LETTER
Synthesis of (E)-1-Aryl Alk-1-en-3-ones
2939
Table 2 Palladium-Catalysed Coupling of Aryl Halides with Pent-1-en-3-one or Hex-1-en-3-one17 (Scheme 1)a (continued)
Entry Aryl bromide
Enone
Ligand
Product
number
Ratio substrate/ Yield (%)b
catalyst
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
4-Bromobenzonitrile
Hex-1-en-3-one
Hex-1-en-3-one
Hex-1-en-3-one
Hex-1-en-3-one
Hex-1-en-3-one
Hex-1-en-3-one
Hex-1-en-3-one
Hex-1-en-3-one
Hex-1-en-3-one
Hex-1-en-3-one
Hex-1-en-3-one
Hex-1-en-3-one
Hex-1-en-3-one
Hex-1-en-3-one
Hex-1-en-3-one
Hex-1-en-3-one
Tedicyp
Tedicyp
Tedicyp
Tedicyp
Tedicyp
Tedicyp
Tedicyp
Tedicyp
Tedicyp
Tedicyp
PPh3
24
250
10000
100000
250
55c
100 (90)
82
4-Bromobenzonitrile
24
4-Bromobenzonitrile
24
4-Bromonitrobenzene
4-Bromonitrobenzene
4-Bromoanisole
2518
2518
26
100 (88)
92
1000
100
100 (90)
37c
4-Bromoanisole
26
250
4-Bromoanisole
26
250
60
4-N,N-Dimethylaminobromobenzene
4-N,N-Dimethylaminobromobenzene
4-N,N-Dimethylaminobromobenzene
4-N,N-Dimethylaminobromobenzene
3-Bromothiophene
2718
2718
2718
2718
28
100
60c
250
76 (68)
10
250
dppe
250
11
Tedicyp
Tedicyp
PPh3
250
100 (87)
42
3-Bromothiophene
28
1000
1000
1000
3-Bromothiophene
28
5
3-Bromothiophene
dppe
28
7
a Conditions: [ClPd(C3H5)]2/Tedicyp = 1:2, see ref. 13 or [ClPd(C3H5)]2/PPh3 = 1:4 or [ClPd(C3H5)]2/dppe = 1:2, aryl halide (1 mmol), pent-1-
en-3-one (4 mmol) or hex-1-en-3-one (2 mmol), NaOAc (2 mmol), hydroquinone (0.08 mmol), DMF, 110 °C, 20 h, argon, GC and NMR yields.
b Isolated yields in parentheses.
c Reaction performed without hydroquinone.
(6) Aslam, M.; Elango, V.; Davenport, K. G. Synthesis 1989,
References and Notes
869.
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Synlett 2006, No. 18, 2935–2940 © Thieme Stuttgart · New York