Palladium-catalyzed vinylselenation of allenes

Article abstract of DOI:10.1016/j.tet.2012.10.003

Pd(0)-catalyzed vinylselenation of allenes was found to proceed efficiently in the presence of P(p-MeC₆H₄)₃ as a ligand to afford the corresponding 2-selenomethyl-1,3-dienes. This reaction is highly regioselective and vinyl selenides added to the terminal double bond of the allenes exclusively to introduce the vinyl group at the inner carbon and the selenium moiety at the terminal carbon. The stereochemistry of the double bond of the vinyl selenides was perfectly retained.

Full text of DOI:10.1016/j.tet.2012.10.003

Tetrahedron 68 (2012) 10523e10529
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Palladium-catalyzed vinylselenation of allenes
Shin-ichi Fujiwara a, Maiko Okuyama b, Susumu Tsuda a, Takanori Iwasaki b, Hitoshi Kuniyasu b,
,
Nobuaki Kambe b
*
a Department of Chemistry, Osaka Dental University, 8-1 Kuzuha-Hanazonocho, Hirakata, Osaka 573-1121, Japan
b Department of Applied Chemistry, Graduate School of Engineering, Osaka University, 2-1 Yamadaoka, Suita, Osaka 565-0871, Japan
a r t i c l e i n f o
a b s t r a c t
Article history:
Pd(0)-catalyzed vinylselenation of allenes was found to proceed efficiently in the presence of
P(p-MeC6H4)3 as a ligand to afford the corresponding 2-selenomethyl-1,3-dienes. This reaction is highly
regioselective and vinyl selenides added to the terminal double bond of the allenes exclusively to
introduce the vinyl group at the inner carbon and the selenium moiety at the terminal carbon. The
stereochemistry of the double bond of the vinyl selenides was perfectly retained.
Ó 2012 Elsevier Ltd. All rights reserved.
Received 10 July 2012
Received in revised form 24 September
2012
Accepted 1 October 2012
Available online 6 October 2012
Keywords:
Vinylselenation
Allene
1,3-Diene
Vinyl selenide
Pd catalyst
1. Introduction
Simultaneous addition of carbon and heteroatom units to al-
kynes with the cleavage of carboneheteroatom bond by transition
metal complexes has attracted great interest in recent organic and
organometallic chemistry.1e5 This reaction proceeds in cis-selective
manner to give multi-functionalized alkenyl heteroatom com-
pounds. For such transformation, introduction of allyl,1 alkynyl,2
acyl,3 and cyano4 groups as carbon units has been well studied.
However the introduction of vinyl group, i.e., addition of the vinyl-
eheteroatom bond across the triple bond, leading to 1,3-dienes
was limited to the cases involving ring-expansion of three- or
four-membered heterocyclic compounds, such as addition of sila-
cyclopropenes,5a methylidenesiliranes,5b allene episulfides,5c and
silacyclobutenes5d to alkynes. In these systems, ring strain of start-
ing compounds may promote the cleavage of the vinyleheteroatom
bond by the metal catalyst.
Scheme 1. Vinylselenation of alkynes.
Allenes as well as alkynes have been shown to be versatile
building blocks in organic synthesis during the past 20 years.8 It is
known that a variety of heteroatom compounds, such as organotin,
-borane, -selenium species add to allenes in the presence of tran-
sition metal catalysts, where an allene double bond inserts into
9
0
R3SneH, R3SieBR2 , and RSeeSeR0 bonds. There are only fewer
examples, however, of allene insertion into carboneheteroatom
bonds,5a,b,10 and in these cases, vinylic heteroatom products were
obtained as the major products rather than allylic compounds. We
also disclosed the first example of carboselenation of allenes
leading to allylic selenides 2, where the selenol ester added to the
terminal CeC double bond of the allene regioselectively to in-
troduce the acyl moiety at the inner carbon and the SePh group at
the terminal carbon (Scheme 2).11,12
We found that an anion stabilizing group on the b-position of
acyclic vinyl sulfides and selenides enhanced oxidative addition to
Pt(0) complex.6 Based on this finding we disclosed Pt(0)-catalyzed
intramolecular cis-vinylselenation of alkynes leading to effective
construction of six-membered lactam framework 1 having a high
degree of unsaturation (Scheme 1).7
These successful results led us to examine the reaction of vinyl
selenides with allenes and found that vinylselenation of allenes
took place when activated vinyl selenides were employed in the
* Corresponding author. E-mail address: kambe@chem.eng.osaka-u.ac.jp
(N. Kambe).
0040-4020/$ e see front matter Ó 2012 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.tet.2012.10.003

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S.-i. Fujiwara et al. / Tetrahedron 68 (2012) 10523e10529
Table 2 summarizes the results obtained using several cis-vinyl
selenides and allenes under optimized conditions. Phenylallene 4b,
1,2-undecadiene 4c, and benzyloxyallene 4d afforded the expected
1,3-dienes 5abe5ad in moderate yields (entries 1e3).18 Vinyl sel-
enides having electron-donating and -withdrawing groups in the
phenyl ring gave rise to 1,3-diene 5ba and 5ca in 78% and 72%
yields, respectively (entries 4 and 5) indicating that aryl group on
selenium exerts little effect on the yield. We then examined the
Scheme 2. Acylselenation of allenes.
effect of the substituent on the b-position of vinyl selenides and
presence of Pd(0) complex as
framework.13
a catalyst to form 1,3-diene
found that amide and sulfonyl groups also afforded the expected
products in good yields (entries 6 and 7); however, in the case of
phenyl group, almost all of 3f was recovered and the expected 1,3-
diene was not obtained probably due to the difficulty of oxidative
addition of 3f to palladium (entry 8). Interestingly selenide 3g
bearing a methoxycarbonyl group at the ortho-position on a phenyl
ring also underwent arylselenation with 4a to give 5ga albeit in
a moderate yield (35%) after 24 h (entry 9). Vinylthiolation of allene
did proceed under similar conditions; however, the yield of the
expected product was poor (15%).
To get information on the stereochemistry of this vinylselenation
we run the reaction of trans-vinyl selenide 3a with cyclohexylallene
4a under similar conditions and the expected 1,3-diene 6aa was
obtained in 94% NMR yield (79% isolated yield) (Scheme 4). From
the results of Table 1 and Eq. 4, the stereochemistry of the vinyl
selenide was retained intact through out the reaction.
2. Results and discussion
Firstly, the reaction of cis-vinyl selenide 3a having an ethox-
ycarbonyl group on the -position of its vinyl moiety with cyclo-
b
hexylallene 4a was examined. Thus CH3CN (0.3 mL) containing cis-
3a (0.3 mmol), cyclohexylallene 4a (2 equiv), and Pt(PPh3)4
(5 mol %) was heated at reflux for 8 h. As a result, only a trace
amount of 1,3-diene 5aa bearing an allyl selenide moiety was ob-
tained.14,15 On the contrary, when Pd(dba)2 (5 mol %)ePPh3
(10 mol %) was employed in place of Pt(PPh3)4, 5aa was obtained in
90% NMR yield (Scheme 3, entry 1 in Table 1).16
The diene products 3 include cis,trans-stereoisomers with re-
spect to the other double bond arising from allenes. When the
vinylselenation shown in entry 6 in Table 1 was stopped at 0.5 h, E/Z
ratio increased to 9/91 (16% yield). The same reaction conducted at
70 ꢀC gave only its Z-isomer in 26% yield as the sole detectable
product by NMR. From these experiments Z-isomer was considered
to be initially formed stereoselectively and isomerized to its E-
isomer thermodynamically. DFT calculations by B3LYP/6-31G(d)
showed Z-5aa was more stable by 0.6 kcal/mol than E-5aa.19
These results do not conflict with the observed stereoselectivity.
A plausible reaction pathway is shown in Scheme 5. This cata-
lytic process is initiated by oxidative addition of the vinyleSe bond
of vinyl selenide 3 to Pd(0), affording the vinylePdeSe complex A.
Scheme 3. Vinylselenation of cyclohexylallene with vinyl selenide cis-3a.
Insertion of allene into the vinylePd bond via B generates
palladium C and/or -allylpalladium D, which undergoes reductive
elimination to give 5.
s-allyl-
Table 1
p
Phosphine ligand optimization for Pd(0)-catalyzed vinylselenation of
cyclohexylallene with vinyl selenide cis-3a
Finally, further transformation of the product was undertaken.
Since allyl selenides are well known to lead to allyl alcohol upon
treatment with oxidizing reagents, such as mCPBA,20 we treated
5aa with mCPBA and found that lactone 7 was produced in 82%
yield probably via in situ formed allyl alcohol 8 (Scheme 6).
Entrya
Phosphine
5aa, yieldb
E/Zc
1
2
3
4
5
6
7
8
9
PPh3
90%
77%
35%
87%
86%
94%(81%)
42%
59%
13%
17/83
19/81
13/87
18/82
14/86
16/84(16/84)
6/94
11/89
1/>99
19/81
PPh3 (20 mol %)
PPh3 (50 mol %)
P(p-FC6H4)
P(p-MeOC6H4)
P(p-MeC6H4)
P(o-MeOC6H4)
PMePh2
3. Conclusion
Vinyl selenides having an electron attracting group at the b-po-
PnBu3
10
PcHex3
3%
sition add to the terminal double bond of allenes with excellent
regioselectivity in the presence of Pd(0)-P(p-MeC6H4)3 catalyst,
producing functionalized 1,3-dienes having an allyl selenide moiety.
This reaction was Z-selective with respect to the internal allene
double bond and the stereochemistry of vinyl selenides were com-
pletely retained in the products. Oxidation of a product by mCPBA
afforded a six-membered unsaturated lactone in a good yield.
a
Reaction conditions: cis-3a (0.3 mmol), cyclohexylallene 4a (0.6 mmol),
Pd(dba)2 (5 mol %), ligand (10 mol %), CH3CN (0.3 mL), reflux, 8 h.
b
NMR yield (isolated yield).
c
E/Z ratio was determined by 1H NMR with regard to the double bond originally
from the allene. Stereochemistry of vinyl selenide was retained in all entries.
Next, we carried out the reaction using other phosphines as the
ligand. As can be seen from Table 1, similar results were obtained
from the aromatic phosphines having either electron-donating or
-withdrawing group at the para position (entries 1 and 4e6). The
use of larger amounts of triphenyl phosphine reduced the yields
of 5aa (entries 2e3). Sterically hindered ortho-tolyl and aliphatic
phosphines were less efficient (entries 7e10). In all entries, Z-iso-
mer was obtained preferentially with the perfect retention of ste-
reochemistry of the vinyl selenide employed.17
4. Experimental section
4.1. Synthesis of vinyl selenide
4.1.1. (Z)-Ethyl 3-(2,6-dimethylphenylseleno)acrylate (3b): typical
procedure A. Into a 1000-mL flask equipped with a reflux con-
denser were placed di(2,6-dimehthyl)phenyl diselenide (60 mmol)
and EtOH (440 mL) under N2. After vigorous stirring and warming

S.-i. Fujiwara et al. / Tetrahedron 68 (2012) 10523e10529
10525
Table 2
Vinylselenation of allenes
Entrya
Vinyl selenide
Allene
Product
Yieldb
E/Zc
1d
56%(48%)
68/32
2e
3a
3a
57%(40%)
61%(56%)
78%(54%)
53/47
15/85
26/74
3
4
5
6
4a
4a
72%(54%)
69%(44%)
27/73
8/92
7
8
4a
4a
70%(63%)
19/81
ND
ND
9f
4a
4a
35%(31%)
14%(5%)
30/70
0/100
10
a
Reaction conditions: vinyl selenide 3 (0.3 mmol), allene 4 (0.6 mmol), Pd(dba)2 (5 mol %), P(p-MeC6H4)3 (10 mol %), CH3CN (0.3 mL), reflux, 8 h.
b
c
d
e
f
NMR yield (isolated yield).
E/Z ratio was determined by 1H NMR with regard to the double bond originally from the allene. Stereochemistry of vinyl selenide was retained in all entries.
Pd(PPh3)4 (5 mol %), 4 h.
Pd(PPh3)4 (5 mol %), 12 h.
24 h.
with water bath (ca. 40 ꢀC), homogeneous redeorange solution was
obtained. After cooling to room temperature, small portions of
NaBH4 were added successively until the solution turned slight
yellow. To the solution was added ethyl propiolate (120 mmol) after
gas emission ceased. Then the mixture was refluxed for 3 h under
stirring (oil bath, 94 ꢀC). EtOH was removed in vacuo and aqueous
residue was obtained. Et2O was poured into the flask and washed
with satd NaCl aq. The combined organic phase was dried over

10526
S.-i. Fujiwara et al. / Tetrahedron 68 (2012) 10523e10529
60.8, 117.7, 126.1 (two peaks overlapped), 131.2, 131.5, 133.1 (two
peaks overlapped), 134.4, 147.7, 164.8; NOE experiment for Z-iso-
mer: irradiation for the vinylic proton doublet at 6.43 resulted in
12.4% enhancements of the signal at 7.72 (vinylic doublet); IR
d
d
(neat) 3019, 1692 (C]O), 1326, 1216, 757, 669 cmꢁ1; MS (EI), m/z
(%)¼145 (22), 199 (22), 225 (37), 251 (21), 279 (37), 322 (49), 324
(Mþ, 100). Anal. Calcd for C12H11F3O2Se: C, 44.60; H, 3.43. Found: C,
44.21; H, 3.36.
Scheme 4. Vinylselenation of cyclohexylallene with vinyl selenide trans-3a.
4.1.3. (Z)-N,N-Diethyl-3-phenylselenoacrylamide
according to the modified literature procedure.7 56% yield: slight-
yellow oil; 1H NMR (400 MHz, CDCl3)
1.53 (br s, 6H), 3.39 (q,
(3d). Prepared
d
J¼7.1 Hz, 2H), 3.49 (q, J¼7.1 Hz, 2H), 6.68 (d, J¼8.8 Hz, 1H),
7.32e7.343 (m, 3H), 7.61e7.65 (m, 3H); 13C NMR (100 MHz, CDCl3)
d
14.8,15.2, 40.9, 42.2, 115.0, 127.7, 129.1, 133.2, 134.5, 147.0, 166.4; IR
(neat) 2973, 1619 (C]O), 1577, 1478, 1429, 1260, 1144, 741,
693 cmꢁ1; MS (EI), m/z (%)¼126 (89), 131 (36), 157 (40), 183 (23),
206 (26), 209 (48), 211 (96), 281 (50), 283 (Mþ, 100); HRMS (EI)
calcd for C13H17NOSe: 283.0475. Found: 283.0471.
4.1.4. (Z)-1-(2-Phenylseleno)-vinylsulfonyl-4-methylbenzene
(3e). Prepared according tothe modified literature procedure.21 57%
yield: white needle crystal; mp 79.4e79.9 ꢀC; 1H NMR (400 MHz,
CDCl3)
d
2.45 (s, 3H), 6.65 (d, J¼9.6 Hz,1H), 7.34e7.37 (m, 5H), 7.57 (d,
J¼8.1 Hz, 2H), 7.65 (d, J¼9.6 Hz, 1H), 7.89 (d, J¼8.1 Hz, 2H); 13C NMR
(100 MHz, CDCl3) d 21.7, 125.9, 127.2 (two peaks overlapped), 128.7,
129.5, 129.9 (two peaks overlapped), 131.3, 133.5 (two peaks over-
lapped), 138.0, 144.7, 145.2, 145.3; IR (neat) 2924, 1286, 1141, 1083,
691 cmꢁ1; MS (EI), m/z (%)¼91 (42), 155 (28), 157 (56), 180 (50), 182
(100), 183 (24), 335 (36), 337 (7), 338 (Mþ, 73). Anal. Calcd for
C15H14O2SSe: C, 53.41; H, 4.18. Found: C, 53.48; H, 4.13.
Scheme 5. A plausible reaction pathway.
4.1.5. Methyl 2-phenylselenobenzoate (3g). Prepared according to
the modified literature procedure.22 7% yield: slight-yellow solid;
mp 69.5e69.8 ꢀC; 1H NMR (400 MHz, CDCl3)
d 3.97 (s, 3H), 6.91 (d,
J¼6.9 Hz, 1H), 7.14e7.72 (m, 7H), 8.05 (d, J¼6.9 Hz, 1H); 13C NMR
(100 MHz, CDCl3) d 30.9, 52.3, 124.7, 127.1, 128.9, 129.0, 129.2, 129.8,
131.3, 132.6, 137.6 (two peaks overlapped), 140.5, 167.3; IR (neat)
1096, 907, 733, 650 cmꢁ1; MS (EI), m/z (%)¼152 (30), 232 (36), 261
(34), 290 (49), 292 (Mþ, 100). Anal. Calcd for C14H12O2Se: C, 57.74;
H, 4.15. Found: C, 57.66; H, 4.04.
4.1.6. (Z)-N,N-Diethyl-3-phenylthioacrylamide
according to the modified literature procedure.7 82% yield: yellow
oil; 1H NMR (400 MHz, CDCl3)
1.17e1.23 (m, 6H), 3.38 (q, J¼6.9 Hz,
2H), 3.48 (q, J¼6.9 Hz, 2H), 6.22 (d, J¼10 Hz, 1H), 7.15 (d, J¼10 Hz,
1H), 7.27e7.52 (m, 5H); 13C NMR (100 MHz, CDCl3)
13.3,14.8, 40.6,
(3h). Prepared
Scheme 6. Further transformation to lactone.
d
d
anhydrous MgSO4. The solvents of filtrate were removed in vacuo.
Purification by silica gel column chromatography (hexane/Et2O¼7/
1) afforded 3b in 24% yield: slight-yellow oil; 1H NMR (400 MHz,
42.3, 112.2, 127.7, 129.1 (two peaks overlapped), 130.9 (two peaks
overlapped), 138.0, 146.7, 165.8; IR (neat) 2973, 2917, 1622 (C]O),
1557, 1478, 1431, 1261, 1144, 747 cmꢁ1; MS (EI), m/z (%)¼126 (45),
163 (100), 235 (Mþ, 45); HRMS (EI) calcd for C13H17NOS: 235.1031.
Found: 235.1029.
CDCl3)
d
1.34 (t, J¼7.3 Hz, 3H), 4.28 (q, J¼7.3 Hz, 2H), 6.37 (d,
J¼9.6 Hz, 1H), 7.12e7.21 (m, 3H), 7.38 (d, J¼9.6 Hz, 1H); 13C NMR
(100 MHz, CDCl3)
d
14.4, 24.6 (two peaks overlapped), 60.4, 117.0,
Vinyl selenides cis- and trans-3a23 and 3f24 were prepared as
reported.
127.9 (two peaks overlapped), 129.1, 133.4, 142.5 (two peaks over-
lapped), 150.6, 167.6; NOE experiment for Z-isomer: irradiation for
the vinylic proton doublet at
d
6.37 resulted in 12.6% enhancements
4.2. Vinylselenation of allene
of the signal at
d
7.38 (vinylic doublet).; IR (neat) 3408, 2917, 1687
(C]O),1461,1215, 907, 733, 650 cmꢁ1; MS (EI), m/z (%)¼77 (22),105
(98), 129 (38), 130 (27), 157 (36), 158 (29), 193 (22), 194 (50), 196
(99), 197 (23), 209 (26), 282 (50), 284 (Mþ, 100). Anal. Calcd for
C13H16O2Se: C, 55.13; H, 5.69. Found: C, 55.01; H, 5.59.
4.2.1. 5-Cyclohexyl-4-phenylselenomethylpenta-2(Z),4-dienoate
(5aa): typical procedure. Into a 3-mL flask equipped with a reflux
condenser were placed Pd(dba)2 (0.015 mmol), P(p-MeC6H4)3
(0.030 mmol) and CH3CN (0.3 mL) at room temperature under N2.
The mixture was stirred for 10 min, added cis-vinyl selenide 3a
(0.3 mmol) and cyclohexylallene 4a (0.6 mmol), and turned brown.
After the mixture was refluxed for 8 h, filtered through the Celite
pad with Et2O, volatiles were removed in vacuo. After the E/Z ratio
were determined by 1H NMR (94% NMR yield, E/Z¼16/84), the crude
4.1.2. (Z)-Ethyl 3-(4-trifluoromethylphenylseleno)acrylate (3c). 12%:
white solid; mp 99.7e100.4 ꢀC; 1H NMR (400 MHz, CDCl3)
d 1.34 (t,
J¼7.3 Hz, 3H), 4.27 (q, J¼7.3 Hz, 2H), 6.43 (d, J¼9.2 Hz, 1H), 7.59 (d,
J¼8.2 Hz, 2H), 7.71e7.73 (m, 3H); 13C NMR (100 MHz, CDCl3)
d 14.3,

S.-i. Fujiwara et al. / Tetrahedron 68 (2012) 10523e10529
10527
product was purified by preparative recycling HPLC (eluted with
d
3.97 resulted in 2.6% enhancements of the signal at
d
1.87e1.91
CHCl3) to afford ethyl 5-cyclohexyl-4-phenylselenomethylpenta-
(multiplet) and irradiation for the vinylic proton doublet at
resulted in 14.5% and 11.3% enhancements of the signal at
d
6.41
5.71
2(Z),4-dienoate (5aa) in 81% yield as a E/Z mixture: colorless oil; 1H
d
NMR (400 MHz, CDCl3)
d
0.89e1.70 (m,13H),1.94e2.02 (m,1H), 3.82
(vinylic doublet) and the signal at
periment for E-isomer: irradiation of the allylic proton (eCH2SePh)
singlet at 3.83 resulted in 5.4% enhancements of the signal at
5.36 (vinylic triplet), irradiation of the vinylic proton triplet at
5.36 resulted in 1.9% and 6.0% enhancements of the signal at
1.87e1.91 (multiplet) and the signal at 3.83 (allylic singlet) and
d 5.77 (vinylic triplet); NOE ex-
(s, 2H, E), 3.98 (s, 2H, Z), 4.11e4.17 (q, 2H), 5.13 (d, J¼9.6 Hz, 1H, E),
5.57 (d, J¼9.6 Hz,1H, Z), 5.71 (d, J¼13 Hz,1H, Z), 5.88 (d, J¼12 Hz,1H,
E), 6.39 (d, J¼13 Hz,1H, Z), 6.72 (d, J¼11 Hz,1H, E), 7.23e7.26 (m, 3H),
7.46e7.48 (m, 2H, E), 7.52e7.55 (m, 2H, Z); 13C NMR (100 MHz,
d
d
d
d
CDCl3)
d
14.1 (E), 14.2 (Z), 25.5 (Z), 25.6 (E), 25.7 (Z), 25.8 (E), 27.0 (Z),
d
32.3 (E), 32.3 (Z), 34.7 (E), 37.5 (Z), 37.9 (E), 60.2 (E), 60.2 (Z),118.2 (Z),
121.3 (E), 127.1 (E), 127.3 (Z), 128.7 (E), 128.8 (Z), 130.3 (E), 131.1 (Z),
132.0 (E), 132.1 (Z), 134.0 (E), 134.2 (Z), 139.1 (E), 141.8 (E), 144.2 (Z),
145.6 (Z), 165.6 (E), 166.4 (Z); NOE experiment for Z-isomer: irra-
irradiation of the vinylic proton doublet at
and 12.4% enhancements of the signal at
d
6.69 resulted in 1.5%
1.87e1.91 (multiplet)
d
and the signal at d 5.90 (vinylic doublet); IR (neat) 2957, 2925, 2854,
1717 (C]O), 1176, 1024 cmꢁ1; MS (CI), m/z (%)¼251 (93), 407 (52),
409 (Mþþ1,100); HRMS (CI) calcd for C22H32O2Se: 408.1567. Found:
409.1642.
diation for the vinylic proton doublet at
10.8% enhancements of the signal at 5.71 (vinylic doublet) and the
signal at 5.57 (vinylic doublet) and irradiation of the allylic proton
(eCH2SePh) singlet at 3.98 resulted in 11.3%, 1.5%, and 3.0% en-
hancements of the signal at 1.94e2.02 (multiplet), the signal at
6.39 (vinylic doublet) and the signal at 7.52e7.55 (multiplet);
NOE experiment for E-isomer: irradiation for the vinylic proton
doublet at 6.72 resulted in 3.2% and 8.9% enhancements of the
signal at 1.94e2.02 (multiplet) and the signal at 5.88 (vinylic
doublet) and irradiation of the allylic proton (eCH2SePh) singlet at
3.82 resulted in 7.8% and 2.2% enhancements of the signal at 5.13
(vinylic doublet) and the signal at 7.46e7.48 (multiplet); IR (neat)
d 6.39 resulted in 7.9% and
d
d
d
4.2.4. Ethyl 5-benzyloxy-4-phenylselenomethylpenta-2(Z),4-dienoate
d
(5ad). 1H NMR (400 MHz, CDCl3)
d 1.23e1.28 (t, 3H), 3.91 (s, 2H, E),
d
d
4.10e4.15 (q, 2H), 4.18 (s, 2H, Z), 4.71 (s, 2H, E), 4.74 (s, 2H, Z), 5.59
(d, J¼13 Hz, 1H, Z), 5.77 (d, J¼13 Hz, 1H, E), 6.04 (s, 1H, E), 6.12 (d,
J¼13 Hz, 1H, Z), 6.79 (d, J¼13 Hz, 1H, E), 6.86 (s, 1H, Z), 7.16e7.56 (m,
d
d
d
10H); 13C NMR (100 MHz, CDCl3)
d 14.3, 24.1 (Z), 30.0 (E), 60.0 (Z),
60.1 (E), 72.7 (E), 74.9 (Z), 112.4 (E), 114.6 (Z), 115.3 (Z), 117.8 (E),
126.8, 127.1, 127.4 (two peaks overlapped), 128.2 (two peaks over-
lapped), 128.5 (two peaks overlapped), 128.6, 129.0, 129.2, 130.7,
132.0, 132.1, 133.8 (two peaks overlapped),134.5, 134.8, 136.0, 136.2,
140.1 (Z), 142.1 (E), 150.3 (E), 155.3 (Z), 166.7; NOE experiment for Z-
isomer: irradiation of the vinylic proton doublet at
14.3% and 13.1% enhancements of the signal at
doublet) and the signal at 6.86 (vinylic singlet) and irradiation for
d
d
d
2925, 2850,1714 (C]O),1526,1626,1447,1175,1032, 738, 691 cmꢁ1
;
MS (CI), m/z (%)¼221 (84), 377 (52), 379 (Mþþ1,100). Anal. Calcd for
C20H26O2Se: C, 63.65; H, 6.94. Found: C, 63.93; H, 6.82.
d
6.12 resulted in
d
5.77 (vinylic
4.2.2. Ethyl 5-phenyl-4-phenylselenomethylpenta-2(Z),4-dienoate
(5ab). 1H NMR (400 MHz, CDCl3)
d
1.24 (m, 3H), 4.05 (s, 2H, Z),
the vinylic proton singlet at
hancements of the signal at
d
6.86 resulted in 17.4% and 13.0% en-
4.14 (s, 2H, E), 4.12e4.81 (two q peaks overlapped, 2H), 5.87 (d,
J¼12 Hz, 1H, E), 5.99 (d, J¼12 Hz, 1H, Z), 6.28 (s, 1H, E), 6.60 (d,
J¼14 Hz, 1H, E), 6.75 (s, 1H, Z), 6.76 (d, J¼12 Hz, 1H, Z), 7.09e7.51 (m,
d 4.74 (benzylic singlet) and the signal
at
d
6.12 (vinylic doublet); NOE experiment for E-isomer: irradia-
3.91 resulted in
6.04 (vinylic singlet), irradi-
6.04 resulted in 5.8% and 8.6%
3.91 (allylic singlet) and the signal
4.71 (benzylic singlet) and irradiation of the vinylic proton
doublet at 6.79 resulted in 11.7% enhancements of the signal at
tion of the allylic proton (eCH2SePh) singlet at
7.2% enhancements of the signal at
ation of the vinylic proton singlet at
enhancements of the signal at
at
d
10H); 13C NMR (100 MHz, CDCl3)
d
14.2 (E),14.3 (Z), 27.9 (Z), 35.5 (E),
d
60.4 (E), 60.5 (Z), 118.6, 120.5, 122.2, 127.1, 127.5, 128.0, 128.3, 128.6,
128.9, 129.2, 129.5, 130.1, 130.2, 132.5, 133.2, 133.3, 134.0 (two peaks
overlapped), 134.5, 135.2, 135.5, 136.1, 136.3, 138.3, 140.1, 143.2,
144.0, 147.1, 166.3, 167.1, 167.2; NOE experiment for Z-isomer: ir-
d
d
d
d
radiation for the vinylic proton doublet at
and 8.6% enhancements of the signal at 5.87 (vinylic doublet) and
the signal at 6.75 (vinylic singlet) and irradiation of the vinylic
proton doublet at 5.87 resulted in 13.7% enhancements of the
signal at 6.75 (vinylic singlet); NOE experiment for E-isomer: ir-
radiation for the vinylic proton doublet at 6.28 resulted in 7.2%
enhancements of the signal at 4.05 (allylic singlet) and irradiation
of the allylic proton (eCH2SePh) singlet at 4.05 resulted in 8.4%
enhancements of the signal at 6.28 (vinylic singlet) and irradia-
tion of the vinylic proton doublet at 5.99 resulted in 13.8% en-
hancements of the signal at 6.76 (vinylic doublet); IR (neat) 2979,
d
6.60 resulted in 14.5%
d 5.77 (vinylic doublet); IR (neat) 2980, 1722 (C]O), 1161, 1022, 737,
d
696 cmꢁ1; MS (CI), m/z (%)¼155 (69), 245 (100), 321 (40), 403
(Mþþ1, 11); HRMS (CI) calcd for C21H22O3Se: 402.0734. Found:
403.0804.
d
d
d
d
4.2.5. Ethyl 5-cyclohexyl-4-(2,6-dimethylphenylselenomethyl)penta-
d
2(Z),4-dienoate (5ba). 1H NMR (400 MHz, CDCl3)
d 0.79e1.57 (m,
d
13H), 1.77e1.85 (m, 1H, Z), 1.94e1.96 (m, 1H, E), 2.52 (s, 6H, E), 2.56
(s, 6H, Z), 3.62 (s, 2H, E), 3.75 (s, 2H, Z), 4.10e4.16 (m, 2H), 4.93 (d,
J¼9.6 Hz, 1H, E), 5.51 (d, J¼10 Hz, 1H, Z), 5.70 (d, J¼13 Hz, 1H, Z),
5.84 (d, J¼12 Hz, 1H, E), 6.40 (d, J¼13 Hz, 1H, Z), 6.71 (d, J¼12 Hz,
d
d
d
1714 (C]O), 1621, 1476, 1446, 1438, 1186, 1030, 739, 693 cmꢁ1; MS
(CI), m/z (%)¼215 (Mþþ1,100); Anal. Calcd for C20H20O2Se: C, 64.69;
H, 5.43. Found: C, 64.63; H, 5.46.
1H, E), 7.04e7.11 (m, 3H); 13C NMR (100 MHz, CDCl3)
d 14.3, 24.6
(two peaks overlapped), 25.8 (two peaks overlapped), 25.8, 32.2,
32.4 (two peaks overlapped), 37.7, 60.2, 117.9, 121.0, 127.4 (two
peaks overlapped), 128.1, 128.4, 131.9, 143.6, 144.7, 145.2, 166.4;
NOE experiment for Z-isomer: irradiation for the vinylic proton
4.2.3. Ethyl 4-phenylselenomethyltrideca-2(Z),4-dienoate (5ac). 1H
NMR (400 MHz, CDCl3)
d
0.86e0.90 (two t peaks overlapped, 2H),
doublet at
d
5.51 resulted in 11.4% enhancements of the signal at
1.19e1.31 (m, 16H), 1.87e1.91 (m, 2H), 3.83 (s, 2H, Z), 3.97 (s, 2H, E),
4.11e4.17 (two q peaks overlapped, 2H), 5.36 (t, J¼7.3 Hz, 1H, Z),
5.71 (d, J¼12 Hz, 1H, E), 5.77 (t, J¼7.3 Hz, 1H, E), 5.90 (d, J¼12 Hz, 1H,
Z), 6.41 (d, J¼13 Hz, 1H, E), 6.69 (d, J¼12 Hz, 1H, Z), 7.23e7.54 (m,
d
6.40 (vinylic doublet) and irradiation of the vinylic proton
doublet at
d 6.40 resulted in 11.1% and 15.2% enhancements of the
d 5.51 (vinylic doublet) and the signal at d 5.70 (vinylic
signal at
doublet); NOE experiment for E-isomer: irradiation for the
vinylic proton doublet at 4.93 resulted in 5.0% enhancements of
the signal at 3.62 (allylic singlet) and irradiation of the vinylic
proton doublet at 6.71 resulted in 3.0% and 12.7% enhancements
of the signal at 1.94e1.96 (multiplet) and the signal at 5.84
5H); 13C NMR (100 MHz, CDCl3)
d
14.1, 14.2 (Z), 14.2 (E), 22.7, 26.9,
d
28.4, 29.0 (three peaks overlapped), 29.1 (E), 29.2, 29.4, 29.4 (Z),
31.9 (E), 34.6, 60.2 (Z), 60.3 (E), 118.2 (E), 121.6 (Z), 127.1 (Z), 127.3 (E),
128.8, 130.3 (Z), 130.4 (E), 131.9 (Z), 132.7 (E), 133.7 (Z), 133.9, 134.3
(E), 140.4, 141.8 (Z), 144.2 (E), 165.7 (E), 166.4 (Z); NOE experiment
for Z-isomer: irradiation of the allylic proton (eCH2SePh) singlet at
d
d
d
d
(vinylic doublet); IR (neat) 2924, 2849, 1716 (C]O), 1616, 1448,
1176, 1029, 769 cmꢁ1; MS (CI), m/z (%)¼221 (83), 405 (51), 407

10528
S.-i. Fujiwara et al. / Tetrahedron 68 (2012) 10523e10529
(Mþþ1, 100). Anal. Calcd for C22H30O2Se: C, 65.17; H, 7.46. Found:
enhancements of the signal at
of the vinylic proton doublet at
ments of the signal at
d
3.75 (allylic singlet) and irradiation
C, 66.16; H, 7.37.
d
6.80 resulted in 15.8% enhance-
d
3.36 (vinylic doublet); IR (neat) 2925, 2851,
4.2.6. Ethyl 5-cyclohexyl-4-(4-trifluoromethylphenylselenomethyl)
1313, 1146, 1086, 909, 732 cmꢁ1; MS (CI), m/z (%)¼147 (23), 303
(90), 304 (20), 305 (94), 458 (20), 459 (51), 461 (Mþþ1, 100); HRMS
(CI) calcd for C24H28O2SSe: 460.0975. Found: 461.1056.
penta-2(Z),4-dienoate (5ca). 1H NMR (400 MHz, CDCl3)
d 0.88e1.63
(m, 13H), 1.97e2.05 (m, 1H), 3.91 (s, 2H, E), 4.07 (s, 2H, Z), 4.09e4.17
(m, 2H), 5.24 (d, J¼9.6 Hz, 1H, E), 5.61 (d, J¼9.6 Hz, 1H, Z), 5.72 (d,
J¼13 Hz, 1H, Z), 5.89 (d, J¼12 Hz, 1H, E), 6.37 (d, J¼13 Hz, 1H, Z), 6.68
(d, J¼12 Hz, 1H, E), 7.46e7.63 (m, 4H); 13C NMR (100 MHz, CDCl3)
4.2.9. Methyl 2-(2-cyclohexyl-1-phenylselenomethylvinyl)benzoate
(5ga). 1H NMR (400 MHz, CDCl3)
d 0.85e1.79 (m, 10H), 2.19e2.26
d
14.2, 25.5 (two peaks overlapped), 25.7, 26.9, 32.3, 32.4 (two
(m, 1H), 3.81 (s, 3H), 3.97 (s, 2H), 5.17 (d, J¼10 Hz, 1H, Z), 5.22 (d,
peaks overlapped), 37.7, 60.4, 118.6, 125.5, 125.6, 126.1, 130.6, 133.1,
133.5 (two peaks overlapped), 144.1, 146.5, 190.9; NOE experiment
J¼10 Hz,1H, E), 7.16e7.93 (m, 9H); 13C NMR (100 MHz, CDCl3)
d 25.8
(two peaks overlapped), 25.9, 30.3, 32.9 (two peaks overlapped),
37.7, 38.0, 51.8, 126.9, 126.9, 127.1, 128.8, 128.9, 130.0, 131.2, 131.4,
131.8, 133.1, 133.5, 135.0, 138.1, 168.2; IR (neat) 2924, 2849, 1725
(C]O), 1446, 1289, 1254, 1081, 734, 690 cmꢁ1; MS (EI), m/z (%)¼225
(34), 257 (100), 414 (Mþ, 1). Anal. Calcd for C23H26O2Se: C, 66.82; H,
6.34. Found: C, 66.90; H, 6.21.
for Z-isomer: irradiation for the vinylic proton doublet at
d 5.61
resulted in 10.8% enhancements of the signal at 6.37 (vinylic
d
doublet) and irradiation of the vinylic proton doublet at
resulted in 10.9% and 14.7% enhancements of the signal at
d
d
6.37
5.61
(vinylic doublet) and the signal at
experiment for E-isomer: irradiation for the vinylic proton doublet
at 5.24 resulted in 5.0% enhancements of the signal at 3.91
(allylic singlet) and irradiation of the vinylic proton doublet at
d 5.72 (vinylic doublet); NOE
d
d
4.2.10. 5-Cyclohexyl-4-phenylthiomethylpenta-2(Z),4(Z)-dienoic acid
diethylamide (5ha). 1H NMR (400 MHz, CDCl3)
d 0.95e1.60 (m,
d
6.68 resulted in 0.8% and 12.6% enhancements of the signal at
1.97e2.05 (multiplet) and the signal at d 5.89 (vinylic doublet); IR
16H), 2.08 (m, 1H), 3.29e3.34 (q, J¼14 Hz, 2H), 3.36e3.41 (q,
J¼14 Hz, 2H), 3.88 (s, 2H), 5.60 (d, J¼9.6 Hz, 1H), 5.84 (d, J¼13 Hz,
1H), 6.12 (d, J¼13 Hz, 1H), 7.15e7.34 (m, 5H); 13C NMR (100 MHz,
d
(neat) 3409, 2925, 1467, 1383, 1326, 907, 733, 651 cmꢁ1; MS (CI), m/
z (%)¼221 (75), 444 (20), 445 (52), 447 (Mþþ1, 100); HRMS (CI)
calcd for C21H25F3O2Se: 446.0972. Found: 447.1049.
CDCl3) d 12.8, 13.9, 25.6, 25.8, 32.6, 32.7, 37.6, 39.1, 42.9, 53.5, 121.5,
126.3, 128.6, 128.7, 129.8, 130.3, 131.8, 135.7, 136.7, 145.1, 145.1,
168.0; IR (neat) 2925, 2850, 1619 (C]O), 1439, 1264, 1145,
749 cmꢁ1; MS (CI), m/z (%)¼248 (21), 358 (Mþþ1, 100); HRMS (CI)
calcd for C22H31NOS: 357.2126. Found: 358.2195.
4.2.7. 5-Cyclohexyl-4-phenylselenomethyl-penta-2(Z),4-dienoic acid
diethylamide (5da). 1H NMR (400 MHz, CDCl3)
d 0.91e1.58 (m,16H),
1.95 (m,1H), 3.34e3.43 (m, 4H), 3.80 (s, 2H, E), 3.89 (s, 2H, Z), 5.10 (d,
J¼9.5 Hz,1H, E), 5.53 (d, J¼9.6 Hz,1H, Z), 5.83 (d, J¼13 Hz,1H, Z), 6.03
(d, J¼13 Hz, 1H, E), 6.11 (d, J¼13 Hz, 1H, Z), 6.47 (d, J¼13 Hz, 1H, E),
4.2.11. Ethyl 5-cyclohexyl-4-phenylselenomethylpenta-2(E),4-
dienoate (6). 1H NMR (400 MHz, CDCl3)
d 0.93e1.74 (m, 13H),
7.23e7.56 (m, 5H); 13C NMR (100 MHz, CDCl3)
d
12.9,13.9, 25.6, 25.8,
2.01e2.05 (m, 1H), 3.61 (s, 2H, E), 3.72 (s, 2H, Z), 4.18e4.27 (q, 2H),
5.36 (d, J¼10 Hz, 1H, E), 5.75 (d, J¼10 Hz, 1H, Z), 5.91 (d, J¼16 Hz, 1H,
Z), 6.06 (d, J¼16 Hz, 1H, E), 7.19e7.29 (m, 3H), 7.47e7.63 (m, 3H); 13C
26.0, 30.9, 32.5, 37.5, 39.1, 42.8, 121.3,127.1,128.8, 129.0,129.2,131.0,
132.0, 132.1, 136.0, 144.3, 167.9; NOE experiment for Z-isomer: ir-
radiation of the allylic proton (eCH2SePh) singlet at
in 7.9% enhancements of the signal at 1.95 (multiplet), irradiation
of the vinylic proton doublet at 5.53 resulted in 11.5% enhance-
ments of the signal at 6.11 (vinylic doublet) and irradiation for the
vinylic proton singlet at 6.11 resulted in 12.9% and 13.7% en-
hancements of the signal at 5.53 (vinylic doublet) and the signal at
5.83 (vinylic doublet); NOE experiment for E-isomer: irradiation of
d
3.89 resulted
NMR (100 MHz, CDCl3) d 14.3, 23.4, 25.4, 25.7, 32.2 (two peaks
d
overlapped), 32.7, 38.0, 60.2, 116.6, 127.6, 128.9, 129.0 (two peaks
overlapped), 131.3, 134.4 (two peaks overlapped), 147.1, 149.7, 167.3;
NOE experiment for Z-isomer: irradiation for the vinylic proton
d
d
d
doublet at
7.24 (vinylic doublet) and irradiation of the allylic proton
(eCH2SePh) singlet at 3.72 resulted in 12.6% enhancements of the
signal at 5.91 (vinylic doublet); NOE experiment for E-isomer:
irradiation for the vinylic proton doublet at 5.35 resulted in 5.4%
enhancements of the signal at 3.61 (allylic singlet) and irradiation
of the vinylic proton doublet at 6.06 resulted in 3.2% enhance-
d 5.75 resulted in 7.9% enhancements of the signal at
d
d
d
d
the vinylic proton singlet at
d
5.11 resulted in 4.9% enhancements of
d
the signal at
proton doublet at
signal at
d
3.80 (allylic singlet) and irradiation of the vinylic
d
d
6.03 resulted in 12.0% enhancements of the
d
d
6.47 (vinylic doublet); IR (neat) 2924, 2849, 1628 (C]O),
d
1475, 1436, 1264, 738, 691 cmꢁ1; MS (CI), m/z (%)¼248 (60), 250
(57), 404 (53), 406 (Mþþ1, 100); HRMS (CI) calcd for C22H31NOSe:
405.1571. Found: 406.1643.
ments of the signal at 3.61 (singlet); IR (neat) 2925, 2979, 2925,
2850, 1711 (C]O), 1626, 1476, 1447, 1310, 1284, 1268, 1246, 1175,
1118, 1038, 979, 739, 691 cmꢁ1; MS (CI), m/z (%)¼221 (39), 377 (52),
379 (Mþþ1, 100). Anal. Calcd for C20H26O2Se: C, 63.65; H, 6.94.
Found: C, 63.94; H, 6.84.
4.2.8. 1-(4-Cyclohexyl-3-phenylselenomethylbuta-1(Z),3-dienyl)sul-
fonyl-4-methylbenzene (5ea). 1H NMR (400 MHz, CDCl3)
d
0.80e1.65 (m, 10H), 1.95e2.03 (m, 1H), 2.38 (s, 3H), 3.68 (s, 2H, Z),
4.2.12. Transformation of 5aa to pyran-2-one (7). Into a 3-mL flask
were placed 5aa (0.2 mmol) and CH2Cl2 (1.5 mL) at room temper-
ature under N2. A solution of m-CPBA (0.22 mmol) in 1.1 mL of
CH2Cl2 was added dropwise at ꢁ78 ꢀC (acetone/CO2) and the
mixture was stirred in the same temperature for 1 h. After the
mixture was stirred at room temperature for 18 h, saturated
NaHCO3 aq and CH2Cl2 were added and washed with brine, and
dried over anhydrous MgSO4. Evaporation of the solvent and pu-
rification by preparative recycling HPLC (eluted with CHCl3) affor-
ded 6-cyclohexyl-5-methylene-5,6-dihydropyran-2-one (7) in 82%
3.75 (s, 2H, E), 5.10 (d, J¼9.6 Hz, 1H, E), 5.76 (d, J¼9.6 Hz, 1H, Z), 6.26
(d, J¼12 Hz, 1H, Z), 6.36 (d, J¼12 Hz, 1H, E), 6.69 (d, J¼12 Hz, 1H, Z),
6.80 (d, J¼12 Hz, 1H, E), 7.20e7.36 (m, 5H), 7.44e7.52 (m, 2H),
7.74e7.79 (m, 2H); 13C NMR (100 MHz, CDCl3)
d 21.6, 25.6, 25.8, 27.7,
32.1, 32.3, 37.8, 127.3, 127.5, 127.6, 127.6 (two peaks overlapped),
128.9, 129.0 (two peaks overlapped), 129.6 (two peaks overlapped),
129.8, 130.1, 134.1 (two peaks overlapped), 134.1, 144.1, 144.6; NOE
experiment for Z-isomer: irradiation for the vinylic proton doublet
at
(vinylic doublet) and irradiation of the vinylic proton doublet at
6.69 resulted in 1.7%, 3.5% and 16.0% enhancements of the signal
at 3.68 (allylic singlet), the signal at 5.76 (vinylic doublet) and
the signal at 6.26 (vinylic doublet); NOE experiment for E-isomer:
irradiation for the vinylic proton doublet at 5.10 resulted in 5.9%
d 6.26 resulted in 14.9% enhancements of the signal at d 6.69
yield as slight yellow oil: 1H NMR (400 MHz, CDCl3)
d 1.04e1.28 (m,
d
5H), 1.62e1.85 (m, 6H), 4.82 (d, J¼5.5 Hz, 2H), 5.25 (s, 1H), 5.46 (s,
d
d
1H), 5.91 (d, J¼10 Hz, 1H), 6.96 (d, J¼10 Hz, 1H); 13C NMR (100 MHz,
d
CDCl3) d 25.9, 27.4, 29.1, 43.9, 75.2, 119.2 (two peaks overlapped),
d
137.1, 142.8, 143.6, 163.2 (two peaks overlapped); IR (neat) 2928,

S.-i. Fujiwara et al. / Tetrahedron 68 (2012) 10523e10529
10529
2853, 1711 (C]O), 1227, 1122, 1031, 834 cmꢁ1; HRMS (EI) calcd for
C12H16O2: 192.1150. Found: 192.1142.
Tetrahedron Lett. 1991, 32, 4573; (d) Liu, J.; Sun, X.; Miyazaki, M.; Liu, L.; Wang,
C.; Xi, Z. J. Org. Chem. 2007, 31, 3137.
6. (a) Kuniyasu, H.; Ohtaka, A.; Nakazono, T.; Kinomoto, M.; Kurosawa, H. J. Am.
Chem. Soc. 2000, 122, 2375; (b) Kuniyasu, H.; Kato, T.; Inoue, M.; Terao, J.;
Kambe, N. J. Organomet. Chem. 2006, 691, 1873 Other examples for the cleavage
of vinylechalcogene bonds by transition metals, see: (c) Boyar, E.; Deeming, A.
J.; Henrick, K.; McPartlin, M.; Scott, A. J. Chem. Soc., Dalton Trans. 1986, 1413; (d)
Planas, J. G.; Marumo, T.; Ichikawa, Y.; Hirano, M.; Komiya, S. J. Chem. Soc.,
Dalton Trans. 2000, 2613; (e) Goj, L. A.; Lail, M.; Pittard, K. A.; Riley, K. C.;
Gunnoe, T. B.; Petersen, J. L. Chem. Commun. 2006, 982.
Acknowledgements
This work was partly supported by Grants-in-Aid (No. 20225004
and No. 21550053) for Scientific Research from the Ministry of
Education, Culture, Sports, Science and Technology, Japan.
7. Toyofuku, M.; Fujiwara, S.; Shin-ike, T.; Kuniyasu, H.; Kambe, N. J. Am. Chem. Soc.
2008, 130, 10504.
8. For recent reviews, see: (a) Ma, S. Chem. Rev. 2005, 105, 2829; (b) Ma, S. Acc.
Chem. Res. 2003, 36, 701; (c) Modern Allene Chemistry; Krause, N., Hashmi, A. S.
K., Eds.; Wiley-VCH: Weinheim, 2004.
Supplementary data
Experimental details and characterization data of all new com-
pounds. Supplementary data related to this article can be found at
http://dx.doi.org/10.1016/j.tet.2012.10.003. These data include MOL
files and InChIKeys of the most important compounds described in
this article.
9. For recent examples, see: (a) Kamiya, I.; Nishinaka, E.; Ogawa, A. Tetrahedron
Lett. 2005, 46, 3649; (b) Kazmaier, U.; Lucas, S.; Klein, M. J. Org. Chem. 2006, 71,
2429; (c) Ohmura, T.; Suginome, M. Org. Lett. 2006, 8, 2503; (d) Ohmura, T.;
Taniguchi, H.; Suginome, M. J. Am. Chem. Soc. 2006, 128, 13682; (e) Komada, S.;
Nishinaka, E.; Nomoto, A.; Sonoda, M.; Ogawa, A. Tetrahedron Lett. 2007, 48,
6312; (f) Abe, Y.; Kuramoto, K.; Ehara, M.; Nakatsuji, H.; Suginome, M.;
Murakami, M.; Ito, Y. Organometallics 2008, 27, 1736 For others, see Refs.1e5.
10. (a) Chatani, N.; Takeyasu, T.; Hanafusa, T. Tetrahedron Lett. 1986, 27, 1841; (b)
Hua, R.; Tanaka, M. Tetrahedron Lett. 2004, 45, 2367; (c) Shirakawa, E.; Nakao,
Y.; Hiyama, T. Chem. Commun. 2001, 263; (d) Shirakawa, E.; Nakao, Y.;
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E.; Tsuchimoto, T.; Hiyama, T. J. Organomet. Chem. 2004, 689, 3701.
11. Toyofuku, M.; Murase, E.; Fujiwara, S.; Shin-ike, T.; Kuniyasu, H.; Kambe, N. Org.
Lett. 2008, 10, 3957.
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Tetrahedron Lett. 2007, 48, 6655.
14. As for solvent, CH3CN gave the best result. The NMR yields of 5aa using other
solvents under identical conditions were as follows: toluene (80%), benzene
(75%), DMSO (74%), NMP (61%), DMA (59%), PhCN (48%), and DMF (30%).
15. As for the amount of allene, when 1 equiv of allene was employed the yield of
5aa was diminished probably due to the oligomerization of the allene.
16. When Ni(COD)2 (5 mol %)-P(p-MeC6H4)3 (10 mol %) was employed as catalyst,
the present transformation did not proceed at all.
17. The structures of the products were confirmed by NOE experiments. See
Experimental section for details.
18. In entries 1 and 2, when Pd(dba)2-P(p-MeC6H4)3 was employed the products
were obtained albeit in lower yields.
2. (a) Shirakawa, E.; Yoshida, H.; Kurahashi, T.; Nakao, Y.; Hiyama, T. J. Am. Chem.
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moto, A. J. Am. Chem. Soc. 2006, 128, 14438.
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19. Calculations were carried out using the Gaussian09 set of programs with the
B3LYP functional, the 6-31G(d) basis set for all nonmetallic atoms (H, C, and O)
and the LANL2DZ basis set for Se.
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Oxford University: Oxford, 1999; pp 207e221.
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