Highly regio- and stereoselective palladium(0)-catalyzed addition of organoboronic acids with 1,2-allenic sulfones, sulfoxides, or alkyl- or aryl-substituted allenes in the presence of acetic acid: An efficient synthesis of E-alkenes

Article abstract of DOI:10.1055/s-2007-983822

Two sets of reaction conditions were established to enable the palladium(0)-catalyzed addition of organoboronic acids with 1,2-allenic sulfones, sulfoxides, or alkyl- or aryl-substituted allenes in the presence of acetic acid. This reaction provides a new

Full text of DOI:10.1055/s-2007-983822

FEATURE ARTICLE
2731
Highly Regio- and Stereoselective Palladium(0)-Catalyzed Addition of
Organoboronic Acids with 1,2-Allenic Sulfones, Sulfoxides, or Alkyl- or
Aryl-Substituted Allenes in the Presence of Acetic Acid: An Efficient Synthesis
of E-Alkenes
P
alladium(0)-Cata
a
lyze
d
A
ddit
o
ion of
O
rganoboro
G
nic
A
cids
w
ith
A
ll
u
e
nes o, Shengming Ma*
State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences,
354 Fenglin Lu, Shanghai 200032, P. R. of China
Fax +86(21)64167510; E-mail: masm@mail.sioc.ac.cn
Received 2 May 2007; revised 10 June 2007
search program on the chemistry of allenes,7 the
Abstract: Two sets of reaction conditions were established to en-
palladium-catalyzed addition of 1,2-allenic sulfones, sulf-
able the palladium(0)-catalyzed addition of organoboronic acids
oxides, or alkyl- or aryl-substituted allenes with orga-
noboronic acids in the presence of acetic acid.
with 1,2-allenic sulfones, sulfoxides, or alkyl- or aryl-substituted al-
lenes in the presence of acetic acid. This reaction provides a new
way for the stereoselective synthesis of tri- or tetrasubstituted E-alk-
enes. With arylboronic acids, the reactions of 1,2-allenic sulfones,
sulfoxides, and alkyl-substituted allenes gave only 1–12% of specif-
ic regioisomers; the reactions of aryl-substituted allenes afforded
only E-alkenes in very high regioselectivity.
Results and Discussion
Reactions of 1,2-Allenic Sulfones or Sulfoxides
Key words: allenes, sulfones, sulfoxides, palladium, addition reac-
Multisubstituted alk-1-enyl sulfoxides or sulfones are
very important in organic synthesis,8 and therefore highly
stereoselective methods for their preparation are highly
desirable. On the other hand, 1,2-allenic sulfones or sul-
foxides show good reactivities.9–11 For example, we have
reported the hydrohalogenation of 1,2-allenic sulfones9a
and sulfoxides9b and the E-halohydroxylation reaction of
1,2-allenic sulfoxides.9c We have also recently reported
the first Heck-type cross-coupling reaction of 1,2-allenic
sulfones with aryl halides.10 Mukai et al. have reported the
intramolecular nucleophilic addition of 1,2-allenic sul-
fones.11 Considering their useful reactivities, we were in-
terested to see whether we could control the regio- and
stereoselectivities in the addition of 1,2-allenic sulfones or
sulfoxides with organoboronic acids in the presence of
acetic acid.
tions, boron
Introduction
The highly stereoselective synthesis of multisubstituted
alkenes is one of the most important topics in organic
chemistry, since many issues need be considered. Recent-
ly, transition-metal-catalyzed addition of organic boronic
reagents with allenes has caught the attention of synthetic
organic chemists. We1 and Oh et al.2 have reported the
palladium-catalyzed reaction of functionalized allenes
with organoboronic acids in the presence of acetic acid. It
provides a new synthetic method for the formation of tri-
or tetrasubstituted E-alkenes. However, the regio- and ste-
reoselectivities have not been satisfactory. Yoshida and
Ihara et al.3 reported the palladium-catalyzed coupling re-
action of allenic alcohols with organoboronic acids, in
which the hydroxy group was used as a leaving group, and
which yielded substituted dienes and trienes. Oh et al.4
also reported the palladium-catalyzed reaction of 1,6-al-
lenynes with organoboronic acids in the presence of acetic
acid, which afforded six-membered-ring products. In the
meantime, some palladium-catalyzed three-component
coupling reactions involving boronic reagents and allenes
have also been reported.5 Very recently, Hayashi et al.6 re-
ported the rhodium-catalyzed asymmetric addition of al-
lenes with arylboronic acids affording (S)-2-aryl-3-
(diphenylphosphinyl)alkenes in high yields and enanti-
oselectivity. We wish to report here, as part of our re-
1,2-Allenic sulfones 2 are readily available by oxidation
of the corresponding sulfoxides 1, which are easily pre-
pared by the reaction of the corresponding propargylic al-
cohols with benzenesulfenyl chloride (PhSCl)
(Scheme 1).12 Six compounds have been synthesized by
this literature procedure.12
Under the catalysis of 10 mol% of tetrakis(triphenylphos-
phine)palladium, the reaction of phenyl propa-1,2-dienyl
sulfone (2a) with phenylboronic acid (3a) in the presence
of 100 mol% acetic acid failed to afford the addition prod-
ucts in dimethyl sulfoxide, dioxane, N,N-dimethylform-
amide, dimethylacetamide (DMA), or ethanol (Table 1,
entries 1–5). Fortunately, the same reaction afforded the
hydroarylation product in solvents such as, acetone, ace-
tonitrile, diethyl ether, toluene, dichloromethane, and tet-
rahydrofuran (Table 1, entries 6–11). The best result was
obtained in tetrahydrofuran, with product (E)-4aa form-
SYNTHESIS 2007, No. 17, pp 2731–2745
Advanced online publication: 30.07.2007
x
x.
x
x
.
2
0
0
7
DOI: 10.1055/s-2007-983822; Art ID: E18607SS
© Georg Thieme Verlag Stuttgart · New York

2732
H. Guo, S. Ma
FEATURE ARTICLE
R2
R3
PhO2S
R1
R2
R3
OH
R2
R3
PhOS
R1
Et3N
H2O2
PhSCl
R1
+
CH2Cl2
–78 °C
AcOH
100 °C
1
2
1a, 2a: R1 = R2 = R3 = H
1b, 2b: R1 = Me, R2 = R3 = H
1c, 2c: R1 = n-Bu, R2 = R3 = H
Scheme 1 Preparation of 1,2-allenic sulfones and sulfoxides
ing in a regioselectivity of 91:9 (4aa/5aa) and a stereose- sulfoxide (1a) with phenylboronic acid (3a) under condi-
lectivity of >99:1 [(E)-4aa/(Z)-4aa] (Table 1, entry 11).
tions A (Table 5, entry 1). This showed that, fortunately,
the reaction can be extended to 1,2-allenic sulfoxides. The
reaction of phenyl propa-1,2-dienyl sulfoxide (1a) with
different organoboronic acids 3 under conditions A af-
forded products 6 in slightly lower yields than those of
products 4 from 2a (Table 5, cf. Table 4). However, when
we tried the reaction of 1,2-allenic sulfoxides 5b and 5c
with phenylboronic acid (3a), none of the expected prod-
ucts formed (Scheme 2). Sulfoxide (E)-6ab can be con-
verted into sulfone (E)-4ab in 52% yield by treatment
with hydrogen peroxide in acetic acid (Scheme 3).
With tetrahydrofuran as the solvent, the same reaction
with other catalysts was also studied. Unfortunately, no
better results were observed (Table 2).
We next studied the effect of the amount of acetic acid on
this reaction (Table 3, entries 1–4), and found that 100
mol% acetic acid was necessary (Table 3, entry 3). The re-
action under reflux afforded the product in lower yield
(Table 3, entry 5).
The results obtained thus far were combined into condi-
tions A [Pd(PPh3)4 (10 mol%), AcOH (100 mol%), THF,
r.t.] and applied in the regio- and stereoselective forma-
tion of E-alkenyl sulfones (E)-4; some of the typical re-
sults are summarized in Table 4. The configurations of the
C=C bonds in 4 were determined by an X-ray diffraction
study of (E)-4ca13 (Figure 1).
PhOS
R
Pd(PPh3)4 (10 mol%)
PhB(OH)2
+
no expected products
AcOH (100 mol%)
THF, r.t.
1b: R = Me
3a
1c: R = n-Bu
Considering that the reactivities of 1,2-allenic sulfoxides
are nearly always the same as those of 1,2-allenic sul-
fones, we tried the addition of phenyl propa-1,2-dienyl
Scheme 2 Reactions of 1,2-allenic sulfoxides 1b and 1c with phe-
nylboronic acid (3a) under conditions A
Biographical Sketches
Hao Guo was born in Tian- degree in 2003, he joined ly
a
Ph.D. student in
jin, China in 1980. After the graduate school of the Professor Shengming Ma’s
graduation from Nankai Shanghai Institute of Organ- research group.
University with a bachelor’s ic Chemistry. He is current-
Shengming Ma is original- After postdoctoral research ary 2003 he has been jointly
ly from Zhejiang Province, at the ETH in Switzerland appointed by the SIOC and
China. He received a B.S. and the Purdue University in Zhejiang University, as Re-
degree in Chemistry from the USA, he joined the fac- search Professor of Chemis-
Hangzhou
University ulty of the Shanghai Insti- try at SIOC and Cheung
(1986), and an M.S. (1988) tute of Organic Chemistry Kong Scholars Program
and a Ph.D. degree (1990) (1997), where he is now the Professor at Zhejiang Uni-
from the Shanghai Institute director of the State Key versity.
of Organic Chemistry, Chi- Laboratory of Organometal-
nese Academy of Sciences. lic Chemistry. Since Febru-
Synthesis 2007, No. 17, 2731–2745 © Thieme Stuttgart · New York

FEATURE ARTICLE
Palladium(0)-Catalyzed Addition of Organoboronic Acids with Allenes
2733
Table 1 Tetrakis(triphenylphosphine)palladium-Catalyzed Addition of Phenyl Propa-1,2-dienyl Sulfone (2a) with Phenylboronic Acid (3a)
in Different Solventsa
PhO2S
Pd(PPh3)4 (10 mol%)
2a
+
+
+
AcOH (100 mol%)
r.t.
SO2Ph
B(OH)2
3a
SO2Ph
SO2Ph
(E)-4aa
(Z)-4aa
5aa
Entry
Solvent
Time (h)
Ratiob 4aa/5aa
Yieldc (%) of (E)-4aa
Ratiob (E)-4aa/(Z)-4aa
d
1
2
DMSO
dioxane
DMF
24
16
9
–
–
–
e
–
–
–
3
–
trace
trace
trace
70
–
4
DMA
9
–
–
5
EtOH
40
65
40
40
55
40
22
–
–
6
acetone
MeCN
Et2O
81:19
82:18
83:17
87:13
90:10
91:9
>99:1
>99:1
>99:1
>99:1
>99:1
>99:1
7
23
8
67
9
toluene
CH2Cl2
THF
48
10
11
48
68
a Reagents and conditions: 2a (0.25 mmol), 3a (2.0 equiv), Pd(PPh3)4 (10 mol%), AcOH (100 mol%), solvent (3 mL), r.t., under N2.
b Determined by 1H NMR (300 MHz) analysis of the crude reaction mixture obtained after filtration and evaporation.
c Isolated yield.
d Allene 2a (32%) was recovered.
e Allene 2a (56%) was recovered.
H2O2, AcOH
40 °C, 24 h
52%
SOPh
(E)-6ab
SO2Ph
(E)-4ab
Scheme 3 The formation of sulfone (E)-4ab from sulfoxide (E)-6ab
Reactions of Alkyl- or Aryl-Substituted Allenes
Non-functionalized allenes are also readily available, but
the reaction of deca-1,2-diene with (4-methoxyphe-
nyl)boronic acid afforded the addition products in low se-
lectivities.1a To further improve the selectivity, we studied
the addition of alkyl-substituted allene 8a with phenylbo-
ronic acid (3a) under conditions A (Table 6, entry 1).
However, this reaction afforded a mixture of regioisomer-
ic products 9aa and 10aa in low yield (Table 6, entry 1).
After some screening (Table 6, entries 2–8), conditions B
[Pd(PPh3)4 (10 mol%), AcOH (100 mol%), dioxane, re-
flux] (Table 6, entry 4) were established for the highly ste-
reoselective addition of organoboronic acids with alkyl-
Figure 1 ORTEP representation of (E)-4ca
Synthesis 2007, No. 17, 2731–2745 © Thieme Stuttgart · New York

2734
H. Guo, S. Ma
FEATURE ARTICLE
Table 2 Addition of Phenyl Propa-1,2-dienyl Sulfone (2a) with Phenylboronic Acid (3a) Catalyzed by Different Palladium Complexesa
PhO2S
[Pd] (10 mol%)
2a
+
+
AcOH (100 mol%)
THF, r.t.
+
SO2Ph
B(OH)2
3a
SO2Ph
(E)-4aa
SO2Ph
5aa
(Z)-4aa
Entry
Palladium catalyst
Pd(PhCN)2Cl2
Pd(OAc)2
Time (h)
Ratiob 4aa/5aa
Yieldc (%) of (E)-4aa
Ratiob (E)-4aa/(Z)-4aa
d
e
f
1
2
3
4
5
6
7
8
65
61
65
65
61
41
9
–
–
–
–
–
–
–
–
–
–
PdCl2
–
–
g
h
i
PdCl2
–
–
g
Pd(PhCN)2Cl2
–
–
j
Pd(dba)2
–
–
g
Pd(dba)2
90:10
90:10
61
78
>99:1
>99:1
g
Pd(OAc)2
12
a Reagents and conditions: 2a (0.25 mmol), 3a (2.0 equiv), Pd catalyst (10 mol%), AcOH (100 mol%), THF (3 mL), r.t., under N2.
b Determined by 1H NMR (300 MHz) analysis of the crude reaction mixture obtained after filtration and evaporation.
c Isolated yield.
d Allene 2a (57%) was recovered.
e Allene 2a (67%) was recovered.
f Allene 2a (79%) was recovered.
g PPh3 (20 mol%) was also used.
h Allene 2a (44%) was recovered.
i Allene 2a (84%) was recovered.
j Complex mixture.
Table 3 Palladium(0)-Catalyzed Addition of Phenyl Propa-1,2-dienyl Sulfone (2a) with Phenylboronic Acid (3a) in the Presence of Different
Amounts of Acetic Acida
PhO2S
Pd(PPh3)4 (10 mol%)
2a
+
+
+
AcOH
SO2Ph
THF, r.t.
B(OH)2
SO2Ph
(E)-4aa
SO2Ph
5aa
(Z)-4aa
3a
Entry
Amount of AcOH (mol%) Time (h)
Ratiob 4aa/5aa
86:14
Yieldc (%) of (E)-4aa
Ratiob (E)-4aa/(Z)-4aa
1
20
50
24
24
22
24
7
65
68
68
57
54
>99:1
>99:1
>99:1
>99:1
>99:1
2
87:13
3
100
200
100
91:9
4
90:10
5d
90:10
a Reagents and conditions: 2a (0.25 mmol), 3a (2.0 equiv), Pd(PPh3)4 (10 mol%), AcOH, THF (3 mL), r.t., 24 h, under N2.
b Determined by 1H NMR (300 MHz) analysis of the crude reaction mixture obtained after filtration and evaporation.
c Isolated yield.
d The reaction was carried out under reflux.
Synthesis 2007, No. 17, 2731–2745 © Thieme Stuttgart · New York

FEATURE ARTICLE
Palladium(0)-Catalyzed Addition of Organoboronic Acids with Allenes
2735
Table 4 Palladium(0)-Catalyzed Addition Reactions of 1,2-Allenic Sulfones 2 with Organoboronic Acids 3 under Conditions Aa
PhO2S
R2
R2
R1
R1
Pd(PPh3)4 (10 mol%)
AcOH (100 mol%)
R1
+
2
SO2Ph
SO2Ph
+
THF, r.t.
R2-B(OH)2
(E)-4
5
3
Entry
R1
H
2
R2
3
Time (h)
22
Product 4 Ratiob 4/5 Yieldc (%) of (E)-4 Ratiob (E)-4/(Z)-4
1
2
2a
2a
2a
2a
2a
2a
2a
2a
2a
2a
2b
2c
Ph
3a
3b
3c
3d
3e
3f
4aa
4ab
4ac
4ad
4ae
4af
4ag
4ah
4ai
91:9
68
62
35
78
66
80
80
73
72
52
50
55
>99:1
>99:1
>99:1
>99:1
>99:1
>99:1
>99:1
>99:1
>99:1
>99:1
>99:1
>99:1
H
4-Tol
22
>99:1
>97:3
93:7
3
H
3-MeOC6H4
4-MeOC6H4
3-O2NC6H4
3-AcC6H4
4-AcC6H4
1-Naph
59
4
H
17.5
19
5
H
94:6
6
H
22
>99:1
94:6
7
H
3g
3h
22
8
H
21.5
25
91:9
9
H
(E)-CH=CH(CH2)4Me 3i
90:10
94:6
10
11
12
H
(E)-CH=CHPh
3j
11
4aj
4ba
4ca
Me
n-Bu
Ph
Ph
3a
3a
72
>99:1
>99:1
96
a Reagents and conditions (conditions A): 2 (0.25 mmol), 3 (2.0 equiv), Pd(PPh3)4 (10 mol%), AcOH (100 mol%), THF, r.t., under N2.
b Determined by 1H NMR (300 MHz) analysis of the crude reaction mixture obtained after filtration and evaporation.
c Isolated yield.
substituted allenes. The configurations of the C=C bonds Conclusion
1
in 9 were determined by the H–1H NOESY spectra of
(E)-9aa (Figure 2). The highest regioselectivity observed We have succeeded in establishing two sets of reaction
was 92:8 (Table 6, entry 4).
conditions for the addition reaction of allenes with orga-
noboronic acids: conditions A for the addition of orga-
noboronic acids with 1,2-allenic sulfones or sulfoxides
affording E-alkenyl sulfones or sulfoxides; conditions B
for the addition of organoboronic acids with alkyl- or aryl-
substituted allenes affording E-alkenes. The generality of
this reaction was studied, with some typical results report-
ed. Further studies in this area and the synthetic applica-
tions of this reaction are being carried out in our
laboratory.
Some typical results of the reactions between alkyl-substi-
tuted allenes 8 and organoboronic acids 3 under condi-
tions B are shown in Table 7. We then tried to extend
conditions B to aryl-substituted allenes; typical results are
shown in Table 8. It should be noted that both the regio-
and stereoselectivities are excellent. Both electron-donat-
ing and electron-withdrawing groups can be attached to
the aryl group (Table 8, entries 6–8).
Melting points were determined on a SGW X-4 apparatus. IR spec-
tra were recorded on a Nicolet Avatar 360 FT-IR spectrometer. 1H
(300 MHz) and 13C (75.4 MHz) NMR spectra of samples in CDCl3
(unless stated otherwise) were recorded on a Varian Mercury
VX300 spectrometer. MS (EI, 70 eV) determinations were carried
out on a HP 5973 spectrometer. HRMS (MALDI) determinations
were carried out on a Ionspec MALDI-FTMS spectrometer. HRMS
(EI) determinations were carried out on a Water GCT CA176 spec-
trometer. Elemental analyses were carried out on a Elementar Vario
EL instrument. Column chromatography was performed on silica
gel (10–40 u). The starting materials 1a,12 1b,12 1c,12 2a,12 2b,12
8a,14 8b,14 8c,14 8d,14 8e,14 11a,15 11b,1511c,15 and 11d15 were pre-
pared according to literature procedures.
H
NOE
H
n-C8H17
(E)-9aa
Figure 2 1H–1H NOESY interaction of (E)-9aa
Synthesis 2007, No. 17, 2731–2745 © Thieme Stuttgart · New York

2736
H. Guo, S. Ma
FEATURE ARTICLE
Table 5 Palladium(0)-Catalyzed Addition Reaction of Phenyl Propa-1,2-dienyl Sulfoxide (1a) with Different Organoboronic Acids 3 under
Conditions Aa
PhOS
R
R
R
1a
Pd(PPh3)4 (10 mol%)
+
+
SOPh
+
AcOH (100 mol%)
THF, r.t.
SOPh
(E)-6
SOPh
R-B(OH)2
(Z)-6
7
3
Entry
R
3
Time (h)
72
Product 6
6aa
Ratiob 6/7
94:6
Yieldc (%) of (E)-6
Ratiob (E)-6/(Z)-6b
>99:1
1
2
3
4
5
6
7
8
9
Ph
3a
3b
3c
3d
3e
3g
3h
3k
3j
50
58
59
52
49
48
41
53
46
4-Tol
36
6ab
>97:3
99:1
>99:1
3-MeOC6H4
4-MeOC6H4
3-O2NC6H4
12
6ac
>99:1
24.5
48
6ad
95:5
>99:1
6ae
>96:4
>99:1
>94:6
>92:8
>94:6
>99:1
4-AcC6H4
48
6ag
>99:1
1-Naph
24
6ah
>99:1
(E)-CH=CH(CH2)3Me
(E)-CH=CHPh
72
6ak
>99:1
50
6aj
>99:1
a Reagents and conditions (conditions A): 1a (0.25 mmol), 3 (2.0 equiv), Pd(PPh3)4 (10 mol%), AcOH (100 mol%), THF, r.t., under N2.
b Determined by 1H NMR (300 MHz) analysis of the crude reaction mixture obtained after filtration and evaporation.
c Isolated yield.
Table 6 Palladium(0)-Catalyzed Addition of Alkyl-Substituted Allene 8a with Phenylboronic Acid (3a) in the Presence of Acetic Acida
n-C8H17
8a
+
+
Pd(PPh3)4 (10 mol%)
n-C8H17
+
AcOH
n-C8H17
10aa
n-C8H17
dioxane
B(OH)2
(E)-9aa
(Z)-9aa
3a
Entry
Amount of AcOH (mol%) Temperature Time (h) Yieldb (%) of 9aa + 10aa
Ratioc 9aa/10aa
91:9
Ratioc (E)-9aa/(Z)-9aa
1d
2d
3
100
100
100
100
100
20
r.t.
60
8
38
75
64
75
68
42
45
44
>99:1
>99:1
>99:1
>99:1
>99:1
>99:1
>99:1
>99:1
reflux
50 °C
reflux
130 °Ce
reflux
reflux
reflux
90:10
18
9
90:10
4
92:8
5
5
90:10
6
9
90:10
7
50
9
92:8
8
200
9
91:9
a Reagents and conditions: 8a (0.25 mmol), 3a (2.0 equiv), Pd(PPh3)4 (10 mol%), dioxane (3 mL), under N2.
b Isolated yield; the isomers could not be separated by flash chromatography (silica gel).
c Determined by 1H NMR (300 MHz) analysis of the crude reaction mixture obtained after evaporation.
d THF was used as solvent.
e The reaction was conducted in a Schlenk tube with a screw cap.
Synthesis 2007, No. 17, 2731–2745 © Thieme Stuttgart · New York

FEATURE ARTICLE
Palladium(0)-Catalyzed Addition of Organoboronic Acids with Allenes
2737
Table 7 Palladium(0)-Catalyzed Addition of Alkyl-Substituted Allenes 8 with Organoboronic Acids 3 under Conditions Ba
R1
R2
R2
R2
Pd(PPh3)4 (10 mol%)
R1
+
8
+
AcOH (100 mol%)
dioxane, reflux, 9 h
R1
(E)-9
R1
+
R2 B(OH)2
10
(Z)-9
3
Entry
R1
(CH2)7Me
8
R2
3
Products 9 and 10
9aa, 10aa
9ab, 10ab
9al, 10al
Yieldb (%) of 9 + 10 Ratioc 9/10
Ratioc (E)-9/(Z)-9
>99:1
1
2
8a
8a
8a
8a
8a
8a
8a
8b
8c
8d
8e
Ph
3a
3b
75
75
66
77
67
62
74
50
34
44
76
92:8
(CH2)7Me
(CH2)7Me
(CH2)7Me
(CH2)7Me
(CH2)7Me
(CH2)7Me
(CH2)11Me
(CH2)15Me
Cy
4-Tol
91:9
>99:1
3
2-MeOC6H4 3l
4-MeOC6H4 3d
91:9
>99:1
4
9ad, 10ad
9ae, 10ae
9ag, 10ag
9ah, 10ah
9ba, 10ba
9cd, 10cd
9dd, 10dd
9ed, 10ed
91:9
>99:1
5
3-O2NC6H4
4-AcC6H4
1-Naph
Ph
3e
3g
3h
3a
89:11
93:7
>99:1
6
>99:1
7
90:10
92:8
>99:1
8
>99:1
9
4-MeOC6H4 3d
4-MeOC6H4 3d
4-MeOC6H4 3d
93:7
>99:1
10
11d
88:12
>93:7
>99:1
Bn
95:5
a Reagents and conditions (conditions B): 8 (0.25 mmol), 3 (2.0 equiv), Pd(PPh3)4 (10 mol%), AcOH (100 mol%), dioxane, reflux, 9 h.
b Isolated yield; the isomers could not be separated by flash chromatography (silica gel).
c Determined by 1H NMR (300 MHz) analysis of the crude reaction mixture obtained after evaporation.
d Reaction time: 6 h.
Hepta-1,2-dien-3-yl Phenyl Sulfone (2c)
though a pad of silica gel, and evaporation to dryness, the resulting
mixture was analyzed by H NMR spectroscopy, from which the
4aa/5aa ratio of 91:9 and (E)-4aa/(Z)-4aa ratio of >99:1 were ob-
tained (see Table 4). Purification of the residue by flash chromatog-
raphy (silica gel, PE–Et2O, 20:1) gave (E)-4aa. Yield: 44 mg
(68%); solid; mp 71–73 °C (Et2O).
1
A soln of 1c (441 mg, 2 mmol) and 30% H2O2 (0.6 mL) in AcOH (5
mL) was stirred at 100 °C for 0.5 h. After complete conversion of
the starting material as monitored by TLC, the mixture was
quenched with ice-water (15 mL) and extracted with CHCl3 (4 × 15
mL). The organic layer was then neutralized by washing with sat.
aq NaHCO3 (4 × 15 mL). The combined organic layer was dried
(MgSO4). Evaporation of the solvent and flash chromatography (sil-
ica gel, PE–Et2O, 2:1) afforded 2c. Yield: 251 mg (53%); solid; mp
41–42 °C (Et2O).
IR (neat): 1601, 1571, 1445, 1303, 1145 cm–1.
1H NMR (300 MHz, CDCl3): d = 8.01–7.94 (m, 2 H), 7.65–7.51 (m,
3 H), 7.45–7.30 (m, 5 H), 6.61 (q, J = 1.2 Hz, 1 H), 2.53 (d, J = 1.2
Hz, 3 H).
13C NMR (75.4 MHz, CDCl3): d = 153.5, 142.1, 140.0, 133.2,
129.9, 129.2, 128.7, 127.4, 127.2, 126.3, 17.2.
IR (neat): 1968, 1943, 1584, 1466, 1447, 1421, 1152 cm–1.
1H NMR (300 MHz, CDCl3): d = 7.88–7.80 (m, 2 H), 7.59–7.44 (m,
3 H), 5.31 (t, J = 3.6 Hz, 2 H), 2.21–2.11 (m, 2 H), 1.34–1.28 (m, 2
H), 1.27–1.17 (m, 2 H), 0.77 (t, J = 7.2 Hz, 3 H).
MS (EI, 70 eV): m/z (%) = 258 [M+] (5.96), 115 (100).
13C NMR (75.4 MHz, CDCl3): d = 207.5, 139.9, 133.3, 128.9,
127.8, 113.1, 84.2, 29.2, 26.1, 21.7, 13.5.
Anal. Calcd for C15H14O2S: C, 69.74; H, 5.46. Found: C, 69.72; H,
5.40.
MS (EI, 70 eV): m/z (%) = 236 [M+] (8.26), 67 (100).
Phenyl (E)-2-(4-Tolyl)prop-1-en-1-yl Sulfone [(E)-4ab]
Anal. Calcd for C13H16O2S: C, 66.07; H, 6.82. Found: C, 66.06; H,
6.74.
Compound (E)-4ab was prepared similarly to compound (E)-4aa
by conditions A. The reaction of 2a (45 mg, 0.25 mmol), 3b (69 mg,
0.51 mmol), Pd(PPh3)4 (29 mg, 0.025 mmol), and AcOH (14 mL,
0.24 mmol) in THF (3 mL) afforded crude 4ab after evaporation of
the solvent, filtration though a pad of silica gel, and evaporation to
dryness [4ab/5ab > 99:1, (E)-4ab/(Z)-4ab > 99:1; by 1H NMR anal-
ysis]. Pure (E)-4ab was isolated by flash chromatography (silica
gel). Yield: 42 mg (62%); solid; mp 70–72 °C (Et2O–PE).
Phenyl (E)-2-Phenylprop-1-en-1-yl Sulfone [(E)-4aa] under
Conditions A; Typical Procedure
Compound 3a (62 mg, 0.51 mmol), 2a (45 mg, 0.25 mmol),
Pd(PPh3)4 (30 mg, 0.026 mmol), AcOH (14 mL, 0.24 mmol), and
THF (3 mL) were added into a dried reaction tube under a N2 atmo-
sphere. The resulting mixture was stirred at r.t. and monitored by
TLC (PE–Et2O, 1:1). After evaporation of the solvent, filtration
IR (neat): 1601, 1562, 1510, 1446, 1314, 1289, 1143 cm–1.
Synthesis 2007, No. 17, 2731–2745 © Thieme Stuttgart · New York

2738
H. Guo, S. Ma
FEATURE ARTICLE
Table 8 Palladium(0)-Catalyzed Addition of Aryl-Substituted Allenes 11 with Organoboronic Acids 3 under Conditions Ba
Ar
R
R
R
Pd(PPh3)4 (10 mol%)
Ar
11
AcOH (100 mol%)
dioxane, reflux, 5 h
+
Ar
(E)-12
Ar
R
B(OH)2
(Z)-12
13
3
Entry
Ar
Ph
Ph
Ph
Ph
Ph
11
R
3
Product 12
12aa
Yieldb (%) of (E)-12
Ratioc 12/13
>99:1
Ratioc (E)-12/(Z)-12
>99:1
1
11a
11a
11a
11a
11a
Ph
3a
41
73
79
44
87
60
66
62
2
4-Tol
3b
3d
3g
3h
3d
3d
3d
12ab
>99:1
>99:1
3
4-MeOC6H4
4-AcC6H4
1-Naph
12ad
>99:1
>99:1
4
12ag
>99:1
>99:1
5
12ah
>99:1
>99:1
6
4-MeOC6H4
11b
11c
11d
4-MeOC6H4
4-MeOC6H4
4-MeOC6H4
12bd
12cd
>99:1
>99:1
7d
8d
4-t-BuC6H4
>99:1
>99:1
4-AcC6H4
12dd
>99:1
>99:1
a Reagents and conditions (conditions B): 11 (0.25 mmol), 3 (2.0 equiv), Pd(PPh3)4 (10 mol%), AcOH (100 mol%), dioxane, reflux, 5 h, under N2.
b Isolated yield.
c Determined by 1H NMR (300 MHz) analysis of the crude reaction mixture obtained after evaporation.
d Reaction time: 2 h.
1H NMR (300 MHz, CDCl3): d = 8.01–7.94 (m, 2 H), 7.67–7.50 (m,
3 H), 7.30 (d, J = 8.0 Hz, 2 H), 7.16 (d, J = 8.0 Hz, 2 H), 6.60 (q,
J = 1.2 Hz, 1 H), 2.51 (d, J = 1.2 Hz, 3 H), 2.35 (s, 3 H).
13C NMR (75.4 MHz, CDCl3): d = 153.4, 142.3, 140.3, 137.0,
133.1, 129.4, 129.2, 127.2, 126.4, 126.2, 21.2, 17.1.
(E)-2-(4-Methoxyphenyl)prop-1-en-1-yl Phenyl Sulfone [(E)-
4ad]
Compound (E)-4ad was prepared similarly to compound (E)-4aa
by conditions A. The reaction of 2a (45 mg, 0.25 mmol), 3d (77 mg,
0.51 mmol), Pd(PPh3)4 (30 mg, 0.026 mmol), and AcOH (14 mL,
0.24 mmol) in THF (3 mL) afforded a crude mixture of 4ad and 5ad
after evaporation of the solvent, filtration though a pad of silica gel,
and evaporation to dryness [4ad/5ad = 93:7, (E)-4ad/(Z)-4ad >
MS (EI, 70 eV): m/z (%) = 272 [M+] (92.36), 115 (100).
Anal. Calcd for C16H16O2S: C, 70.56; H, 5.92. Found: C, 70.16; H,
5.90.
1
99:1; by H NMR analysis]. Pure (E)-4ad was isolated by flash
chromatography (silica gel). Yield: 56 mg (78%); liquid.
IR (neat): 1599, 1568, 1511, 1445, 1297, 1258, 1143 cm–1.
(E)-2-(3-Methoxyphenyl)prop-1-en-1-yl Phenyl Sulfone [(E)-
4ac]
1H NMR (300 MHz, CDCl3): d = 8.01–7.93 (m, 2 H), 7.65–7.49 (m,
3 H), 7.37 (d, J = 9.0 Hz, 2 H), 6.87 (d, J = 9.0 Hz, 2 H), 6.58 (q,
J = 1.2 Hz, 1 H), 3.81 (s, 3 H), 2.49 (d, J = 1.2 Hz, 3 H).
13C NMR (75.4 MHz, CDCl3): d = 161.1, 152.9, 142.4, 133.0,
131.9, 129.1, 127.8, 127.1, 125.3, 114.0, 55.4, 16.9.
MS (EI, 70 eV): m/z (%) = 288 [M+] (100).
HRMS (EI): m/z calcd for C16H16O3S+ [M+]: 288.0815; found:
Compound (E)-4ac was prepared similarly to compound (E)-4aa by
conditions A. The reaction of 2a (45 mg, 0.25 mmol), 3c (76 mg,
0.50 mmol), Pd(PPh3)4 (29 mg, 0.025 mmol), and AcOH (14 mL,
0.24 mmol) in THF (3 mL) afforded crude 4ac after evaporation of
the solvent, filtration though a pad of silica gel, and evaporation to
dryness [4ac/5ac > 97:3, (E)-4ac/(Z)-4ac > 99:1; by 1H NMR anal-
ysis]. Pure (E)-4ac was isolated by flash chromatography (silica
gel). Yield: 25 mg (35%); liquid.
288.0828.
IR (neat): 1602, 1576, 1483, 1446, 1430, 1303, 1145 cm–1.
1H NMR (300 MHz, CDCl3): d = 7.99–7.92 (m, 2 H), 7.64–7.50 (m,
3 H), 7.29–7.21 (m, 1 H), 6.98–6.85 (m, 3 H), 6.59 (q, J = 1.5 Hz, 1
H), 3.79 (s, 3 H), 2.49 (d, J = 1.5 Hz, 3 H).
13C NMR (75.4 MHz, CDCl3): d = 159.6, 153.4, 142.0, 141.5,
133.2, 129.7, 129.2, 127.5, 127.2, 118.7, 115.1, 112.1, 55.3, 17.3.
MS (EI, 70 eV): m/z (%) = 288 [M+] (100).
HRMS (MALDI): m/z calcd for C16H16O3SNa+ [M+ + Na]:
(E)-2-(3-Nitrophenyl)prop-1-en-1-yl Phenyl Sulfone [(E)-4ae]
Compound (E)-4ae was prepared similarly to compound (E)-4aa by
conditions A. The reaction of 2a (45 mg, 0.25 mmol), 3e (84 mg,
0.50 mmol), Pd(PPh3)4 (29 mg, 0.025 mmol), and AcOH (14 mL,
0.24 mmol) in THF (3 mL) afforded a crude mixture of 4ae and 5ae
after evaporation of the solvent, filtration though a pad of silica gel,
and evaporation to dryness [4ae/5ae = 94:6, (E)-4ae/(Z)-4ae >
99:1; by H NMR analysis]. Pure (E)-4ae was isolated by flash
chromatography (silica gel). Yield: 50 mg (66%); liquid.
IR (neat): 1611, 1530, 1479, 1446, 1352, 1306, 1148, 1085 cm–1.
1
311.0712; found: 311.0712.
Synthesis 2007, No. 17, 2731–2745 © Thieme Stuttgart · New York

FEATURE ARTICLE
Palladium(0)-Catalyzed Addition of Organoboronic Acids with Allenes
2739
1H NMR (300 MHz, CDCl3): d = 8.27–8.20 (m, 2 H), 8.03–7.96 (m,
2 H), 7.77–7.53 (m, 5 H), 6.67 (q, J = 1.5 Hz, 1 H), 2.60 (d, J = 1.5
Hz, 3 H).
13C NMR (75.4 MHz, CDCl3): d = 154.6, 141.9, 139.6, 133.6,
133.4, 130.4, 129.6, 129.3, 128.9, 128.5, 127.2, 126.7, 126.2, 125.1,
124.5, 124.2, 20.6.
13C NMR (75.4 MHz, CDCl3): d = 150.4, 148.4, 141.8, 141.4,
MS (EI, 70 eV): m/z (%) = 308 [M+] (6.57), 167 (100).
HRMS (MALDI): m/z calcd for C19H16O2SNa+ [M+ + Na]:
133.7, 132.2, 129.9, 129.8, 129.4, 127.4, 124.4, 121.3, 17.2.
MS (EI, 70 eV): m/z (%) = 303 [M+] (29.41), 115 (100).
331.0763; found: 331.0783.
HRMS (MALDI): m/z calcd for C15H13NO4SNa+ [M+ + Na]:
326.0458; found: 326.0477.
(1E,3E)-2-Methylnona-1,3-dien-1-yl Phenyl Sulfone [(E)-4ai]
Compound (E)-4ai was prepared similarly to compound (E)-4aa by
conditions A. The reaction of 2a (45 mg, 0.25 mmol), 3i (72 mg,
0.51 mmol), Pd(PPh3)4 (30 mg, 0.026 mmol), and AcOH (14 mL,
0.24 mmol) in THF (3 mL) afforded a crude mixture of 4ai and 5ai
after evaporation of the solvent, filtration though a pad of silica gel,
and evaporation to dryness [4ai/5ai = 90:10, (E)-4ai/(Z)-4ai > 99:1;
by H NMR analysis]. Pure (E)-4ai was isolated by flash chroma-
tography (silica gel). Yield: 50 mg (72%); liquid.
IR (neat): 1637, 1587, 1461, 1446, 1305, 1145, 1085 cm–1.
1H NMR (300 MHz, CDCl3): d = 7.95–7.88 (m, 2 H), 7.63–7.48 (m,
3 H), 6.20 (s, 1 H), 6.17 (dt, J = 6.6, 15.0 Hz, 1 H), 5.98 (d, J = 15.0
Hz, 1 H), 2.21 (d, J = 0.9 Hz, 3 H), 2.19–2.08 (m, 2 H), 1.46–1.18
(m, 6 H), 0.87 (t, J = 6.6 Hz, 3 H).
13C NMR (75.4 MHz, CDCl3): d = 150.4, 142.5, 139.8, 133.0,
131.3, 129.1, 127.2, 127.1, 33.0, 31.3, 28.4, 22.4, 14.0, 13.2.
MS (EI, 70 eV): m/z (%) = 278 [M+] (14.12), 77 (100).
HRMS (MALDI): m/z calcd for C16H22O2SNa+ [M+ + Na]:
(E)-2-(3-Acetylphenyl)prop-1-en-1-yl Phenyl Sulfone [(E)-4af]
Compound (E)-4af was prepared similarly to compound (E)-4aa by
conditions A. The reaction of 2a (45 mg, 0.25 mmol), 3f (82 mg,
0.50 mmol), Pd(PPh3)4 (29 mg, 0.025 mmol), and AcOH (14 mL,
0.24 mmol) in THF (3 mL) afforded crude 4af after evaporation of
the solvent, filtration though a pad of silica gel, and evaporation to
dryness [4af/5af > 99:1, (E)-4af/(Z)-4af > 99:1; by 1H NMR analy-
sis]. Pure (E)-4af was isolated by flash chromatography (silica gel).
Yield: 60 mg (80%); liquid.
1
IR (neat): 1686, 1608, 1479, 1446, 1424, 1305, 1147 cm–1.
1H NMR (300 MHz, CDCl3): d = 8.02–7.91 (m, 4 H), 7.69–7.47 (m,
4 H), 7.48 (t, J = 8.1 Hz, 1 H), 6.64 (q, J = 1.1 Hz, 1 H), 2.61 (s, 3
H), 2.57 (d, J = 1.1 Hz, 3 H).
13C NMR (75.4 MHz, CDCl3): d = 197.4, 152.3, 141.8, 140.8,
137.5, 133.4, 130.7, 129.6, 129.3, 129.1, 128.6, 127.3, 125.9, 26.7,
17.3.
MS (EI, 70 eV): m/z (%) = 300 [M+] (66.66), 285 (100).
301.1233; found: 301.1257.
HRMS (MALDI): m/z calcd for C17H17O3S+ [M+ + H]: 301.0893;
found: 301.0880.
(1E,3E)-2-Methyl-4-phenylbuta-1,3-dien-1-yl Phenyl Sulfone
[(E)-4aj]8b
Compound (E)-4aj was prepared similarly to compound (E)-4aa by
conditions A. The reaction of 2a (45 mg, 0.25 mmol), 3j (77 mg,
0.49 mmol), Pd(PPh3)4 (29 mg, 0.025 mmol), and AcOH (14 mL,
0.24 mmol) in THF (3 mL) afforded a crude mixture of 4aj and 5aj
after evaporation of the solvent, filtration though a pad of silica gel,
and evaporation to dryness [4aj/5aj = 94:6, (E)-4aj/(Z)-4aj > 99:1;
by 1H NMR analysis]. Pure (E)-4aj was isolated by flash chroma-
tography (silica gel). Yield: 37 mg (52%); solid; mp 123–124 °C
(Et2O) (Lit.8b 128–130 °C).
(E)-2-(4-Acetylphenyl)prop-1-en-1-yl Phenyl Sulfone [(E)-4ag]
Compound (E)-4ag was prepared similarly to compound (E)-4aa by
conditions A. The reaction of 2a (45 mg, 0.25 mmol), 3g (82 mg,
0.50 mmol), Pd(PPh3)4 (29 mg, 0.025 mmol), and AcOH (14 mL,
0.24 mmol) in THF (3 mL) afforded a crude mixture of 4ag and 5ag
after evaporation of the solvent, filtration though a pad of silica gel,
and evaporation to dryness [4ag/5ag = 94:6, (E)-4ag/(Z)-4ag >
99:1; by H NMR analysis]. Pure (E)-4ag was isolated by flash
chromatography (silica gel). Yield: 60 mg (80%); solid; mp 124–
126 °C (CH2Cl2–pentane).
1
IR (neat): 1623, 1579, 1494, 1447, 1303, 1144 cm–1.
IR (neat): 1685, 1604, 1559, 1446, 1405, 1304, 1146 cm–1.
1H NMR (300 MHz, CDCl3): d = 8.00–7.92 (m, 2 H), 7.66–7.49 (m,
3 H), 7.46–7.39 (m, 2 H), 7.38–7.28 (m, 3 H), 6.96 (d, J = 16.1 Hz,
1 H), 6.68 (d, J = 16.1 Hz, 1 H), 6.42 (s, 1 H), 2.36 (s, 3 H).
13C NMR (75.4 MHz, CDCl3): d = 149.7, 142.4, 135.8, 135.53,
135.51, 133.1, 129.4, 129.2, 129.1, 128.8, 127.2, 127.1, 13.2.
1H NMR (300 MHz, CDCl3): d = 8.01–7.96 (m, 2 H), 7.94 (d,
J = 8.6 Hz, 2 H), 7.72–7.53 (m, 3 H), 7.47 (d, J = 8.6 Hz, 2 H), 6.64
(q, J = 1.2 Hz, 1 H), 2.60 (s, 3 H), 2.56 (d, J = 1.2 Hz, 3 H).
13C NMR (75.4 MHz, CDCl3): d = 197.3, 152.1, 144.5, 141.7,
137.8, 133.5, 129.3, 129.1, 128.7, 127.3, 126.6, 26.7, 17.2.
MS (EI, 70 eV): m/z (%) = 284 [M+] (11.16), 55 (100).
MS (EI, 70 eV): m/z (%) = 300 [M+] (58.00), 285 (100).
Phenyl (E)-3-Phenylbut-2-en-2-yl Sulfone [(E)-4ba]
Anal. Calcd for C17H16O3S: C, 67.98; H, 5.37. Found: C, 67.74; H,
5.42.
Compound (E)-4ba was prepared similarly to compound (E)-4aa
by conditions A. The reaction of 2b (49 mg, 0.25 mmol), 3a (61 mg,
0.50 mmol), Pd(PPh3)4 (29 mg, 0.025 mmol), and AcOH (14 mL,
0.24 mmol) in THF (3 mL) afforded crude 4ba after evaporation of
the solvent, filtration though a pad of silica gel, and evaporation to
dryness [4ba/5ba > 99:1, (E)-4ba/(Z)-4ba > 99:1; by 1H NMR anal-
ysis]. Pure (E)-4ba was isolated by flash chromatography (silica
gel). Yield: 34 mg (50%); liquid.
(E)-2-(1-Naphthyl)prop-1-en-1-yl Phenyl Sulfone [(E)-4ah]
Compound (E)-4ah was prepared similarly to compound (E)-4aa
by conditions A. The reaction of 2a (45 mg, 0.25 mmol), 3h (87 mg,
0.51 mmol), Pd(PPh3)4 (29 mg, 0.025 mmol), and AcOH (14 mL,
0.24 mmol) in THF (3 mL) afforded a crude mixture of 4ah and 5ah
after evaporation of the solvent, filtration though a pad of silica gel,
and evaporation to dryness [4ah/5ah = 91:9, (E)-4ah/(Z)-4ah >
IR (neat): 1620, 1598, 1490, 1445, 1303, 1159, 1127, 1080 cm–1.
1
99:1; by H NMR analysis]. Pure (E)-4ah was isolated by flash
1H NMR (300 MHz, CDCl3): d = 7.99–7.92 (m, 2 H), 7.67–7.52 (m,
3 H), 7.40–7.24 (m, 3 H), 7.10–7.03 (m, 2 H), 2.47 (q, J = 1.5 Hz, 3
H), 1.86 (q, J = 1.5 Hz, 3 H).
13C NMR (75.4 MHz, CDCl3): d = 149.8, 142.8, 141.4, 133.7,
133.1, 129.1, 128.5, 127.7, 127.1, 126.5, 22.6, 17.7.
chromatography (silica gel). Yield: 56 mg (73%); liquid.
IR (neat): 1614, 1508, 1442, 1308, 1148 cm–1.
1H NMR (300 MHz, CDCl3): d = 8.07–8.01 (m, 2 H), 7.88–7.78 (m,
2 H), 7.72–7.56 (m, 4 H), 7.53–7.37 (m, 3 H), 7.27–7.20 (m, 1 H),
6.49 (q, J = 1.5 Hz, 1 H), 2.62 (d, J = 1.5 Hz, 3 H).
MS (EI, 70 eV): m/z (%) = 272 [M+] (27.39), 91 (100).
Synthesis 2007, No. 17, 2731–2745 © Thieme Stuttgart · New York

2740
H. Guo, S. Ma
FEATURE ARTICLE
HRMS (MALDI): m/z calcd for C16H17O2S+ [M+ + H]: 273.0944;
found: 273.0945.
(E)-2-(3-Methoxyphenyl)prop-1-en-1-yl Phenyl Sulfoxide [(E)-
6ac]
Compound (E)-6ac was prepared similarly to compound (E)-4aa by
conditions A. The reaction of 1a (41 mg, 0.25 mmol), 3c (76 mg,
0.50 mmol), Pd(PPh3)4 (29 mg, 0.025 mmol), and AcOH (14 mL,
0.24 mmol) in THF (3 mL) afforded crude 6ac after evaporation of
the solvent, filtration though a pad of silica gel, and evaporation to
dryness [6ac/7ac = 99:1, (E)-6ac/(Z)-6ac > 99:1; by 1H NMR anal-
ysis]. Pure (E)-6ac was isolated by flash chromatography (silica
gel). Yield: 41 mg (59%); liquid.
Phenyl (E)-2-Phenylhept-2-en-3-yl Sulfone [(E)-4ca]
Compound (E)-4ca was prepared similarly to compound (E)-4aa by
conditions A. The reaction of 2c (59 mg, 0.25 mmol), 3a (61 mg,
0.50 mmol), Pd(PPh3)4 (29 mg, 0.025 mmol), and AcOH (14 mL,
0.24 mmol) in THF (3 mL) afforded crude 4ca after evaporation of
the solvent, filtration though a pad of silica gel, and evaporation to
dryness [4ca/5ca > 99:1, (E)-4ca/(Z)-4ca > 99:1; by 1H NMR anal-
ysis]. Pure (E)-4ca was isolated by flash chromatography (silica
gel). Yield: 43 mg (55%); solid; mp 83–85 °C (Et2O).
IR (neat): 1601, 1574, 1485, 1475, 1443, 1428, 1039 cm–1.
1H NMR (300 MHz, CDCl3): d = 7.67–7.61 (m, 2 H), 7.55–7.41 (m,
3 H), 7.26 (t, J = 7.8 Hz, 1 H), 7.04–6.99 (m, 1 H), 6.96–6.93 (m, 1
H), 6.91–6.85 (m, 1H), 6.53 (q, J = 1.5 Hz, 1 H), 3.78 (s, 3 H), 2.55
(d, J = 1.5 Hz, 3 H).
13C NMR (75.4 MHz, CDCl3): d = 159.6, 147.9, 144.4, 140.7,
133.2, 130.6, 129.6, 129.3, 124.0, 118.6, 114.7, 111.9, 55.3, 18.1.
MS (EI, 70 eV): m/z (%) = 272 [M+] (1.91), 224 (100).
HRMS (MALDI): m/z calcd for C16H16O2SNa+ [M+ + Na]:
IR (neat): 1612, 1598, 1490, 1445, 1301, 1154, 1132, 1083 cm–1.
1H NMR (300 MHz, CDCl3): d = 8.00–7.92 (m, 2 H), 7.66–7.51 (m,
3 H), 7.39–7.24 (m, 3 H), 7.09–7.02 (m, 2 H), 2.32–2.21 (m, 5 H),
1.49–1.36 (m, 2 H), 1.13–0.99 (m, 2 H), 0.66 (t, J = 7.2 Hz, 3 H).
13C NMR (75.4 MHz, CDCl3): d = 150.5, 142.7, 142.6, 139.7,
132.9, 129.0, 128.5, 127.6, 127.0, 126.1, 32.2, 30.7, 23.4, 22.5,
13.4.
MS (EI, 70 eV): m/z (%) = 314 [M+] (30.10), 91 (100).
295.0763; found: 295.0759.
Anal. Calcd for C19H22O2S: C, 72.57; H, 7.05. Found: C, 72.38; H,
7.07.
(E)-2-(4-Methoxyphenyl)prop-1-en-1-yl Phenyl Sulfoxide [(E)-
6ad]
Phenyl (E)-2-Phenylprop-1-en-1-yl Sulfoxide [(E)-6aa]16
Compound (E)-6ad was prepared similarly to compound (E)-4aa
by conditions A. The reaction of 1a (41 mg, 0.25 mmol), 3d (76 mg,
0.50 mmol), Pd(PPh3)4 (29 mg, 0.025 mmol), and AcOH (14 mL,
0.24 mmol) in THF (3 mL) afforded a crude mixture of 6ad and 7ad
after evaporation of the solvent, filtration though a pad of silica gel,
and evaporation to dryness [6ad/7ad = 95:5, (E)-6ad/(Z)-6ad >
Compound (E)-6aa was prepared similarly to compound (E)-4aa by
conditions A. The reaction of 1a (41 mg, 0.25 mmol), 3a (61 mg,
0.50 mmol), Pd(PPh3)4 (29 mg, 0.025 mmol), and AcOH (14 mL,
0.24 mmol) in THF (3 mL) afforded a crude mixture of 6aa and 7aa
after evaporation of the solvent, filtration though a pad of silica gel,
and evaporation to dryness [6aa/7aa = 94:6, (E)-6aa/(Z)-6aa >
1
99:1; by H NMR analysis]. Pure (E)-6ad was isolated by flash
1
99:1; by H NMR analysis]. Pure (E)-6aa was isolated by flash
chromatography (silica gel). Yield: 35 mg (52%); liquid.
chromatography (silica gel). Yield: 30 mg (50%); liquid.
IR (neat): 1597, 1571, 1475, 1442, 1083, 1038 cm–1.
1H NMR (300 MHz, CDCl3): d = 7.70–7.63 (m, 2 H), 7.57–7.41 (m,
5 H), 7.40–7.31 (m, 3 H), 6.54 (q, J = 1.2 Hz, 1 H), 2.58 (d, J = 1.2
Hz, 3 H).
13C NMR (75.4 MHz, CDCl3): d = 148.0, 144.6, 139.3, 133.2,
130.6, 129.5, 129.3, 128.6, 126.2, 124.1, 18.1.
MS (EI, 70 eV): m/z (%) = 242 [M+] (2.27), 194 (100).
IR (neat): 1604, 1567, 1513, 1463, 1442, 1255, 1183, 1034 cm–1.
1H NMR (300 MHz, CDCl3): d = 7.69–7.61 (m, 2 H), 7.56–7.44 (m,
3 H), 7.42 (d, J = 9.0 Hz, 2 H), 6.87 (d, J = 9.0 Hz, 2 H), 6.49 (q,
J = 0.9 Hz, 1 H), 3.81 (s, 3 H), 2.56 (d, J = 0.9 Hz, 3 H).
13C NMR (75.4 MHz, CDCl3): d = 160.6, 147.5, 144.9, 131.3,
131.1, 130.5, 129.2, 127.6, 124.0, 113.9, 55.3, 17.8.
MS (EI, 70 eV): m/z (%) = 273 (3.15), 272 [M+] (1.82), 224 (100).
HRMS (MALDI): m/z calcd for C16H17O2S+ [M+ + H]: 273.0944;
found: 273.0961.
Phenyl (E)-2-(4-Tolyl)prop-1-en-1-yl Sulfoxide [(E)-6ab]
Compound (E)-6ab was prepared similarly to compound (E)-4aa
by conditions A. The reaction of 1a (41 mg, 0.25 mmol), 3b (69 mg,
0.51 mmol), Pd(PPh3)4 (29 mg, 0.025 mmol), and AcOH (14 mL,
0.24 mmol) in THF (3 mL) afforded a crude mixture of 6ab and 7ab
after evaporation of the solvent, filtration though a pad of silica gel,
and evaporation to dryness [6ab/7ab > 97:3, (E)-6ab/(Z)-6ab >
99:1; by H NMR analysis]. Pure (E)-6ab was isolated by flash
chromatography (silica gel). Yield: 37 mg (58%); liquid.
IR (neat): 1608, 1582, 1563, 1514, 1475, 1442, 1083, 1039 cm–1.
(E)-2-(3-Nitrophenyl)prop-1-en-1-yl Phenyl Sulfoxide [(E)-6ae]
Compound (E)-6ae was prepared similarly to compound (E)-4aa by
conditions A. The reaction of 1a (41 mg, 0.25 mmol), 3e (85 mg,
0.51 mmol), Pd(PPh3)4 (29 mg, 0.025 mmol), and AcOH (14 mL,
0.24 mmol) in THF (3 mL) afforded a crude mixture of 6ae and 7ae
after evaporation of the solvent, filtration though a pad of silica gel,
and evaporation to dryness [6ae/7ae > 96:4, (E)-6ae/(Z)-6ae > 99:1;
by 1H NMR analysis]. Pure (E)-6ae was isolated by flash chroma-
tography (silica gel). Yield: 35 mg (49%); liquid.
1
1H NMR (300 MHz, CDCl3): d = 7.69–7.62 (m, 2 H), 7.55–7.41 (m,
3 H), 7.35 (d, J = 8.1 Hz, 2 H), 7.16 (d, J = 8.1 Hz, 2 H), 6.52 (q,
J = 0.9 Hz, 1 H), 2.56 (d, J = 0.9 Hz, 3 H), 2.35 (s, 3 H).
13C NMR (75.4 MHz, CDCl3): d = 148.0, 144.7, 139.7, 136.3,
132.2, 130.6, 129.8, 129.3, 126.1, 124.1, 21.2, 18.0.
IR (neat): 1615, 1530, 1476, 1443, 1351, 1083, 1038 cm–1.
1H NMR (300 MHz, CDCl3): d = 8.27–8.24 (m, 1 H), 8.20–8.15 (m,
1 H), 7.79–7.72 (m, 1 H), 7.69–7.62 (m, 2 H), 7.57–7.43 (m, 4 H),
6.61 (q, J = 1.5 Hz, 1 H), 2.60 (d, J = 1.5 Hz, 3 H).
13C NMR (75.4 MHz, CDCl3): d = 144.8, 144.0, 142.2, 140.8,
135.9, 131.9, 131.0, 129.7, 129.5, 123.94, 123.90, 121.1, 18.0.
MS (EI, 70 eV): m/z (%) = 256 [M+] (2.95), 208 (100).
HRMS (MALDI): m/z calcd for C16H17OS+ [M+ + H]: 257.0995;
MS (EI, 70 eV): m/z (%) = 288 (5.97), 287 [M+] (2.64), 239 (100).
found: 257.0985.
HRMS (MALDI): m/z calcd for C15H14O3SN+ [M+ + H]: 288.0689;
found: 288.0672.
Synthesis 2007, No. 17, 2731–2745 © Thieme Stuttgart · New York

FEATURE ARTICLE
Palladium(0)-Catalyzed Addition of Organoboronic Acids with Allenes
2741
(E)-2-(4-Acetylphenyl)prop-1-en-1-yl Phenyl Sulfoxide [(E)-
6ag]
(1E,3E)-2-Methyl-4-phenylbuta-1,3-dien-1-yl Phenyl Sulfoxide
[(E)-6aj]
Compound (E)-6ag was prepared similarly to compound (E)-4aa by
conditions A. The reaction of 1a (41 mg, 0.25 mmol), 3g (83 mg,
0.51 mmol), Pd(PPh3)4 (29 mg, 0.025 mmol), and AcOH (14 mL,
0.24 mmol) in THF (3 mL) afforded crude 6ag after evaporation of
the solvent, filtration though a pad of silica gel, and evaporation to
dryness [6ag/7ag > 99:1, (E)-6ag/(Z)-6ag > 99:1; by 1H NMR anal-
ysis]. Pure (E)-6ag was isolated by flash chromatography (silica
gel). Yield: 34 mg (48%); liquid.
Compound (E)-6aj was prepared similarly to compound (E)-4aa by
conditions A. The reaction of 1a (40 mg, 0.24 mmol), 3j (78 mg,
0.50 mmol), Pd(PPh3)4 (29 mg, 0.025 mmol), and AcOH (14 mL,
0.24 mmol) in THF (3 mL) afforded a crude mixture of 6aj and 7aj
after evaporation of the solvent, filtration though a pad of silica gel,
and evaporation to dryness [6aj/7aj > 94:6, (E)-6aj/(Z)-6aj > 99:1;
by 1H NMR analysis]. Pure (E)-6aj was isolated by flash chroma-
tography (silica gel). Yield: 31 mg (46%); liquid.
IR (neat): 1683, 1604, 1557, 1475, 1443, 1405, 1358, 1268, 1039
cm–1.
1H NMR (300 MHz, CDCl3): d = 7.93 (d, J = 8.4 Hz, 2 H), 7.70–
7.63 (m, 2 H), 7.57–7.46 (m, 5 H), 6.60 (q, J = 1.2 Hz, 1 H), 2.59
(d, J = 1.2 Hz, 3 H), 2.59 (s, 3 H).
13C NMR (75.4 MHz, CDCl3): d = 197.3, 146.6, 144.2, 143.7,
137.4, 135.1, 130.9, 129.4, 128.6, 126.4, 124.1, 26.7, 18.1.
IR (neat): 1623, 1599, 1579, 1494, 1474, 1443, 1082, 1036 cm–1.
1H NMR (300 MHz, CDCl3): d = 7.67–7.60 (m, 2 H), 7.55–7.37 (m,
5 H), 7.38–7.24 (m, 3 H), 6.87 (d, J = 16.2 Hz, 1 H), 6.73 (d,
J = 16.2 Hz, 1 H), 6.32 (s, 1 H), 2.39 (s, 3 H).
13C NMR (75.4 MHz, CDCl3): d = 145.3, 144.6, 135.9, 135.8,
134.4, 130.6, 129.24, 129.16, 128.75, 128.72, 126.9, 124.0, 14.7.
MS (EI, 70 eV): m/z (%) = 268 [M+] (1.03), 91 (100).
HRMS (EI): m/z calcd for C17H16OS+ [M+]: 268.0922; found:
MS (EI, 70 eV): m/z (%) = 285 (3.31), 284 [M+] (1.43), 236 (100).
HRMS (MALDI): m/z calcd for C17H17O2S+ [M+ + H]: 285.0944;
268.0923.
found: 285.0928.
(E)-2-Phenylundec-2-ene [(E)-9aa] under Conditions B; Typi-
cal Procedure17
(E)-2-(1-Naphthyl)prop-1-en-1-yl Phenyl Sulfoxide [(E)-6ah]
Compound (E)-6ah was prepared similarly to compound (E)-4aa
by conditions A. The reaction of 1a (41 mg, 0.25 mmol), 3h (86 mg,
0.50 mmol; should be recrystallized from H2O immediately before
use), Pd(PPh3)4 (29 mg, 0.025 mmol), and AcOH (14 mL, 0.24
mmol) in THF (3 mL) afforded a crude mixture of 6ah and 7ah after
evaporation of the solvent, filtration though a pad of silica gel, and
evaporation to dryness [6ah/7ah > 94:6, (E)-6ah/(Z)-6ah > 99:1; by
1H NMR analysis]. Pure (E)-6ah was isolated by flash chromatog-
raphy (silica gel). Yield: 30 mg (41%); liquid.
Compound 3a (61 mg, 0.50 mmol), 8a (38 mg, 0.25 mmol),
Pd(PPh3)4 (29 mg, 0.025 mmol), AcOH (14 mL, 0.24 mmol), and di-
oxane (3 mL) were added into a dried reaction tube under a N2 at-
mosphere. The resulting mixture was stirred under reflux and
monitored by TLC (PE). After evaporation to dryness, the crude
1
mixture was analyzed by H NMR spectroscopy, from which the
9aa/10aa ratio of 92:8 and (E)-9aa/(Z)-9aa ratio of >99:1 was ob-
tained (see Table 7). Purification of the residue by flash chromatog-
raphy (silica gel, PE) gave a mixture of (E)-9aa and 10aa. Yield: 43
mg (75%); (E)-9aa/10aa = 96:4; liquid.
IR (neat): 1613, 1590, 1507, 1475, 1442, 1083, 1040 cm–1.
IR (neat): 1597, 1494, 1465, 1445, 1378 cm–1.
1H NMR (300 MHz, CDCl3): d = 7.91–7.72 (m, 5 H), 7.62–7.40 (m,
6 H), 7.30–7.26 (m, 1 H), 6.41 (q, J = 1.2 Hz, 1 H), 2.67 (d, J = 1.2
Hz, 3 H).
13C NMR (75.4 MHz, CDCl3): d = 149.4, 144.6, 139.0, 136.6,
133.6, 130.7, 129.8, 129.4, 128.6, 128.5, 126.5, 126.1, 125.1, 124.7,
124.4, 124.0, 21.4.
MS (EI, 70 eV): m/z (%) = 293 (3.07), 292 [M+] (6.94), 165 (100).
HRMS (MALDI): m/z calcd for C19H17OS+ [M+ + H]: 293.0995;
1H NMR (300 MHz, CDCl3): d [(E)-9aa] = 7.43–7.36 (m, 2 H),
7.35–7.25 (m, 2 H), 7.25–7.17 (m, 1 H), 5.80 (qt, J = 1.1, 6.6 Hz, 1
H), 2.26–2.15 (m, 2 H), 2.04 (d, J = 1.1 Hz, 3 H), 1.51–1.20 (m, 12
H), 0.90 (t, J = 6.6 Hz, 3 H); d (10aa) = 5.27 (s, 1 H), 5.07 (s, 1 H),
2.51 (t, J = 7.5 Hz, 2 H).
13C NMR (75.4 MHz, CDCl3): d = 144.0, 134.4, 128.8, 128.1,
126.4, 125.5, 31.9, 29.62, 29.56, 29.4, 29.3, 28.8, 22.7, 15.7, 14.1.
MS (EI, 70 eV): m/z (%) = 230 [M+] (35.01), 118 (100).
found: 293.0981.
(E)-2-(4-Tolyl)undec-2-ene [(E)-9ab]
(1E,3E)-2-Methylocta-1,3-dien-1-yl Phenyl Sulfoxide [(E)-6ak]
Compound (E)-6ak was prepared similarly to compound (E)-4aa
by conditions A. The reaction of 1a (41 mg, 0.25 mmol), 3k (64 mg,
0.50 mmol), Pd(PPh3)4 (29 mg, 0.025 mmol), and AcOH (14 mL,
0.24 mmol) in THF (3 mL) afforded a crude mixture of 6ak and 7ak
after evaporation of the solvent, filtration though a pad of silica gel,
and evaporation to dryness [6ak/7ak > 92:8, (E)-6ak/(Z)-6ak >
99:1; by 1H NMR analysis]. Pure (E)-6al was isolated by flash chro-
matography (silica gel). Yield: 33 mg (53%); liquid.
Compound (E)-9ab was prepared similarly to compound (E)-9aa
by conditions B. The reaction of 3b (68 mg, 0.50 mmol), 8a (38 mg,
0.25 mmol), Pd(PPh3)4 (29 mg, 0.025 mmol), and AcOH (14 mL,
0.24 mmol) in dioxane (3 mL) afforded a crude mixture of 9ab and
10ab after evaporation [9ab/10ab = 91:9, (E)-9ab/(Z)-9ab > 99:1;
by 1H NMR analysis]. A mixture of (E)-9ab and 10ab was isolated
by flash chromatography (silica gel). Yield: 46 mg (75%); (E)-9ab/
10ab = 93:7; liquid.
IR (neat): 1512, 1465, 1377 cm–1.
IR (neat): 1638, 1581, 1475, 1466, 1443, 1379, 1183, 1039 cm–1.
1H NMR (300 MHz, CDCl3): d [(E)-9ab] = 7.29 (d, J = 8.4 Hz, 2
H), 7.13 (d, J = 8.4 Hz, 2 H), 5.77 (qt, J = 1.2, 7.2 Hz, 1 H), 2.35 (s,
3 H), 2.25–2.14 (m, 2 H), 2.02 (d, J = 1.2 Hz, 3 H), 1.54–1.17 (m,
12 H), 0.90 (t, J = 6.9 Hz, 3 H); d (10ab) = 5.25 (s, 1 H), 5.02 (s, 1
H), 2.49 (t, J = 7.5 Hz, 2 H).
13C NMR (75.4 MHz, CDCl3): d = 141.2, 136.0, 134.2, 128.8,
128.0, 125.4, 31.9, 29.7, 29.6, 29.4, 29.3, 28.8, 22.7, 21.0, 15.7,
14.1.
1H NMR (300 MHz, CDCl3): d = 7.63–7.55 (m, 2 H), 7.54–7.39 (m,
3 H), 6.13–6.03 (m, 3 H), 2.25 (d, J = 0.6 Hz, 3 H), 2.19–2.08 (m, 2
H), 1.45–1.19 (m, 4 H), 0.88 (t, J = 7.2 Hz, 3 H).
13C NMR (75.4 MHz, CDCl3): d = 146.1, 144.8, 138.1, 133.5,
131.1, 130.5, 129.2, 124.1, 32.6, 31.0, 22.2, 14.7, 13.8.
MS (EI, 70 eV): m/z (%) = 249 (3.30), 248 [M+] (1.39), 143 (100).
HRMS (MALDI): m/z calcd for C15H21OS+ [M+ + H]: 249.1308;
MS (EI, 70 eV): m/z (%) = 244 [M+] (24.78), 145 (100).
found: 249.1299.
HRMS (EI): m/z calcd for C18H28 [M+]: 244.2191; found: 244.2184.
Synthesis 2007, No. 17, 2731–2745 © Thieme Stuttgart · New York

2742
H. Guo, S. Ma
FEATURE ARTICLE
MS (EI, 70 eV): m/z (%) = 275 [M+] (4.11), 163 (100).
(E)-2-(2-Methoxyphenyl)undec-2-ene [(E)-9al]
Compound (E)-9al was prepared similarly to compound (E)-9aa by
conditions B. The reaction of 3l (76 mg, 0.50 mmol), 8a (38 mg,
0.25 mmol), Pd(PPh3)4 (29 mg, 0.025 mmol), and AcOH (14 mL,
0.24 mmol) in dioxane (3 mL) afforded a crude mixture of 9al and
10al after evaporation [9al/10al = 91:9, (E)-9al/(Z)-9al > 99:1; by
1H NMR analysis]. A mixture of (E)-9al and 10al was isolated by
flash chromatography (silica gel). Yield: 43 mg (66%); (E)-9al/
10al = 91:9; liquid.
HRMS (EI): m/z calcd for C17H25NO2 [M+]: 275.1885; found:
275.1888.
+
(E)-2-(4-Acetylphenyl)undec-2-ene [(E)-9ag]
Compound (E)-9ag was prepared similarly to compound (E)-9aa by
conditions B. The reaction of 3g (82 mg, 0.50 mmol), 8a (38 mg,
0.25 mmol), Pd(PPh3)4 (29 mg, 0.025 mmol), and AcOH (14 mL,
0.24 mmol) in dioxane (3 mL) afforded a crude mixture of 9ag and
10ag after evaporation [9ag/10ag = 93:7, (E)-9ag/(Z)-9ag > 99:1;
by 1H NMR analysis]. Pure (E)-9ag was isolated by flash chroma-
tography (silica gel). Yield: 42 mg (62%); liquid.
IR (neat): 1597, 1578, 1489, 1464, 1434, 1031 cm–1.
1H NMR (300 MHz, CDCl3): d [(E)-9al] = 7.20–7.12 (m, 1 H),
7.10–7.03 (m, 1 H), 6.90–6.77 (m, 2 H), 5.41 (qt, J = 1.5, 7.2 Hz, 1
H), 3.76 (s, 3 H), 2.17–2.06 (m, 2 H), 1.92 (d, J = 1.5 Hz, 3 H),
1.45–1.08 (m, 12 H), 0.84 (t, J = 7.2 Hz, 3 H); d (10al) = 5.08 (s, 1
H), 4.95 (s, 1 H), 2.42 (t, J = 6.9 Hz, 2 H).
13C NMR (75.4 MHz, CDCl3): d = 156.6, 135.1, 134.6, 130.3,
129.7, 127.7, 120.5, 110.6, 55.4, 31.9, 29.6, 29.5, 29.40, 29.36,
28.3, 22.7, 17.0, 14.1.
IR (neat): 1684, 1602, 1466, 1408, 1267 cm–1.
1H NMR (300 MHz, CDCl3): d = 7.90 (d, J = 8.7 Hz, 2 H), 7.46 (d,
J = 8.7 Hz, 2 H), 5.92 (qt, J = 1.2, 7.2 Hz, 1 H), 2.59 (s, 3 H), 2.27–
2.16 (m, 2 H), 2.05 (d, J = 1.2 Hz, 3 H), 1.54–1.22 (m, 12 H), 0.89
(t, J = 6.6 Hz, 3 H).
13C NMR (75.4 MHz, CDCl3): d = 197.8, 148.7, 135.1, 133.7,
131.4, 128.4, 125.5, 31.9, 29.5, 29.4, 29.3, 28.9, 26.6, 22.7, 15.5,
14.1.
MS (EI, 70 eV): m/z (%) = 260 [M+] (51.17), 161 (100).
HRMS (EI): m/z calcd for C18H28O+1 [M+]: 260.2140; found:
260.2162.
MS (EI, 70 eV): m/z (%) = 272 [M+] (3.45), 181 (100).
HRMS (MALDI): m/z calcd for C19H29O+ [M+ + H]: 273.2213;
found: 273.2222.
(E)-2-(4-Methoxyphenyl)undec-2-ene [(E)-9ad]
Compound (E)-9ad was prepared similarly to compound (E)-9aa
by conditions B. The reaction of 3d (76 mg, 0.50 mmol), 8a (38 mg,
0.25 mmol), Pd(PPh3)4 (29 mg, 0.025 mmol), and AcOH (14 mL,
0.24 mmol) in dioxane (3 mL) afforded a crude mixture of 9ad and
10ad after evaporation [9ad/10ad = 91:9, (E)-9ad/(Z)-9ad > 99:1;
by 1H NMR analysis]. A mixture of (E)-9ad and 10ad was isolated
by flash chromatography (silica gel). Yield: 50 mg (77%); (E)-9ad/
10ad = 97:3; liquid.
(E)-2-(1-Naphthyl)undec-2-ene [(E)-9ah]
Compound (E)-9ah was prepared similarly to compound (E)-9aa
by conditions B. The reaction of 3h (86 mg, 0.50 mmol), 8a (38 mg,
0.25 mmol), Pd(PPh3)4 (29 mg, 0.025 mmol), and AcOH (14 mL,
0.24 mmol) in dioxane (3 mL) afforded a crude mixture of 9ah and
10ah after evaporation [9ah/10ah = 90:10, (E)-9ah/(Z)-9ah > 99:1;
by 1H NMR analysis]. A mixture of (E)-9ah and 10ah was isolated
by flash chromatography (silica gel). Yield: 52 mg (74%), (E)-9ah/
10ah = 92:8; liquid.
IR (neat): 1608, 1512, 1464, 1441, 1246 cm–1.
1H NMR (300 MHz, CDCl3): d [(E)-9ad] = 7.32 (d, J = 9.0 Hz, 2
H), 6.85 (d, J = 9.0 Hz, 2 H), 5.71 (qt, J = 1.2, 6.9 Hz, 1 H), 3.81 (s,
3 H), 2.23–2.11 (m, 2 H), 2.00 (d, J = 1.2 Hz, 3 H), 1.50–1.20 (m,
12 H), 0.89 (t, J = 6.6 Hz, 3 H); d (10ad) = 5.19 (s, 1 H), 4.96 (s, 1
H), 2.46 (t, J = 7.5 Hz, 2 H).
13C NMR (75.4 MHz, CDCl3): d = 158.3, 136.6, 133.7, 127.2,
126.5, 113.4, 55.2, 31.9, 29.7, 29.6, 29.4, 29.3, 28.8, 22.7, 15.8,
14.1.
IR (neat): 1591, 1578, 1506, 1465, 1394, 1376 cm–1.
1H NMR (300 MHz, CDCl3): d [(E)-9ah] = 8.07–7.97 (m, 1 H),
7.92–7.83 (m, 1 H), 7.77 (d, J = 7.8 Hz, 1 H), 7.59–7.38 (m, 3 H),
7.30 (d, J = 6.9 Hz, 1 H), 5.56 (t, J = 6.9 Hz, 1 H), 2.38–2.27 (m, 2
H), 2.13 (s, 3 H), 1.64–1.24 (m, 12 H), 0.95 (t, J = 6.6 Hz, 3 H);
d (10ah) = 5.43 (s, 1 H), 5.11 (s, 1 H), 2.55 (t, J = 7.5 Hz, 2 H).
13C NMR (75.4 MHz, CDCl3): d = 144.3, 134.6, 133.7, 131.3,
128.3, 127.8, 126.6, 125.9, 125.8, 125.5, 125.4, 124.9, 31.9, 29.61,
29.57, 29.45, 29.39, 28.5, 22.7, 18.9, 14.2.
MS (EI, 70 eV): m/z (%) = 260 [M+] (48.79), 161 (100).
HRMS (EI): m/z calcd for C18H28O+ [M+]: 260.2140; found:
260.2128.
MS (EI, 70 eV): m/z (%) = 280 [M+] (51.05), 181 (100).
HRMS (MALDI): m/z calcd for C21H29+ [M+ + H]: 281.2264; found:
281.2256.
(E)-2-(3-Nitrophenyl)undec-2-ene [(E)-9ae]
Compound (E)-9ae was prepared similarly to compound (E)-9aa by
conditions B. The reaction of 3e (84 mg, 0.50 mmol), 8a (38 mg,
0.25 mmol), Pd(PPh3)4 (29 mg, 0.025 mmol), and AcOH (14 mL,
0.24 mmol) in dioxane (3 mL) afforded a crude mixture of 9ae and
10ae after evaporation [9ae/10ae = 89:11, (E)-9ae/(Z)-9ae > 99:1;
by 1H NMR analysis]. A mixture of (E)-9ae and 10ae was isolated
by flash chromatography (silica gel). Yield: 46 mg (67%); (E)-9ae/
10ae = 93:7; liquid.
(E)-2-Phenylpentadec-2-ene [(E)-9ba]
Compound (E)-9ba was prepared similarly to compound (E)-9aa
by conditions B. The reaction of 3a (61 mg, 0.50 mmol), 8b (52 mg,
0.25 mmol), Pd(PPh3)4 (29 mg, 0.025 mmol), and AcOH (14 mL,
0.24 mmol) in dioxane (3 mL) afforded a crude mixture of 9ba and
10ba after evaporation [9ba/10ba = 92:8, (E)-9ba/(Z)-9ba > 99:1;
by 1H NMR analysis]. A mixture of (E)-9ba and 10ba was isolated
by flash chromatography (silica gel). Yield: 36 mg (50%); (E)-9ba/
10ba = 93:7; liquid.
IR (neat): 1530, 1465, 1349 cm–1.
1H NMR (300 MHz, CDCl3): d [(E)-9ae] = 8.24–8.20 (m, 1 H),
8.09–8.03 (m, 1 H), 7.72–7.66 (m, 1 H), 7.45 (t, J = 8.1 Hz, 1 H),
5.92 (qt, J = 1.2, 7.5 Hz, 1 H), 2.28–2.17 (m, 2 H), 2.07 (d, J = 1.2
Hz, 3 H), 1.51–1.22 (m, 12 H), 0.89 (t, J = 6.9 Hz, 3 H); d (10ae) =
5.38 (s, 1 H), 5.20 (s, 1 H), 2.52 (t, J = 7.2 Hz, 2 H).
13C NMR (75.4 MHz, CDCl3): d = 145.5, 132.6, 131.57, 131.48,
128.9, 121.1, 120.4, 31.9, 29.5, 29.41, 29.37, 29.28, 28.9, 22.7,
15.6, 14.1.
IR (neat): 1597, 1493, 1465, 1442 cm–1.
1H NMR (300 MHz, CDCl3): d [(E)-9ba] = 7.43–7.35 (m, 2 H),
7.36–7.27 (m, 2 H), 7.26–7.17 (m, 1 H), 5.80 (t, J = 7.2 Hz, 1 H),
2.26–2.14 (m, 2 H), 2.04 (s, 3 H), 1.60–1.18 (m, 20 H), 0.89 (t,
J = 6.6 Hz, 3 H); d (10ba) = 5.27 (s, 1 H), 5.06 (s, 1 H), 2.50 (t,
J = 7.5 Hz, 2 H).
Synthesis 2007, No. 17, 2731–2745 © Thieme Stuttgart · New York

FEATURE ARTICLE
Palladium(0)-Catalyzed Addition of Organoboronic Acids with Allenes
2743
13C NMR (75.4 MHz, CDCl3): d = 144.0, 134.4, 128.8, 128.1,
126.4, 125.6, 31.9, 29.69, 29.66, 29.63, 29.60, 29.43, 29.37, 28.8,
22.7, 15.7, 14.1.
13C NMR (75.4 MHz, CDCl3): d = 158.5, 141.2, 136.1, 134.9,
128.42, 128.40, 126.7, 125.9, 125.1, 113.5, 55.3, 34.9, 16.0.
MS (EI, 70 eV): m/z (%) = 238 [M+] (94.32), 223 (100).
HRMS (EI): m/z calcd for C17H18O+ [M+]: 238.1358; found:
MS (EI, 70 eV): m/z (%) = 286 [M+] (37.23), 118 (100).
+
HRMS (EI): m/z calcd for C21H34 [M+]: 286.2661; found:
238.1378.
286.2651.
(E)-1,2-Diphenylprop-1-ene [(E)-12aa]18
(E)-2-(4-Methoxyphenyl)nonadec-2-ene [(E)-9cd]
Compound (E)-12aa was prepared similarly to compound (E)-9aa
by conditions B. The reaction of 3a (61 mg, 0.50 mmol), 11a (29
mg, 0.25 mmol), Pd(PPh3)4 (29 mg, 0.025 mmol), and AcOH (14
mL, 0.24 mmol) in dioxane (3 mL) afforded crude 12aa after evap-
oration [12aa/13aa > 99:1, (E)-12aa/(Z)-12aa > 99:1; by 1H NMR
analysis]. Pure (E)-12aa was isolated by flash chromatography (sil-
ica gel). Yield: 20 mg (41%); solid; mp 84–86 °C (Et2O) (Lit.18a
83.5–84 °C).
Compound (E)-9cd was prepared similarly to compound (E)-9aa by
conditions B. The reaction of 3d (76 mg, 0.50 mmol), 8c (66 mg,
0.25 mmol), Pd(PPh3)4 (29 mg, 0.025 mmol), and AcOH (14 mL,
0.24 mmol) in dioxane (3 mL) afforded a crude mixture of 9cd and
10cd after evaporation [9cd/10cd = 93:7, (E)-9cd/(Z)-9cd > 99:1;
by 1H NMR analysis]. A mixture of (E)-9cd and 10cd was isolated
by flash chromatography (silica gel); yield: 32 mg (34%); (E)-9cd/
10cd = 95:5. Pure (E)-9cd was obtained by recrystallization (Et2O);
solid; mp 45–47 °C (Et2O).
IR (neat): 1598, 1566, 1494, 1483, 1444 cm–1.
1H NMR (300 MHz, CDCl3): d = 7.57–7.51 (m, 2 H), 7.43–7.35 (m,
6 H), 7.34–7.25 (m, 2 H), 6.85 (q, J = 0.9 Hz, 1 H), 2.30 (d, J = 0.9
Hz, 3 H).
13C NMR (75.4 MHz, CDCl3): d = 143.9, 138.3, 137.4, 129.1,
128.3, 128.2, 127.7, 127.2, 126.5, 126.0, 17.5.
IR (neat): 1609, 1516, 1471, 1464 cm–1.
1H NMR (300 MHz, CDCl3): d = 7.33 (d, J = 9.2 Hz, 2 H), 6.86 (d,
J = 9.2 Hz, 2 H), 5.70 (t, J = 6.9 Hz, 1 H), 3.80 (s, 3 H), 2.24–2.12
(m, 2 H), 2.00 (s, 3 H), 1.51–1.18 (m, 28 H), 0.88 (t, J = 6.9 Hz, 3
H).
13C NMR (75.4 MHz, CDCl3): d = 158.3, 136.6, 133.7, 127.3,
126.5, 113.4, 55.2, 31.9, 29.70, 29.66, 29.60, 29.43, 29.37, 28.8,
22.7, 15.8, 14.1.
MS (EI, 70 eV): m/z (%) = 194 [M+] (100).
(E)-1-Phenyl-2-(4-tolyl)prop-1-ene [(E)-12ab]19
Compound (E)-12ab was prepared similarly to compound (E)-9aa
by conditions B. The reaction of 3b (67 mg, 0.49 mmol), 11a (29
mg, 0.25 mmol), Pd(PPh3)4 (30 mg, 0.026 mmol), and AcOH (14
mL, 0.24 mmol) in dioxane (3 mL) afforded crude 12ab after evap-
oration [12ab/13ab > 99:1, (E)-12ab/(Z)-12ab > 99:1; by 1H NMR
analysis]. Pure (E)-12ab was isolated by flash chromatography (sil-
ica gel). Yield: 38 mg (73%); solid; mp 67–69 °C (Et2O), (Lit.19 66–
66.5 °C).
MS (EI, 70 eV): m/z (%) = 372 [M+] (36.55), 161 (100).
Anal. Calcd for C26H44O: C, 83.80; H, 11.90. Found: C, 83.52; H,
11.82
(E)-1-Cyclohexyl-2-(4-methoxyphenyl)prop-1-ene [(E)-9dd]
Compound (E)-9dd was prepared similarly to compound (E)-9aa
by conditions B. The reaction of 3d (76 mg, 0.50 mmol), 8d (31 mg,
0.25 mmol), Pd(PPh3)4 (29 mg, 0.025 mmol), and AcOH (14 mL,
0.24 mmol) in dioxane (3 mL) afforded a crude mixture of 9dd and
10dd after evaporation [9dd/10dd = 88:12, (E)-9dd/(Z)-9dd >
IR (neat): 1510, 1486, 1444 cm–1.
1H NMR (300 MHz, CDCl3): d = 7.43 (d, J = 8.1 Hz, 2 H), 7.40–
7.33 (m, 4 H), 7.29–7.20 (m, 1 H), 7.19 (d, J = 8.1 Hz, 2 H), 6.83
(q, J = 1.2 Hz, 1 H), 2.38 (s, 3 H), 2.28 (d, J = 1.2 Hz, 3 H).
13C NMR (75.4 MHz, CDCl3): d = 141.0, 138.4, 137.2, 136.9,
129.1, 129.0, 128.1, 126.9, 126.3, 125.8, 21.1, 17.4.
1
99:1; by H NMR analysis]. A mixture of (E)-9dd and 10dd was
isolated by flash chromatography (silica gel). Yield: 25 mg (44%);
(E)-9dd/10dd = 92:8; liquid.
IR (neat): 1607, 1511, 1463, 1447, 1246 cm–1.
1H NMR (300 MHz, CDCl3): d [(E)-9dd] = 7.33 (d, J = 8.4 Hz, 2
H), 6.85 (d, J = 8.4 Hz, 2 H), 5.56 (d, J = 9.0 Hz, 1 H), 3.81 (s, 3 H),
2.40–2.26 (m, 1 H), 2.02 (s, 3 H), 1.81–1.50 (m, 4 H), 1.42–1.04 (m,
6 H); d (10dd) = 5.20 (s, 1 H), 4.93 (s, 1 H).
13C NMR (75.4 MHz, CDCl3): d = 158.3, 136.6, 133.1, 132.0,
126.5, 113.4, 55.3, 37.7, 33.2, 26.1, 26.0, 15.8.
MS (EI, 70 eV): m/z (%) = 208 [M+] (100).
(E)-2-(4-Methoxyphenyl)-1-phenylprop-1-ene [(E)-12ad]20
Compound (E)-12ad was prepared similarly to compound (E)-9aa
by conditions B. The reaction of 3d (76 mg, 0.50 mmol), 11a (29
mg, 0.25 mmol), Pd(PPh3)4 (29 mg, 0.025 mmol), and AcOH (14
mL, 0.24 mmol) in dioxane (3 mL) afforded crude 12ad after evap-
oration [12ad/13ad > 99:1, (E)-12ad/(Z)-12ad > 99:1; by 1H NMR
analysis]. Pure (E)-12ad was isolated by flash chromatography (sil-
ica gel). Yield: 44 mg (79%); solid; mp 93–94 °C (Et2O) (Lit.20 95–
98 °C).
MS (EI, 70 eV): m/z (%) = 230 [M+] (100).
HRMS (EI): m/z calcd for C16H22O+ [M+]: 230.1671; found:
230.1683.
IR (neat): 1619, 1605, 1514, 1446, 1414, 1261, 1181, 1028 cm–1.
(E)-3-(4-Methoxyphenyl)-1-phenylbut-2-ene [(E)-9ed]
Compound (E)-9ed was prepared similarly to compound (E)-9aa by
conditions B. The reaction of 3d (76 mg, 0.50 mmol), 8e (33 mg,
0.25 mmol), Pd(PPh3)4 (29 mg, 0.025 mmol), and AcOH (14 mL,
0.24 mmol) in dioxane (3 mL) afforded a crude mixture of 9ed and
10ed after evaporation [9ed/10ed > 93:7, (E)-9ed/(Z)-9ed 95:5;
by 1H NMR analysis]. Pure (E)-9ed was isolated by flash chroma-
tography (silica gel). Yield: 45 mg (76%); liquid.
1H NMR (300 MHz, CDCl3): d = 7.49 (d, J = 9.0 Hz, 2 H), 7.43–
7.34 (m, 4 H), 7.30–7.20 (m, 1 H), 6.93 (d, J = 9.0 Hz, 2 H), 6.81
(q, J = 1.2 Hz, 1 H), 3.85 (s, 3 H), 2.28 (d, J = 1.2 Hz, 3 H).
13C NMR (75.4 MHz, CDCl3): d = 158.9, 138.5, 136.7, 136.3,
129.1, 128.1, 127.0, 126.22, 126.18, 113.6, 55.3, 17.4.
MS (EI, 70 eV): m/z (%) = 224 [M+] (100).
IR (neat): 1607, 1574, 1511, 1494, 1453, 1441, 1245 cm–1.
Anal. Calcd for C16H16O: C, 85.68; H, 7.19. Found: C, 85.38; H,
7.21.
1H NMR (300 MHz, CDCl3): d = 7.41–7.17 (m, 7 H), 6.84 (d,
J = 8.7 Hz, 2 H), 5.92 (t, J = 7.5 Hz, 1 H), 3.81 (s, 3 H), 3.56 (d,
J = 7.5 Hz, 2 H), 2.13 (s, 3 H).
(E)-2-(4-Acetylphenyl)-1-phenylprop-1-ene [(E)-12ag]
Compound (E)-12ag was prepared similarly to compound (E)-9aa
by conditions B. The reaction of 3g (82 mg, 0.50 mmol), 11a (29
Synthesis 2007, No. 17, 2731–2745 © Thieme Stuttgart · New York

2744
H. Guo, S. Ma
FEATURE ARTICLE
mg, 0.25 mmol), Pd(PPh3)4 (29 mg, 0.025 mmol), and AcOH (14
mL, 0.24 mmol) in dioxane (3 mL) afforded crude 12ag after evap-
oration [12ag/13ag > 99:1, (E)-12ag/(Z)-12ag > 99:1; by 1H NMR
analysis]. Pure (E)-12ag was isolated by flash chromatography (sil-
ica gel). Yield: 26 mg (44%); solid; mp 104–106 °C (Et2O).
1H NMR (300 MHz, CDCl3): d = 7.49 (d, J = 8.6 Hz, 2 H), 7.42 (d,
J = 8.3 Hz, 2 H), 7.32 (d, J = 8.3 Hz, 2 H), 6.93 (d, J = 8.6 Hz, 2 H),
6.78 (s, 1 H), 3.85 (s, 3 H), 2.30 (s, 3 H), 1.37 (s, 9 H).
13C NMR (75.4 MHz, CDCl3): d = 158.8, 149.1, 136.6, 136.1,
135.6, 128.8, 127.0, 126.0, 125.0, 113.6, 55.3, 34.5, 31.3, 17.5.
IR (neat): 1677, 1599, 1450, 1410, 1357, 1272 cm–1.
MS (EI, 70 eV): m/z (%) = 280 [M+] (80.12), 265 (100).
1H NMR (300 MHz, CDCl3): d = 7.96 (d, J = 8.4 Hz, 2 H), 7.61 (d,
J = 8.4 Hz, 2 H), 7.45–7.35 (m, 4 H), 7.32–7.25 (m, 1 H), 6.95 (q,
J = 1.5 Hz, 1 H), 2.63 (s, 3 H), 2.31 (d, J = 1.5 Hz, 3 H).
Anal. Calcd for C20H24O: C, 85.67; H, 8.63. Found: C, 85.95; H,
8.66.
13C NMR (75.4 MHz, CDCl3): d = 197.7, 148.5, 137.7, 136.3,
135.7, 129.6, 129.1, 128.5, 128.2, 126.9, 126.0, 26.6, 17.3.
(E)-1-(4-Acetylphenyl)-2-(4-methoxyphenyl)prop-1-ene [(E)-
12dd]
Compound (E)-12dd was prepared similarly to compound (E)-9aa
by conditions B. The reaction of 3d (75 mg, 0.49 mmol), 11d (40
mg, 0.25 mmol), Pd(PPh3)4 (30 mg, 0.026 mmol), and AcOH (14
mL, 0.24 mmol) in dioxane (3 mL) afforded crude 12dd after evap-
oration [12dd/13dd > 99:1, (E)-12dd/(Z)-12dd > 99:1; by 1H NMR
analysis]. Pure (E)-12dd was isolated by flash chromatography (sil-
ica gel). Yield: 41 mg (62%); solid; mp 110–113 °C (Et2O).
MS (EI, 70 eV): m/z (%) = 236 [M+] (93.22), 43 (100).
Anal. Calcd for C17H16O: C, 86.40; H, 6.82. Found: C, 86.47; H,
6.96.
(E)-2-(1-Naphthyl)-1-phenylprop-1-ene [(E)-12ah]
Compound (E)-12ah was prepared similarly to compound (E)-9aa
by conditions B. The reaction of 3h (85 mg, 0.49 mmol), 11a (29
mg, 0.25 mmol), Pd(PPh3)4 (29 mg, 0.025 mmol), and AcOH (14
mL, 0.24 mmol) in dioxane (3 mL) afforded crude 12ah after evap-
oration [12ah/13ah > 99:1, (E)-12ah/(Z)-12ah > 99:1; by 1H NMR
analysis]. Pure (E)-12ah was isolated by flash chromatography (sil-
ica gel). Yield: 53 mg (87%); liquid.
IR (neat): 1678, 1597, 1514, 1406, 1262 cm–1.
1H NMR (300 MHz, CDCl3): d = 7.96 (d, J = 8.7 Hz, 2 H), 7.48 (d,
J = 8.6 Hz, 2 H), 7.43 (d, J = 8.6 Hz, 2 H), 6.92 (d, J = 8.7 Hz, 2 H),
6.79 (s, 1 H), 3.84 (s, 3 H), 2.62 (s, 3 H), 2.29 (s, 3 H).
13C NMR (75.4 MHz, CDCl3): d = 197.7, 159.2, 143.5, 139.2,
135.8, 134.8, 129.2, 128.3, 127.1, 125.2, 113.7, 55.3, 26.6, 17.7.
IR (neat): 1598, 1506, 1491, 1443 cm–1.
1H NMR (300 MHz, CDCl3): d = 8.21–8.13 (m, 1 H), 8.00–7.87 (m,
1 H), 7.88 (d, J = 8.1 Hz, 1 H), 7.62–7.46 (m, 8 H), 7.41–7.34 (m, 1
H), 6.70 (q, J = 1.2 Hz, 1 H), 2.48 (d, J = 1.2 Hz, 3 H).
13C NMR (75.4 MHz, CDCl3): d = 144.1, 137.9, 137.8, 133.8,
131.0, 130.4, 129.0, 128.4, 128.3, 127.2, 126.6, 125.82, 125.75,
125.7, 125.4, 124.8, 20.9.
MS (EI, 70 eV): m/z (%) = 266 [M+] (100).
Anal. Calcd for C18H18O2: C, 81.17; H, 6.81. Found: C, 81.15; H,
6.83.
Synthesis of Sulfone (E)-4ab from Sulfoxide (E)-6ab
A soln of (E)-6ab (101 mg, 0.4 mmol) and 30% H2O2 (5 mL) in
AcOH (5 mL) was stirred at 40 °C for 24 h. After complete conver-
sion of the starting material as monitored by TLC (PE–Et2O, 1:1),
the mixture was quenched with H2O (15 mL), and extracted with
CHCl3 (6 × 25 mL). The organic layer was then neutralized by
washing with sat. aq NaHCO3. The combined organic layer was
dried (MgSO4). Evaporation of the solvent and flash chromatogra-
phy (silica gel, PE–Et2O, 3:1) afforded of (E)-4ab; yield: 57 mg
(52%).
MS (EI, 70 eV): m/z (%) = 244 [M+] (94.43), 229 (100).
+
HRMS (EI): m/z calcd for C19H16 [M+]: 224.1252; found:
244.1255.
(E)-1,2-Bis(4-methoxyphenyl)prop-1-ene [(E)-12bd]21
Compound (E)-12bd was prepared similarly to compound (E)-9aa
by conditions B. The reaction of 3d (75 mg, 0.49 mmol), 11b (37
mg, 0.25 mmol), Pd(PPh3)4 (30 mg, 0.026 mmol), and AcOH (14
mL, 0.24 mmol) in dioxane (3 mL) afforded crude 12bd after evap-
oration [12bd/13bd > 99:1, (E)-12bd/(Z)-12bd > 99:1; by 1H NMR
analysis]. Pure (E)-12bd was isolated by flash chromatography (sil-
ica gel). Yield: 38 mg (60%); solid; mp 121–122 °C (Et2O) (Lit.21a
122–123 °C).
Acknowledgment
We are grateful to the National Natural Science Foundation of Chi-
na (Grant No. 20121202 and 20332060).
IR (neat): 1608, 1511, 1452, 1252 cm–1.
1H NMR (300 MHz, CDCl3): d = 7.47 (d, J = 8.7 Hz, 2 H), 7.31 (d,
J = 8.7 Hz, 2 H), 6.96–6.87 (m, 4 H), 6.74 (s, 1 H), 3.84 (s, 6 H),
2.26 (s, 3 H).
13C NMR (75.4 MHz, CDCl3): d = 158.7, 158.0, 136.6, 135.3,
131.1, 130.3, 126.9, 125.8, 113.6, 113.5, 55.3, 55.2, 17.4.
References
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MS (EI, 70 eV): m/z (%) = 254 [M+] (100).
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Compound (E)-12cd was prepared similarly to compound (E)-9aa
by conditions B. The reaction of 3d (77 mg, 0.51 mmol), 11c (43
mg, 0.25 mmol), Pd(PPh3)4 (29 mg, 0.025 mmol), and AcOH (14
mL, 0.24 mmol) in dioxane (3 mL) afforded crude 12cd after evap-
oration [12cd/13cd > 99:1, (E)-12cd/(Z)-12cd > 99:1; by 1H NMR
analysis]. Pure (E)-12cd was isolated by flash chromatography (sil-
ica gel). Yield: 46 mg (66%); solid; mp 100–101 °C (Et2O).
IR (neat): 1605, 1513, 1463, 1247 cm–1.
Synthesis 2007, No. 17, 2731–2745 © Thieme Stuttgart · New York

FEATURE ARTICLE
Palladium(0)-Catalyzed Addition of Organoboronic Acids with Allenes
2745
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(11) Å, b = 9.9879 (11) Å, c = 10.6025 (12) Å, a = 102.675
(2)°, b = 101.020 (2)°, g = 116.035 (2)°, V = 838.98 (16) Å3,
T = 293 (2) K, Z = 2, reflections collected/unique: 5004/
3565 (Rint = 0.0485), no observation [I > 2s(I)] 3565,
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Synthesis 2007, No. 17, 2731–2745 © Thieme Stuttgart · New York