
6
7
8
9
Pd(OAc)2
Pd(acac)2
Pd(COD)Cl2
Pd(CH3CN)2Cl2
PdBr2
DMF
DMF
DMF
DMF
DMF
DMF
DMF
DMF
DMF
DMF
DMF
13
28
30
60
80
63
50
45
88
1
8
35
35
20
18
27
30
33
10
10
this process is that water is the only waste when dioxygen is
used as the terminal oxidant.9
PdOI2
In 2002, Myers and co-workers reported a Pd-catalyzed
decarboxylative Heck coupling of benzoic acids with olefins,
providing an attractive alternative to traditional Heck
couplings.10 Since then, this protocol has been widely inves-
tigated by using carboxylic acids as the aryl sources (eq 3).11
Similarly, decarbonylative Heck-type reactions were also
developed using carbonyl compounds such as carbonic acid
chlorides,12 anhydrides,13 and esters14 as substrates.
PdCl2
PPh3
PdCl2
dppe
PdCl2
dppb
10 PdCl2
11 PdCl2
12 PdCl2
13 PdCl2
14 PdCl2
15 PdCl2
16 PdCl2
17 PdCl2
18c PdCl2
DPEphos
1,10-Phen
L-phenylalanine DMF
n.d. 60
1,4-dioxane 77 22
DPEphos
DPEphos
DPEphos
DPEphos
DPEphos
DPEphos
DMSO
diglyme
anisole
70
90
95
28
1
Arenesulfonyl chlorides are active compounds and are
used as starting materials for preparing compounds con-
taining a sulfonyl group. The sulfonyl group is common in
organic materials, bioactive molecules, and pharmaceu-
ticals.15 Arenesulfonyl chlorides are also used as aryl
sources for C-C bond forming reactions via desulfitative
Heck-type reactions. The first palladium-catalyzed desul-
fitative C-C double bond-forming reactions with arene-
sulfonyl chlorides were developed by Kasahara et al. and
Miura and co-workers under high reaction temperature
(>130 °C).16 Compared to the active and moisture
n.d.
n.d.
30
anisole/H2O 90
anisole 50
a Conditions: 1a (0.4 mmol), 2a (0.2 mmol), catalyst (5 mol %),
ligand (5 mol %), solvent (0.4 mL), 85 °C, 24 h under an atmosphere of
oxygen unless otherwise noted. b GC yield based on 2a. n.d. = not
detected (below 1% yield), the E/Z ratio is >20:1 as determined by 1H
NMR. c Under air.
sensitive arenesulfonyl chloride, sulfinic acid sodium salts
are stable and easy to handle. Thus, sulfinic acid sodium
salts have the potential to serve as the ideal aryl sources for
(9) For oxidative Heck-type reaction using oxygen as terminal
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Angew. Chem., Int. Ed. 2003, 42, 3512. (b) Yokota, T.; Tani, M.;
Sakaguchi, S.; Ishii, Y. J. Am. Chem. Soc. 2003, 125, 1476. (c) Tani,
M.; Sakaguchi, S.; Ishii, Y. J. Org. Chem. 2004, 69, 1221. (d) Ferreira,
E. M.; Stoltz, B. M. J. Am. Chem. Soc. 2003, 125, 9578. (e) Weissman, H.;
Song, X.; Milstein, D. J. Am. Chem. Soc. 2001, 123, 337. (f) Wang, D.;
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2002, 124, 11250.
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H.; Itoh, K.; Nomura, M. J. Chem. Soc., Perkin Trans.1 1990, 8, 2207.
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(e) Dubbaka, S.; Steunenberg, P.; Vogel, P. Synlett 2004, 1235. (f)
Dubbaka, S.; Vogel, P. Adv. Synth. Catal. 2004, 346, 1793. (g) Dubbaka,
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ꢀ
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(13) Stephan, M.; Teunissen, A.; Verzijl, G.; de Vries, J. Angew.
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(14) (a) Goossen, L. J.; Paetzold, J. Angew. Chem., Int. Ed. 2002, 41,
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(a) Sandrinelli, F.; Perrio, S.; Beslin, P. Org. Lett. 1999, 1, 1177. (b)
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ꢀ
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