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Palladium-Catalyzed Hiyama Cross-Couplings of Aryl Arenesulfonates With Arylsilanes
Palladium-Catalyzed Hiyama Cross-Couplings of Aryl Arenesulfonates With Arylsilanes
Fudan University.
Chinese Academy of Sciences.
12250
entry
[Pd] catalyst
ligand
yield (%)b
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20c
21d
Pd(OAc)2 (2 mol %)
Pd(OAc)2 (2 mol %)
Pd(OAc)2 (2 mol %)
Pd(OAc)2 (2 mol %)
Pd(OAc)2 (2 mol %)
Pd(OAc)2 (2 mol %)
Pd(OAc)2 (2 mol %)
Pd(OAc)2 (2 mol %)
Pd(OAc)2 (2 mol %)
Pd(OAc)2 (2 mol %)
Pd(OAc)2 (2 mol %)
Pd(OAc)2 (4 mol %)
Pd(PPh3)4 (4 mol %)
Pd2(dba)3 (4 mol %)
Pd(PPh3)2Cl2 (4 mol %)
Pd(PhCN)2Cl2 (4 mol %)
[Pd(C3H5)Cl]2 (4 mol %)
PdCl2 (4 mol %)
Pd(dppf)Cl2 (4 mol %)
Pd(OAc)2 (4 mol %)
Pd(OAc)2 (4 mol %)
S-Phos (5 mol %)
XPhos (5 mol %)
JohnPhos (5 mol %)
CyJohnPhos (5 mol %)
PCy3 (5 mol %)
P(o-tolyl)3
DPPP
DPPF
IPr HCl
SIPr HCl
IMes HCl
XPhos (10 mol %)
XPhos (10 mol %)
XPhos (10 mol %)
XPhos (10 mol %)
XPhos (10 mol %)
XPhos (10 mol %)
XPhos (10 mol %)
XPhos (10 mol %)
XPhos (10 mol %)
XPhos (10 mol %)
13
67
trace
trace
trace
trace
trace
trace
trace
trace
nr
88
34
trace
trace
81
58
26
16
trace
trace
a
Reaction conditions: tBuC6H4OTs 1a (0.30 mmol), PhSi(OMe)3 2a
(2.0 equiv), TBAF (1.0 M in THF, 2.0 equiv), 80 C, 10 h. b Isolated
yield based on aryl tosylate 1a. c The reaction performed at 30 C. d The
reaction performed at 50 C.
COMMUNICATIONS
Table 2. Pd-Catalyzed Hiyama Cross-Coupling Reactions of
Arenesulfonate 1 with Arylsilane 2
entry
R1/Ar
1
2
3
4
5
6
7
8
4-t-BuC6H4/4-MeC6H4 1a
4-PhC6H4/4-MeC6H4 1b
4-EtO2CC6H4/4-MeC6H4 1c
4-NCC6H4/4-MeC6H4 1d
R-naphthyl/4-MeC6H4 1e
R-naphthyl/C6H5 1f
-naphthyl/4-MeC6H4 1g
3-morpholinylphenyl/
4-MeC6H4 1h
3-MeOC6H4/4-MeC6H4 1i
4-tert-pentylphenyl/
4-MeC6H4 1j
4-CF3C6H4/4-MeC6H4 1k
-naphthyl/4-MeC6H4 1g
R-naphthyl/4-MeC6H4 1e
3-MeC6H4/4-MeC6H4 1l
3-morpholinylphenyl/
4-MeC6H4 1h
-naphthyl/4-MeC6H4 1g
R-naphthyl/C6H5 1f
R-naphthyl/4-MeC6H4 1e
3-MeOC6H4/4-MeC6H4 1i
4-t-BuC6H4/4-MeC6H4 1a
2-MeC6H4/4-MeC6H4 1m
3-pyridinyl/4-MeC6H4 1n
-naphthyl/4-MeC6H4 1g
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
a
R2/R
C6H5/Me
C6H5/Me
C6H5/Me
C6H5/Me
C6H5/Me
C6H5/Me
C6H5/Me
C6H5/Me
Scheme 1
yield (%)a
2a
2a
2a
2a
2a
2a
2a
2a
88 (3a)
67 (3b)
62 (3c)
72 (3d)
88 (3e)
94 (3e)
95 (3f)
97 (3g)
C6H5/Me 2a
C6H5/Et 2b
85 (3h)
81 (3i)
C6H5/Et 2b
C6H5/Et 2b
4-MeOC6H4/Me 2c
4-MeOC6H4/Me 2c
4-MeC6H4/Me 2d
81 (3j)
99 (3f)
81 (3k)
68 (3l)
81 (3m)
4-MeC6H4/Me 2d
4-MeC6H4/Me 2d
4-CF3C6H4/Me 2e
4-CF3C6H4/Me 2e
2-MeC6H4/Me 2f
C6H5/Me 2a
C6H5/Me 2a
2-thiophenyl/Et 2g
78 (3n)
63 (3o)
91 (3p)
85 (3q)
53 (3r)
30 (3s)
31 (3t)
trace
JA804672M
12251