Synthetic transformation of homopropargylic selenides to conjugated diene-substituted alcohols and amines using diisopropoxy(η2- alkyne)titanium intermediates

Article abstract of DOI:10.1016/j.tet.2013.03.060

The reaction of homopropargylic selenides with the low-valent titanium reagent, derived from Ti(O-i-Pr)₄ and 2 equiv of i-PrMgCl, proceeded via titanium-alkyne complexes, followed by the reaction with electrophiles, such as aldehydes and imines to afford allylic alcohols and amines having a phenylseleno group in moderate to high yields with excellent regioselectivity (up to >99:1). Especially, the reaction of the silyl-substituted alkynes with imines provided the desired products in almost complete regioselectivity. The resulting products were subjected to oxidation with H₂O₂ to lead conjugated diene-substituted alcohols and amines via selenoxide elimination in high yields. In addition, the isomer ratio of products was nearly completely maintained under the oxidative deselenation conditions.

Full text of DOI:10.1016/j.tet.2013.03.060

Tetrahedron 69 (2013) 4311e4324
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Tetrahedron
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Synthetic transformation of homopropargylic selenides to
conjugated diene-substituted alcohols and amines using
diisopropoxy(h
2-alkyne)titanium intermediates
*
Kazuki Shintaku, Yoko Nishino, Hajime Maeda, Masahito Segi
Division of Material Sciences, Graduate School of Natural Science and Technology, Kanazawa University, Kakuma-machi, Kanazawa,
Ishikawa 920-1192, Japan
a r t i c l e i n f o
a b s t r a c t
Article history:
The reaction of homopropargylic selenides with the low-valent titanium reagent, derived from Ti(O-i-
Pr)4 and 2 equiv of i-PrMgCl, proceeded via titaniumealkyne complexes, followed by the reaction with
electrophiles, such as aldehydes and imines to afford allylic alcohols and amines having a phenylseleno
group in moderate to high yields with excellent regioselectivity (up to >99:1). Especially, the reaction of
the silyl-substituted alkynes with imines provided the desired products in almost complete re-
gioselectivity. The resulting products were subjected to oxidation with H2O2 to lead conjugated diene-
substituted alcohols and amines via selenoxide elimination in high yields. In addition, the isomer ratio
of products was nearly completely maintained under the oxidative deselenation conditions.
Ó 2013 Elsevier Ltd. All rights reserved.
Received 4 December 2012
Received in revised form 12 March 2013
Accepted 15 March 2013
Available online 20 March 2013
Keywords:
Homopropargylic selenide
Carbotitanation
Titaniumealkyne complexes
Phenylseleno group
Selenoxide elimination
Conjugated dienes
1. Introduction
for synthesis of polyfunctionalized compounds (Scheme 1), because
several reactive moieties of them will play important roles in func-
Titaniumealkyne complexes are very valuable intermediates in
tional group transformations.7,8 Those are (1) carbonecarbon bond
formation via hydrometallation of a terminal triple bond, (2) forma-
tion of olefins and allylicalcohols via selenoxideelimination and[2,3]-
sigmatropic rearrangement, respectively, and (3) elongation of carbon
chain via abstraction of acidic protons.
organic synthesis.1 In 1995, Sato and co-workers reported that the
titanium complexes known as diisopropoxy(h
2-alkyne)titaniums
are readily prepared from internal alkynes and the low-valent ti-
tanium reagent, generated in situ from Ti(O-i-Pr)4 and 2 equiv of i-
PrMgCl. These complexes can react with various electrophiles, such
as aldehydes,2 ketones,2 imines,3 and so on,4 to afford a variety of
di-, tri-, and tetrasubstituted alkenes. Internal alkynes are suitable
substrates for this reaction, and the reports of the use of terminal
alkynes are limited.5 In addition, for a titanium complexes arising
from an unsymmetrical alkyne, the reaction with ketones, un-
saturated, and aromatic aldehydes indicated generally significantly
high regioselectivity, which raised with increasing the steric hin-
drance when saturated aldehydes was used.2
Scheme 1. Terminal alkynes having a phenylseleno group.
Especially, the CH2CH2SePh moiety of 2 can be converted into
the CH]CH2 functional group via selenoxide elimination by oxi-
dation, and thus is regarded as a vinylic equivalent. On the other
hand, it has been reported that the reaction of conjugated eny-
neetitanium alkoxide complex with aldehydes gave the allenyl
alcohol derivatives.9 In this reported reaction, conjugated diene
derivatives are not obtained. We herein present the efficient and
facile synthetic procedure of conjugated dienes having an allylic
alcohol or amine moiety, in combination with titaniumealkyne
On the other hand, organoselenium chemistry has become a very
powerful tool in organic synthesis.6 In particular, 3-phenylseleno-1-
propyne 1 (propargylic selenide) and 4-phenylseleno-1-butyne 2
(homopropargylicselenide)areexpectedtobeversatileintermediates
* Corresponding author. Tel.: þ81 76 234 4787; fax: þ81 76 234 4800; e-mail
addresses: segi@se.kanazawa-u.ac.jp, segi@t.kanazawa-u.ac.jp (M. Segi).
0040-4020/$ e see front matter Ó 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.tet.2013.03.060

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K. Shintaku et al. / Tetrahedron 69 (2013) 4311e4324
complex formation by the reaction of homopropargylic selenide
derivatives with the low-valent titanium reagent and selenoxide
elimination via oxidation of phenylseleno group.
2. Results and discussion
The internal alkynes 3aee were prepared by the introduction of
some groups to the terminal alkyne carbon of 4-phenylseleno-1-
butyne 2 (Scheme 2). Treatment of 2 with 1.1 equiv of n-BuLi in
THF at ꢀ78 ꢁC generated the alkynyl anion, followed by reacting
with silyl chlorides to give the corresponding silyl-substituted al-
kynes 3aec in excellent yields. According to Linstrumelle’s pro-
cedure, the phenyl-substituted alkyne 3d was prepared by the
reaction with iodobenzene in the presence of 5 mol % of Pd(PPh3)4
in pyrrolidine at 50 ꢁC in 99% yield.10 The alkyl-substituted alkyne
3e was obtained in 95% yield by abstraction of terminal acidic
proton on 2 and the subsequent reaction with n-octyl bromide in
the presence of hexamethylphosphoric triamide (HMPA).
Scheme 3. Synthetic transformation to conjugated diene-substituted alcohols from 3.
The plausible mechanism for the carbotitanation of 3 with
benzaldehyde is shown in Scheme 4. The titaniumealkyne complex
5 is formed by ligand exchange of coordinated propene in the low-
valent titanium reagent 4 with the internal alkyne 3 (3a: R1¼SiMe3,
3d: R1¼Ph). When the carbonyl group of aldehydes inserts to one of
the two carbonetitanium bonds, a couple of presumable oxatita-
nacyclopentene intermediates A and B are possible. When the silyl-
substituted alkyne 3a was used, the addition of a carbonyl carbon to
Scheme 2. Introduction of some groups to the terminal alkyne carbon of 4-
phenylseleno-1-butyne 2.
the CeTi bond at b-position to the silyl group would selectively
The internal alkynes 3aed reacted with the low-valent titanium
reagent 4, generated in situ from Ti(O-i-Pr)4 (2 equiv) and i-PrMgCl
(4 equiv), in Et2O at ꢀ50 ꢁC for 2 h to produce titaniumealkyne
complexes 5, which were then reacted with various aldehydes at
ꢀ70 ꢁC for 1 h to give allylic alcohols 7 and 8 via oxatitanacyclo-
pentene intermediates 6 and 60, respectively (Scheme 3, Table 1).11
However, when the octyl-substituted alkyne 3e was used as a sub-
strate, the reaction did not proceed and the starting alkyne 3e was
completely recovered. These results are summarized in Table 1. The
regioselectivity of giving products 7 and 8 was depended on both
the substituent groups (R1) of internal alkynes 3 and the steric
hindrance of aldehydes. Namely, the silyl-substituted alkynes 3aec
proceed via the intermediate A1 to prevent forming B1 because of
steric interruption between silyl and phenyl groups, followed by
the treatment with H2O to obtain the corresponding allylic alcohol
7aa. In contrast, the complex 5 from phenyl-substituted alkyne 3d
preferentially reacted with benzaldehyde at the carbon having the
phenyl group to give the intermediate B2, followed by treatment
with H2O to afford mainly the allylic alcohol 8da. This notable
regioselectivity is consistent with the previous reports using un-
symmetrical alkynes.1e,2
In this way, the resulting products 7 and 8 having a phenylseleno
group were oxidized by H2O2 in THF to give conjugated diene de-
rivatives 9 and 10 bearing an allylic alcohol moiety in high to excel-
lent yields via syn elimination of the corresponding selenoxides
without isomerization of alkene (Scheme 3). The results are shown in
Table 2. The structure of products 9 and 10 was identified by 1H NMR
analysis and that ratio of the isomers (9, 10) was almost completely
maintained under the oxidative deselenation conditions.
The results on the reaction of alkynes 3 with various imines
instead of aldehydes as electrophiles using the low-valent titanium
reagent were summarized in Table 3. In this reaction, two possible
allylic amine derivatives 11 and 12 were produced. Similar to the
above results using aldehydes, the reaction of the silyl-substituted
alkynes 3aec with imines showed excellent regioselectivity
(>96:4), of which titaniumealkyne complexes underwent elec-
selectively underwent the addition of aldehydes at
silyl group to lead intermediates 6, whereas the phenyl-substituted
alkyne 3d preferentially reacted at -carbon to the phenyl group to
b-carbon to the
a
give allylic alcohols 8 via intermediates 60, accompanying the
regioisomer 7. It was revealed that the combination of the alkynes
3aec bearing a silyl group and sterically hindered aldehydes pro-
vided allylic alcohols 7 in extremely high regioselectivity, but the
selectivity decreased when primary aliphatic aldehyde was used
(entries 2, 5, and 8). In the case of the alkyl-substituted alkyne 3e,
the starting alkyne was completely recovered (entries 13 and 14).
This may be due to no stabilizing advantages arising from alkyl
substituent influences for the complex 5. Accordingly, the alkyne
complex 5 substituted by an alkyl group was not formed from the
treatment of the low-valent titanium reagent and 3e, and the
subsequent quench by H2O afforded the starting alkyne 3e.
trophilic addition by imines at
b-carbon to the silyl group regard-
less of the size of imines, to give the corresponding allylic amines 11

K. Shintaku et al. / Tetrahedron 69 (2013) 4311e4324
4313
Table 1
Synthesis of allylic alcohol derivatives using various alkynes 3 and aldehydes
Entry
1
3
R2
Product (Major) (7:8)a
7aa (>99 : 1)
7ab (93 : 7)
Yieldb (%)
3a
Ph
66
62
2
3
4
5
6
3a
3a
3b
3b
3b
n-C5H11
t-Bu
48
89
87
47
7ac (>99 : 1)
7ba (>99 : 1)
Ph
n-C5H11
7bb (80 : 20)
7bc (>99 : 1)
t-Bu
7
8
9
3c
3c
3c
Ph
78
61
43
7ca (>99 : 1)
n-C5H11
7cb (64 : 36)
7cc (>99 : 1)
t-Bu
10
11
3d
3d
Ph
68
8da (17 : 83)
8db (14 : 86)
n-C5H11
75
(continued on next page)

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K. Shintaku et al. / Tetrahedron 69 (2013) 4311e4324
Table 1 (continued )
Entry
3
R2
Product (Major) (7:8)a
Yieldb (%)
12
3d
t-Bu
63
8dc (43 : 57)
13
14
3e
3e
Ph
n-C5H11
0c
0c
Product ratio of 7 and 8 was determined by 1H NMR.
Isolated yield.
The starting alkyne 3e was recovered.
a
b
c
Scheme 4. Plausible mechanism for carbotitanation of alkynes 3 with benzaldehyde.
Table 2
Synthesis of conjugated diene alcohols via selenoxide elimination
Entry
1
Substrate (7:8)
aa (>99:1)
Product (Major) (9:10)a
Yieldb (%)
98
9aa (>99 : 1)
2
ab (93:7)
75
9ab (93 : 7)

K. Shintaku et al. / Tetrahedron 69 (2013) 4311e4324
4315
Table 2 (continued )
Entry
Substrate (7:8)
ac (>99:1)
Product (Major) (9:10)a
Yieldb (%)
3
4
5
69
94
81
9ac (>99 : 1)
9ba (>99 : 1)
9bb (80 : 20)
9bc (>99 : 1)
9ca (>99 : 1)
9cb (64 : 36)
9cc (>99 : 1)
ba (>99:1)
bb (80:20)
6
7
8
bc (>99:1)
ca (>99:1)
cb (64:36)
92
78
88
9
cc (>99:1)
76
10
11
da (17:83)
db (14:86)
98
99
10da (17 : 83)
10db (14 : 86)
12
dc (43:57)
99
10dc (43 : 57)
a
Product ratio of 9 and 10 was determined by 1H NMR.
Isolated yield.
b
in good yields (entries 1e9).12 When the phenyl-substituted alkyne
3d was used as the starting alkyne, isomeric allylic amines 12 were
preferentially obtained in moderate yields through the addition of
imines at the carbon having phenyl group in complex 5 (entries
10e12).11 These outcomes are similar to the above results using
aldehyde as an electrophile. The reaction using alkyl-substituted
alkyne 3e and imine did not proceed at all (entry 13). Sub-
sequently, the oxidative deselenation of obtained allylic amine
derivatives 11 and 12 with H2O2 efficiently proceeded to afford the
corresponding conjugated dienes 13 and 14 having an allylic amine
moiety in good to excellent yields (Table 4). The ratios of the iso-
mers 13 and 14 were also maintained through oxidation.

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K. Shintaku et al. / Tetrahedron 69 (2013) 4311e4324
Table 3
Synthesis of allylic amine derivatives using various alkynes 3 and imines
Entry
1
3
R3
R4
Product (Major) (11:12)a
Yieldb (%)
3a
Ph
PhCH2
61
11ad (>99 : 1)
11ae (>99 : 1)
11af (>99 : 1)
2
3
3a
3a
Ph
n-Pr
72
57
C5H11
PhCH2
4
3b
Ph
PhCH2
71
11bd (>99 : 1)
11be (>99 : 1)
11bf (96 : 4)
5
6
3b
3b
Ph
n-Pr
65
62
C5H11
PhCH2
7
3c
Ph
PhCH2
56
11cd (>99 : 1)
11ce (>99 : 1)
8
3c
3c
3d
Ph
n-Pr
69
60
49
9
C5H11
PhCH2
PhCH2
11cf (>99 : 1)
12dd (9 : 91)
10
Ph

K. Shintaku et al. / Tetrahedron 69 (2013) 4311e4324
4317
Table 3 (continued )
Entry
3
R3
R4
Product (Major) (11:12)a
12de (19 : 81)
Yieldb (%)
11
12
3d
Ph
n-Pr
43
3d
3e
C5H11
Ph
PhCH2
PhCH2
32
0c
12df (14 : 86)
13
a
Product ratio of 11 and 12.
Isolated yield.
The starting alkyne 3e was recovered.
b
c
Table 4
Synthesis of conjugated diene amines via selenoxide elimination
Entry
1
Substrate (11:12)
ad (>99:1)
Product (Major) (13:14)a
Yieldb (%)
85
13ad (>99 : 1)
13ae (93 : 7)
2
ae (>99:1)
93
3
4
5
6
af (>99:1)
bd (>99:1)
be (>99:1)
bf (96:4)
89
97
99
13af (>99 : 1)
13bd (>99 : 1)
13be (>99 : 1)
80
(continued on next page)
13bf (96 : 4)

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K. Shintaku et al. / Tetrahedron 69 (2013) 4311e4324
Table 4 (continued )
Entry
Substrate (11:12)
cd (>99:1)
Product (Major) (13:14)a
Yieldb (%)
7
63
13cd (>99 : 1)
13ce (>99 : 1)
8
ce (>99:1)
cf (>99:1)
dd (9:91)
de (19:81)
99
76
79
68
9
13cf (>99 : 1)
14dd (9 : 91)
10
11
14de (19 : 81)
14df (14 : 86)
12
df (14:86)
73
a
Product ratio of 9 and 10 was determined by 1H NMR.
Isolated yield.
b
On the other hand, we attempted to similar reactions by using
functional group is in situ efficiently formed. On the other hand, the
complex formed from propargyl selenide 1 is difficult to coordinate
with the intramolecular selenium atom because of the shortage of
spatial length.
propargylic selenide 1. The carbotitanation of trimethylsilyl-
substituted alkyne 15 with low-valent titanium reagent 4 and
benzaldehyde did not proceed, resulting in the recovery of starting
alkyne. To confirm the formation of titaniumealkyne complex
generated from 15 and 4, the protonolysis of that complex with H2O
was carried out and resulted in the formation of cis allylic selenide
16 in 15% yield and the almost recovery of starting alkyne 15
(Scheme 5).13 This different reactivity between 1 and 2 would be
due to the stabilization in the corresponding alkyne complexes.14 In
the case of the homopropargyl selenide 2, the alkyne complex
stabilized by intramolecular coordination of the selenium
3. Conclusion
In conclusion, an efficient and useful method for stereoselective
syntheses of conjugated dienes having oxygen or nitrogen func-
tionality was developed by the electrophilic addition of aldehydes
or imines to titaniumealkyne complexes, generated from internal
alkyne bearing a phenylseleno group and low-valent titanium re-
agent, followed by selenoxide elimination via oxidation.
4. Experimental section
4.1. General
1H, 13C, and 77Se NMR spectra were recorded on JEOL JNM-FX-270
(1H; 270.1 MHz and 13C; 67.8 MHz) and JNM-GX-400 (1H; 399.7 MHz,
13C; 100.4 MHz, and 77Se; 76.2 MHz, respectively) spectrometers.
Chemical shifts were reported in parts per million relative to tetra-
methylsilane as internal standard, and were referenced to diphenyl
diselenide as external standard for 77Se (464.1 ppm in CDCl3). IR
spectra were obtained on a SHIMADZU FTIR-8300 spectrometer.
Mass spectra (EI) were recorded on a JEOL JMS-700 or JMS-SX 102A
mass spectrometer. Column chromatography was conducted by
Scheme 5. Reaction of propargylic selenide 15 with low-valent titanium reagent.

K. Shintaku et al. / Tetrahedron 69 (2013) 4311e4324
4319
using Fuji Silysia Chemical silica gel BW-127ZH. THF and Et2O were
distilled from sodium benzophenone ketyl under nitrogen. Other
reagents were commercially available and used without further
purification. Isopropylmagnesium chloride (2.0 M solution in Et2O)
was purchased from SigmaeAldrich Co., Inc. and n-butyllithium
(1.6 M solution in hexane) was purchased from Kanto Chemical Co.,
Inc. All reactions were performed under argon atmosphere with
flame-dried glassware using a vacuum pump unless otherwise de-
scribed. Propargylic selenide 1 and homopropargylic selenide 2 were
synthesized according to published procedure.7,8
7.6 Hz, 2H), 7.27e7.28 (m, 6H), 7.37e7.39 (m, 2H), 7.55e7.57 (m, 2H);
dC (100 MHz, CDCl3) 21.2, 26.0, 81.6, 88.7, 123.5, 127.2, 127.8, 128.2,
129.1, 129.5, 131.6, 133.1; dSe (76 MHz, CDCl3) 315.4; nmax (neat) 3055,
2936, 1578, 1477, 1439, 1072, 1022, 756, 734, 691 cmꢀ1; m/z (EI) 77
(20), 91 (24), 128 (100), 158 (10), 171 (11), 205 (19), 286 (78%, Mþ).
80
HRMS (EI): Mþ, found 286.0268. C16
H Se requires 286.0261.
14
4.4. General procedure for carbotitanation of internal alkynes
with low-valent titanium reagent and various aldehydes
To a stirred solution of an internal alkyne 3 (0.30 mmol) and
Ti(O-i-Pr)4 (0.154 g, 0.54 mmol) in Et2O (5 mL) was added i-PrMgCl
(2.0 M solution in Et2O, 0.6 mL, 1.2 mmol) dropwise at ꢀ78 ꢁC. The
reaction mixture was warmed up to ꢀ50 ꢁC over 30 min and stirred
for 2 h at this temperature. Then an aldehyde (0.50 mmol) was
added at ꢀ78 ꢁC and the reaction mixture was stirred for 1 h at
ꢀ70 ꢁC. The reaction was quenched with H2O at ꢀ70 ꢁC. The organic
layer was separated and the aqueous layer was further extracted
with ether. The combined organic layers were washed with brine,
dried over MgSO4, concentrated, and purified by column chroma-
tography on silica gel to afford allyl alcohols 7 and 8.
4.2. General procedure for the preparation of silyl-
substituted alkynes 3aec
To a stirred solution of 4-phenylseleno-1-butyne 2 (2.0 mmol) in
THF (10 mL) was added n-BuLi (1.6 M solution in hexane, 2.2 mmol)
dropwise at ꢀ78 ꢁC. The reaction mixture was stirred 20 min at
ꢀ78 ꢁC, and then a silyl chloride (2.4 mmol) was slowly added. After
stirring for 10 min, the mixture was warmed up to 0 ꢁC and
quenched with H2O. The organic layer was separated and the
aqueous layer was further extracted with ether. The combined or-
ganic layers were washed with brine, dried over MgSO4, concen-
trated, and purified by column chromatography on silica gel to
afford alkyne 3aec.
4.4.1. (E)-1-Phenyl-4-(phenylselanyl)-2-[(trimethylsilyl)methylene]
butan-1-ol (7aa). Pale yellow oil, 66% yield; dH (400 MHz, CDCl3)
0.10 (s, 9H), 2.01 (br s, 1H), 2.29e2.36 (m, 1H), 2.46e2.53 (m, 1H),
2.77e2.82 (m, 2H), 5.14 (s, 1H), 5.89 (s, 1H), 7.24e7.44 (m, 10H); dC
(100 MHz, CDCl3) 0.1, 27.2, 33.8, 78.4, 125.6, 126.8, 127.0, 127.8,
128.5, 129.0, 129.6, 133.2, 141.9, 157.5; dSe (76 MHz, CDCl3) 314.8;
nmax (neat) 3418, 3059, 2955, 2897,1616,1477,1450,1250,1022, 837,
737, 698 cmꢀ1; m/z (EI) 73 (100), 107 (43), 143 (40), 233 (64), 375
(9), 390 (13%, Mþ). HRMS (EI): Mþ, found 390.0920. C20H26OSi80Se
requires 390.0918.
4.2.1. Trimethyl[4-(phenylselanyl)but-1-yn-1-yl]silane (3a). Pale yel-
low oil, 99% yield; dH (400 MHz, CDCl3) 0.14 (s, 9H), 2.59 (t, J¼7.7 Hz,
2H), 3.02 (t, J¼7.7 Hz, 2H), 7.26e7.27 (m, 3H), 7.52e7.53 (m, 2H); dC
(100 MHz, CDCl3) 0.01, 21.7, 25.8, 85.7,105.6,127.2,129.1,129.4,133.2;
dSe (76 MHz, CDCl3) 317.0; nmax (neat) 3071, 2959, 2897, 2176, 1578,
1477, 1250, 760, 737, 691 cmꢀ1; m/z (EI) 73 (93), 109 (47), 158 (23),
267 (15), 282 (100%, Mþ). HRMS (EI): Mþ, found 282.0335.
C13H18Si80Se requires 282.0343.
4.4.2. (E)-1-(Phenylselanyl)-3-[(trimethylsilyl)methylene]nonan-4-ol
(7ab). Mixture of regioisomers (7ab:8ab¼93:7). Pale yellow oil,
62% yield; Major regioisomer; dH (400 MHz, CDCl3) 0.06 (s, 9H),
0.88 (t, J¼6.8 Hz, 3H), 1.26e1.51 (m, 8H), 1.53 (br s, 1H), 2.39e2.47
(m, 1H), 2.55e2.63 (m, 1H), 2.90e3.03 (m, 2H), 4.04 (dd, J¼4.6,
7.6 Hz, 1H), 5.56 (s, 1H), 7.23e7.29 (m, 3H), 7.50e7.55 (m, 2H); dC
(100 MHz, CDCl3) 0.1, 14.0, 22.6, 25.4, 27.5, 31.7, 33.8, 36.2, 76.4,
125.1, 127.1, 129.0, 129.7, 133.3, 159.4; dSe (76 MHz, CDCl3) 313.1;
nmax (neat) 3402, 3071, 2955, 2858, 1612, 1578, 1477, 1439, 1250,
1022, 856, 733, 691 cmꢀ1; m/z (EI) 73 (98), 211 (53), 227 (100), 369
(16), 384 (26%, Mþ). HRMS (EI): Mþ, found 384.1389. C19H32OSi80Se
requires 384.1388.
4.2.2. tert-Butyldimethyl[4-(phenylselanyl)but-1-yn-1-yl]silane
(3b). Pale yellow oil, 97% yield; dH (400 MHz, CDCl3) 0.08 (s, 6H), 0.93
(s, 9H), 2.60 (t, J¼7.7 Hz, 2H), 3.02 (t, J¼7.7 Hz, 2H), 7.25e7.27 (m, 3H),
7.50e7.53 (m, 2H); dC (100 MHz, CDCl3) ꢀ4.5, 16.5, 21.6, 26.1, 84.0,
106.1, 127.2, 129.1, 129.5, 133.2; dSe (76 MHz, CDCl3) 315.8; nmax (neat)
3071, 2951, 2928, 2855, 2172, 1578, 1474, 1250, 837, 775, 737,
691 cmꢀ1; m/z (EI) 109 (58), 129 (31), 239 (15), 267 (100), 324 (20%,
Mþ). HRMS (EI): Mþ, found 324.0820. C16H24Si80Se requires 324.0812.
4.2.3. Dimethyl(phenyl)[4-(phenylselanyl)but-1-yn-1-yl]silane
(3c). Pale yellow oil, 99% yield; dH (400 MHz, CDCl3) 0.38 (s, 6H),
2.64 (t, J¼7.8 Hz, 2H), 3.04 (t, J¼7.8 Hz, 2H), 7.25e7.27 (m, 3H),
7.36e7.38 (m, 3H), 7.51e7.54 (m, 2H), 7.61e7.63 (m, 2H); dC
(100 MHz, CDCl3) ꢀ0.8, 21.7, 25.8, 83.8, 107.4, 127.2, 127.8, 129.1,
129.3, 133.2, 133.7, 137.2; dSe (76 MHz, CDCl3) 317.0; nmax (neat)
3067, 2959, 2176, 1578, 1477, 1427, 1250, 818, 733, 698 cmꢀ1; m/z
(EI) 135 (81), 159 (100), 171 (74), 329 (22), 344 (97%, Mþ). HRMS
(EI): Mþ, found 344.0495. C18H20Si80Se requires 344.0499.
4.4.3. (Z)-1-(Phenylselanyl)-4-(trimethylsilyl)dec-3-en-5-ol
(8ab). Minor regioisomer; dH (400 MHz, CDCl3) 0.11 (s, 9H), 0.88 (t,
J¼6.8 Hz, 3H), 1.26e1.51 (m, 8H), 1.53 (br s, 1H), 2.39e2.47 (m, 1H),
2.55e2.63 (m, 1H), 2.90e3.03 (m, 2H), 4.12 (dd, J¼2.6, 7.1 Hz, 1H),
6.18 (t, J¼7.4 Hz, 1H), 7.23e7.29 (m, 3H), 7.50e7.55 (m, 2H).
4.4.4. (E)-2,2-Dimethyl-6-(phenylselanyl)-4-[(trimethylsilyl)methy-
lene]hexan-3-ol (7ac). Yellow oil, 48% yield; dH (400 MHz, CDCl3)
0.08 (s, 9H), 0.85 (s, 9H), 2.29e2.36 (m, 1H), 2.62e2.69 (m, 1H),
2.90e3.02 (m, 2H), 3.75 (s, 1H), 5.56 (s, 1H), 7.25e7.28 (m, 3H),
7.52e7.55 (m, 2H); dC (100 MHz, CDCl3) 0.2, 26.1, 28.3, 35.8, 36.1,
82.4, 127.1, 127.6, 129.0, 129.8, 133.3, 158.9; dSe (76 MHz, CDCl3)
308.6; nmax (neat) 3476, 3059, 2955, 2870, 1609, 1477, 1439, 1250,
1007, 860, 841, 737, 691 cmꢀ1; m/z (EI) 73 (99), 213 (100), 313 (83),
355 (27), 370 (37%, Mþ). HRMS (EI): Mþ, found 370.1235.
C18H30OSi80Se requires 370.1231.
4.3. General procedure for the preparation of the phenyl-
substituted alkyne 3d
To a stirred solution of iodobenzene (0.071 g, 1.2 mmol) and
tetrakis(triphenylphosphine)palladium (0.060 g, 0.05 mmol) in
pyrrolidine (1.0 mL) was added a solution of 4-phenylseleno-1-
butyne 2 (0.210 g, 1.0 mmol) in pyrrolidine (1.5 mL). After stirring
at room temperature for 15 min, the mixture was hydrolyzed with
a satd NH4Cl and extracted with diethyl ether. The combined organic
layers were washed with brine, dried over MgSO4, concentrated, and
purified by column chromatography on silica gel to afford phenyl(4-
phenylbut-3-yn-1-yl)selane 3d (0.282 g, 99% yield) as pale yellow
oil; dH (400 MHz, CDCl3) 2.79 (td, J¼3.3, 7.6 Hz, 2H), 3.11 (td, J¼3.3,
4.4.5. (E)-2-[(tert-Butyldimethylsilyl)methylene]-1-phenyl-4-(phenyl-
selanyl)butan-1-ol (7ba). Pale yellow oil, 89% yield; dH (400 MHz,
CDCl3) 0.037 (s, 3H), 0.042 (s, 3H), 0.88 (s, 9H), 1.97 (br s, 1H),

4320
K. Shintaku et al. / Tetrahedron 69 (2013) 4311e4324
2.26e2.33 (m, 1H), 2.46e2.53 (m, 1H), 2.81 (t, J¼8.6 Hz, 2H), 5.15 (s,
1H), 5.90 (s, 1H), 7.24e7.33 (m, 8H), 7.41e7.44 (m, 2H); dC (100 MHz,
CDCl3) ꢀ4.4, ꢀ4.3, 17.0, 26.5, 27.3, 33.9, 78.6, 122.6, 126.7, 127.0, 127.8,
128.5, 129.0, 129.7, 133.2, 142.0, 158.4; dSe (76 MHz, CDCl3) 314.9; nmax
(neat) 3429, 3059, 2951, 2855, 1616, 1578, 1474, 1250, 1022, 826, 737,
698 cmꢀ1; m/z (EI) 143 (35), 187 (19), 217 (15), 375 (100), 417 (2), 432
(1%, Mþ). HRMS (EI): Mþ, found 432.1379. C23H32OSi80Se requires
432.1388.
(m, 2H), 2.70 (t, J¼7.4 Hz, 2H), 4.14 (dd, J¼4.8, 7.2 Hz, 1H), 6.27 (t,
J¼7.4 Hz, 1H), 7.18e7.49 (m, 10H); dSe NMR (76 MHz, CDCl3) 300.5.
4.4.12. (E)-4-[(Dimethylphenylsilyl)methylene]-2,2-dimethyl-6-(phe-
nylselanyl)hexan-3-ol (7cc). Pale yellow oil, 43% yield; dH (400 MHz,
CDCl3) 0.35 (s, 6H), 0.86 (s, 9H), 1.61 (br s, 1H), 2.20e2.27 (m, 1H),
2.54e2.62 (m, 1H), 2.71e2.84 (m, 2H), 3.76 (s, 1H), 5.74 (s, 1H),
7.22e7.23 (m, 3H), 7.33e7.35 (m, 3H), 7.41e7.44 (m, 2H), 7.49e7.51
(m, 2H); dC (100 MHz, CDCl3) ꢀ1.0, 26.2, 27.8, 35.9, 36.1, 82.5, 125.6,
126.9, 127.9, 129.0, 129.9, 133.0, 133.7, 139.2, 160.8; dSe (76 MHz,
CDCl3) 308.7; nmax (neat) 3464, 3067, 2955, 2870, 1607, 1578, 1477,
1250, 1111, 1007, 833, 733, 698 cmꢀ1; m/z (EI) 75 (43), 135 (100), 197
(50), 297 (47), 417 (6), 432 (7%, Mþ). HRMS (EI): Mþ, found
432.1387. C23H32OSi80Se requires 432.1388.
4.4.6. (E)-3-[(tert-Butyldimethylsilyl)methylene]-1-(phenylselanyl)
nonan-4-ol (7bb). Mixture of regioisomers (7bb:8bb¼80:20). Pale
yellow oil, 87% yield; Major regioisomer; dH (400 MHz, CDCl3) 0.02
(s, 6H), 0.85 (s, 9H), 0.85e0.89 (m, 3H), 1.26e1.62 (m, 12H),
2.38e2.46 (m, 1H), 2.52e2.64 (m, 1H), 2.88e3.04 (m, 2H), 4.07 (dd,
J¼5.5, 6.9 Hz, 1H), 5.58 (s, 1H), 7.24e7.39 (m, 3H), 7.50e7.55 (m,
2H); dSe (76 MHz, CDCl3) 313.3; nmax (neat) 3422, 3059, 2928, 2855,
1612, 1578, 1470, 1250, 1022, 837, 737, 691 cmꢀ1; m/z (EI) 369 (100),
411 (3), 426 (2%, Mþ). HRMS (EI): Mþ, found 426.1861.
C22H38OSi80Se requires 426.1857.
4.4.13. (E)-1,2-Diphenyl-5-(phenylselanyl)pent-2-en-1-ol
(8da). Mixture of regioisomers (7da:8da¼17:83). Pale yellow oil,
68% yield; Major regioisomer; dH (400 MHz, CDCl3) 1.96 (br s, 1H),
2.35 (q, J¼7.6 Hz, 2H), 2.90 (t, J¼7.6 Hz, 2H), 5.39 (s, 1H), 5.91 (td,
J¼1.0, 7.6 Hz, 1H), 6.87e6.89 (m, 2H), 7.18e7.39 (m, 13H); dSe
(76 MHz, CDCl3) 297.1; nmax (neat) 3414, 3055, 3028, 2928, 2870,
1578, 1477, 1439, 1072, 1022, 733, 702 cmꢀ1; m/z (EI) 237 (100), 287
(17), 394 (26%, Mþ). HRMS (EI): Mþ, found 394.0839. C23H22O80Se
requires 394.0836.
4.4.7. (Z)-4-(tert-Butyldimethylsilyl)-1-(phenylselanyl)dec-3-en-5-ol
(8bb). Minor regioisomer; dH (400 MHz, CDCl3) 0.06 (s, 3H), 0.10 (s,
3H), 0.88 (s, 9H), 0.85e0.89 (m, 3H), 1.26e1.62 (m, 12H), 2.38e2.46
(m, 1H), 2.52e2.64 (m, 1H), 2.88e3.04 (m, 2H), 4.08e4.13 (m, 1H),
6.41 (t, J¼7.3 Hz, 1H), 7.24e7.39 (m, 3H), 7.50e7.55 (m, 2H); dSe
(76 MHz, CDCl3) 302.0.
4.4.14. (E)-2-Benzylidene-1-phenyl-4-(phenylselanyl)butan-1-ol
(7da). Minor regioisomer; dH (400 MHz, CDCl3), characteristic
signals: 2.46e2.54 (m, 1H), 2.57e2.65 (m, 1H), 2.70e2.88 (m, 2H),
5.32 (s, 1H), 6.81 (s, 1H); dSe (76 MHz, CDCl3) 314.8.
4.4.8. (E)-4-[(tert-Butyldimethylsilyl)methylene]-2,2-dimethyl-6-
(phenylselanyl)hexan-3-ol (7bc). Pale yellow oil, 47% yield; dH
(400 MHz, CDCl3) 0.03 (s, 3H), 0.05 (s, 3H), 0.86 (s, 9H), 0.87 (s, 9H),
1.60 (br s, 1H), 2.28e2.35 (m, 1H), 2.63e2.71 (m, 1H), 2.90e3.00 (m,
2H), 3.77 (s, 1H), 5.59 (s, 1H), 7.26e7.30 (m, 3H), 7.52e7.55 (m, 2H);
dC (100 MHz, CDCl3) ꢀ4.2, 17.0, 26.2, 26.5, 28.2, 36.0, 36.4, 82.4,
124.5, 127.1, 129.0, 129.8, 133.3, 160.1; dSe (76 MHz, CDCl3) 309.6;
nmax (neat) 3476, 3059, 2943, 2855, 1609, 1578, 1477, 1250, 1007,
837, 737, 698 cmꢀ1; m/z (EI) 73 (65), 75 (91), 215 (11), 285 (6), 355
(100), 412 (1%, Mþ). HRMS (EI): Mþ, found 412.1695. C21H36OSi80Se
requires 412.1701.
4.4.15. (E)-4-Phenyl-1-(phenylselanyl)dec-3-en-5-ol (8db). Mixture
of regioisomers (7db:8db¼14:86). Pale yellow oil, 75% yield; Major
regioisomer; dH (400 MHz, CDCl3) 0.84e0.90 (m, 3H), 1.23e1.55 (m,
8H), 1.63 (br s, 1H), 2.87 (q, J¼7.3 Hz, 2H), 2.88 (t, J¼7.3 Hz, 2H), 4.26
(s, 1H), 5.71 (t, J¼7.3 Hz, 1H), 7.10e7.40 (m, 10H); dSe (76 MHz,
CDCl3) 297.1; nmax (neat) 3418, 3055, 2955, 2858, 1578, 1439, 1022,
737, 702 cmꢀ1; m/z (EI) 231 (100), 289 (55), 388 (42%, Mþ). HRMS
(EI): Mþ, found 388.1299. C22H28O80Se requires 388.1305.
4.4.9. (E)-2-[(Dimethylphenylsilyl)methylene]-1-phenyl-4-(phenyl-
selanyl)butan-1-ol (7ca). Pale yellow oil, 78% yield; dH (400 MHz,
CDCl3) 0.36 (s, 6H), 2.01 (br s, 1H), 2.18e2.25 (m, 1H), 2.37e2.44 (m,
1H), 2.53e2.66 (m, 2H), 5.13 (s, 1H), 6.06 (s, 1H), 7.17e7.35 (m, 13H),
7.49e7.52 (m, 2H); dC (100 MHz, CDCl3) ꢀ1.09, ꢀ1.06, 26.7, 33.9,
78.4, 123.3, 126.80, 126.85, 127.88, 127.92, 128.5, 128.95, 129.01,
129.8, 132.9, 133.7, 139.1, 141.8, 159.2; dSe (76 MHz, CDCl3) 315.7;
nmax (neat) 3425, 3067, 2955, 1612, 1578, 1477, 1250, 1111, 1022, 833,
733, 698 cmꢀ1; m/z (EI) 135 (100), 203 (41), 217 (60), 295 (30), 437
(3), 452 (2%, Mþ). HRMS (EI): Mþ, found 452.1077. C25H28OSi80Se
requires 452.1075.
4.4.16. (E)-4-Benzylidene-2,2-dimethyl-6-(phenylselanyl)hexan-3-ol
(7db). Minor regioisomer; dH (400 MHz, CDCl3), characteristic
signal: 6.54 (s, 1H); dSe (76 MHz, CDCl3) 314.1.
4.4.17. (E)-2,2-Dimethyl-4-phenyl-7-(phenylselanyl)hept-4-en-3-ol
(8dc). Mixture of regioisomers (7dc:8dc¼43:57). Pale yellow oil,
63% yield; Major regioisomer; dH (400 MHz, CDCl3) 0.79 (s, 9H),1.64
(br s, 1H), 2.39e2.59 (m, 2H), 2.87e2.94 (m, 2H), 4.14 (s, 1H), 5.75 (t,
J¼7.4 Hz, 1H), 7.16e7.39 (m, 10H); dSe (76 MHz, CDCl3) 296.8; nmax
(neat) 3464, 3055, 3020, 2955, 2866, 1578, 1477, 1439, 1003, 737,
702 cmꢀ1; m/z (EI) 159 (100), 317 (83), 374 (51%, Mþ). HRMS (EI):
Mþ, found 374.1146. C21H26O80Se requires 374.1149.
4.4.10. (E)-3-[(Dimethylphenylsilyl)methylene]-1-(phenylselanyl)
nonan-4-ol (7cb). Mixture of regioisomers (7cb:8cb¼64:36). Pale
yellow oil, 61% yield; Major regioisomer; dH (400 MHz, CDCl3)
0.32 (s, 6H), 0.87 (t, J¼6.1 Hz, 3H), 1.25e1.53 (m, 8H), 1.71 (br s,
1H), 2.30e2.38 (m, 1H), 2.47e2.55 (m, 1H), 2.75e2.81 (m, 2H),
4.05 (dd, J¼4.9, 7.3 Hz, 1H), 5.73 (d, J¼1.0 Hz, 1H), 7.18e7.49 (m,
10H); dSe (76 MHz, CDCl3) 313.5; nmax (neat) 3425, 3067, 2955,
2928, 2858, 1612, 1578, 1477, 1427, 1250, 1111, 1022, 837, 733,
698 cmꢀ1; m/z (EI) 135 (99), 197 (40), 211 (98), 289 (34), 446 (12%,
Mþ). HRMS (EI): Mþ, found 446.1553. C25H28OSi80Se requires
446.1544.
4.4.18. (E)-4-Benzylidene-2,2-dimethyl-6-(phenylselanyl)hexan-3-ol
(7dc). Minor regioisomer; dH (400 MHz, CDCl3) 0.95 (s, 9H), 1.64 (br
s, 1H), 2.39e2.59 (m, 2H), 2.87e2.94 (m, 2H), 3.91 (s, 1H), 6.53 (s,
1H), 7.16e7.39 (m, 10H); dSe (76 MHz, CDCl3) 308.9.
4.5. General procedure for carbotitanation of internal alkynes
with low-valent titanium reagent and various imines
To a solution of an internal alkynes 3 (0.30 mmol) and Ti(O-i-
Pr)4 (0.153 g, 0.54 mmol) in Et2O (10 mL) was added i-PrMgCl
(2.0 M solution in Et2O, 0.6 mL, 1.2 mmol) dropwise at ꢀ78 ꢁC. The
reaction mixture was warmed up to ꢀ50 ꢁC over 30 min and stirred
for 2 h at this temperature. Then an imine (0.5 mmol) was added at
ꢀ50 ꢁC. After stirring for 1 h, the mixture was slowly warmed up to
4.4.11. (Z)-4-(Dimethylphenylsilyl)-1-(phenylselanyl)dec-3-en-5-ol
(8cb). Minor regioisomer; dH (400 MHz, CDCl3) 0.37 (s, 6H), 0.87
(t, J¼6.1 Hz, 3H), 1.25e1.53 (m, 8H), 1.71 (br s, 1H), 2.30e2.38

K. Shintaku et al. / Tetrahedron 69 (2013) 4311e4324
4321
ꢀ10 ꢁC and quenched with H2O. The organic layer was separated
and the aqueous layer was further extracted with ether. The com-
bined organic layers were washed with brine, dried over MgSO4,
concentrated, and purified by column chromatography on silica gel
to afford allyl amine 11 and 12.
473 (17%, Mþ). HRMS (EI): Mþ, found 473.2020. C26H39NSi80Se re-
quires 473.2017.
4.5.6. (E)-N-Benzyl-3-[(tert-butyldimethylsilyl)methylene]-1-(phenyl-
selanyl)nonan-4-amine (11bf). Mixture of regioisomers (11bf:12bf
¼96:4). Pale yellow oil, 62% yield; Major regioisomer; dH (400 MHz,
CDCl3) 0.03 (s, 6H), 0.85 (t, J¼7.2 Hz, 3H), 0.87 (s, 9H), 1.19e1.48 (m,
9H), 2.37 (td, J¼5.6, 12.8 Hz, 1H), 2.54 (td, J¼5.6, 12.8 Hz, 1H),
2.87e3.04 (m, 3H), 3.63 (ABq, J¼13.2 Hz, 2H), 5.57 (s, 1H), 7.22e7.30
(m, 8H), 7.48e7.50 (m, 2H); dC (100 MHz, CDCl3) ꢀ4.25, ꢀ4.21, 14.0,
17.0, 22.6, 26.0, 26.5, 27.5, 31.8, 34.7, 35.7, 51.4, 65.6,123.2,126.9,128.2,
128.4, 129.0, 129.9, 133.2, 140.6, 158.9; dSe (76 MHz, CDCl3) 315.6; nmax
4.5.1. (E)-N-Benzyl-1-phenyl-4-(phenylselanyl)-2-[(trimethylsilyl)
methylene]butan-1-amine (11ad). Pale yellow oil, 61% yield; dH
(400 MHz, CDCl3) 0.07 (s, 9H), 2.22e2.29 (m, 1H), 2.41e2.48 (m,
1H), 2.68e2.76 (m, 2H), 3.65 (d, J¼5.6 Hz, 2H), 4.13 (s, 1H), 5.90 (d,
J¼1.0 Hz, 1H), 7.19e7.34 (m, 13H), 7.38e7.41 (m, 2H); dC (100 MHz,
CDCl3) 0.2, 27.3, 34.8, 51.6, 68.3, 125.4, 126.9, 127.0, 127.3, 127.7,
128.2, 128.37, 128.38, 129.0, 129.8, 133.3, 140.4, 142.1, 157.4; dSe
(76 MHz, CDCl3) 314.7; nmax (neat) 3059, 3024, 2951, 1609, 1454,
1250, 837, 737, 698 cmꢀ1; m/z (EI) 196 (100), 322 (16), 388 (27), 406
(7), 479 (30%, Mþ). HRMS (EI): Mþ, found 479.1544. C27H33NSi80Se
requires 479.1747.
(neat) 3063, 3028, 2951, 2855, 1609, 1462, 1250, 837, 733, 694 cmꢀ1
;
m/z (EI) 91 (81), 190 (62), 244 (72), 286 (100), 515 (1%, Mþ). HRMS
(EI): Mþ, found 515.2491. C29H45NSi80Se requires 515.2486.
4.5.7. (Z)-N-Benzyl-4-(tert-butyldimethylsilyl)-1-(phenylselanyl)dec-
3-en-5-amine (12bf). Minor regioisomer; dH (400 MHz, CDCl3),
characteristic signal: 6.44 (t, J¼7.4 Hz, 1H).
4.5.2. (E)-1-Phenyl-4-(phenylselanyl)-N-propyl-2-[(trimethylsilyl)
methylene]butan-1-amine (11ae). Pale yellow oil, 72% yield; dH
(400 MHz, CDCl3) 0.11 (s, 9H), 0.88 (t, J¼7.7 Hz, 3H), 1.48 (sext,
J¼7.7 Hz, 2H), 2.23e2.29 (m, 1H), 2.37e2.48 (m, 3H), 2.74e2.79 (m,
2H), 4.09 (s, 1H), 5.84 (s, 1H), 7.18e7.29 (m, 8H), 7.41e7.44 (m, 2H);
dC (100 MHz, CDCl3) 0.2,11.8, 23.2, 27.3, 34.9, 49.8, 69.3,124.8,126.9,
127.2, 127.7, 128.3, 129.0, 129.8, 133.2, 142.4, 157.6; dSe (76 MHz,
CDCl3) 314.7; nmax (neat) 3058, 3024, 2955, 1612, 1582, 1477, 1454,
1250, 837, 733, 698 cmꢀ1; m/z (EI) 58 (64), 73 (26), 84 (50), 148
(100), 200 (24), 273 (17), 431 (10%, Mþ). HRMS (EI): Mþ, found
431.1546. C23H33NSi80Se requires 431.1547.
4.5.8. (E)-N-Benzyl-2-[(dimethylphenylsilyl)methylene]-1-phenyl-4-
(phenylselanyl)butan-1-amine (11cd). Pale yellow oil, 56% yield; dH
(400 MHz, CDCl3) 0.35 (s, 6H), 2.14e2.21 (m, 1H), 2.34e2.42 (m,
1H), 2.47e2.58 (m, 2H), 3.66 (ABq, J¼13.4 Hz, 2H), 4.14 (s, 1H), 6.12
(s, 1H), 7.16e7.34 (m, 18H), 7.47e7.50 (m, 2H); dC (100 MHz, CDCl3)
ꢀ0.97, ꢀ0.89, 26.7, 35.0, 51.6, 68.4, 123.1, 126.8, 126.9, 127.3, 127.7,
127.8, 128.1, 128.35, 128.37, 128.88, 128.90, 129.9, 133.0, 133.7, 139.4,
140.3, 141.9, 159.1; dSe (76 MHz, CDCl3) 316.0; nmax (neat) 3063,
3024, 2951, 2847, 1609, 1578, 1454, 1250, 1111, 837, 733, 698 cmꢀ1
;
m/z (EI) 248 (100), 307 (14), 383 (38), 541 (3%, Mþ). HRMS (EI): Mþ,
4.5.3. (E)-N-Benzyl-1-(phenylselanyl)-3-[(trimethylsilyl)methylene]
nonan-4-amine (11af). Colorless liquid, 57% yield; dH (400 MHz,
CDCl3) 0.07 (s, 9H), 0.85 (t, J¼7.0 Hz, 3H),1.19e1.46 (m, 9H), 2.38 (td,
J¼5.2, 12.6 Hz, 1H), 2.53 (td, J¼5.2, 12.6 Hz, 1H), 2.88 (td, J¼5.2,
12.6 Hz, 1H), 2.94e3.01 (m, 3H), 3.62 (ABq, J¼13.4 Hz, 2H), 5.53 (s,
1H), 7.23e7.30 (m, 8H), 7.48e7.50 (m, 2H); dC (100 MHz, CDCl3) 0.2,
14.0, 22.5, 26.0, 27.5, 31.8, 34.4, 35.5, 51.4, 65.5, 126.3, 126.8, 126.9,
128.1, 128.3, 129.0, 129.9, 133.2, 140.7, 158.3; dSe (76 MHz, CDCl3)
315.0; nmax (neat) 3059, 3028, 2955, 2928, 2855, 1609, 1578, 1454,
1246, 853, 694 cmꢀ1; m/z (EI) 91 (94), 190 (91), 244 (100), 402 (16),
473 (2%, Mþ). HRMS (EI): Mþ, found 473.2022. C26H39NSi80Se re-
quires 473.2017.
found 541.1706. C32H35NSi80Se requires 541.1704.
4.5.9. (E)-2-[(Dimethylphenylsilyl)methylene]-1-phenyl-4-(phenyl-
selanyl)-N-propylbutan-1-amine (11ce). Pale yellow oil, 69% yield;
dH (400 MHz, CDCl3) 0.34 (s, 6H), 0.87 (t, J¼7.4 Hz, 3H), 1.41 (br s,
1H), 1.42e1.52 (m, 2H), 2.14e2.21 (m, 1H), 2.34e2.42 (m, 2H),
2.44e2.64 (m, 3H), 4.09 (s, 1H), 6.04 (d, J¼1.0 Hz, 1H), 7.17e7.33 (m,
13H), 7.48e7.50 (m, 2H); dC (100 MHz, CDCl3) ꢀ1.0, ꢀ0.9, 11.8, 23.2,
26.7, 35.0, 49.8, 69.4, 122.4, 126.7, 127.2, 127.6, 127.7, 128.3, 128.8,
128.9, 129.9, 132.8, 132.9, 133.7, 139.5, 142.3, 159.6; dSe (76 MHz,
CDCl3) 316.0; nmax (neat) 3067, 2955, 2932, 1609, 1477, 1454, 1250,
1111, 833, 733, 698 cmꢀ1; m/z (EI) 135 (54), 148 (100), 200 (99), 306
(68), 335 (34), 493 (10%, Mþ). HRMS (EI): Mþ, found 493.1705.
C28H35NSi80Se requires 493.1704.
4.5.4. (E)-N-Benzyl-2-[(tert-butyldimethylsilyl)methylene]-1-
phenyl-4-(phenylselanyl)butan-1-amine (11bd). Pale yellow oil,
71% yield; dH (400 MHz, CDCl3) 0.03 (s, 3H), 0.04 (s, 3H), 0.88 (s,
9H), 2.22e2.27 (m, 1H), 2.42e2.50 (m, 1H), 2.67e2.78 (m, 2H),
3.67 (ABq, J¼13.4 Hz, 2H), 4.14 (s, 1H), 5.98 (s, 1H), 7.19e7.34 (m,
13H), 7.39e7.41 (m, 2H); dC (100 MHz, CDCl3) ꢀ4.3, ꢀ4.2, 17.1,
26.6, 27.3, 34.8, 51.6, 68.5, 122.4, 126.92, 126.94, 127.2, 127.7, 128.1,
128.33, 128.35, 128.9, 129.8, 133.3, 140.4, 142.3, 157.9; dSe (76 MHz,
CDCl3) 315.3; nmax (neat) 3069, 3028, 2928, 2855, 1612, 1454,
1250, 833, 737 cmꢀ1; m/z (EI) 196 (100), 248 (44), 364 (9), 521
(12%, Mþ). HRMS (EI): Mþ, found 521.2012. C30H39NSi80Se re-
quires 521.2017.
4.5.10. (E)-N-Benzyl-3-[(dimethylphenylsilyl)methylene]-1-(phenyl-
selanyl)nonan-4-amine (11cf). Pale yellow oil, 60% yield; dH
(400 MHz, CDCl3) 0.34 (s, 6H), 0.86 (t, J¼7.1 Hz, 3H), 1.21e1.44 (m,
9H), 2.31 (td, J¼5.6, 12.4 Hz, 1H), 2.47 (td, J¼5.6, 12.4 Hz, 1H), 2.75
(td, J¼5.6, 12.4 Hz, 2H), 3.03 (t, J¼7.1 Hz, 1H), 3.64 (ABq, J¼13.2 Hz,
2H), 5.72 (s, 1H), 7.17e7.38 (m, 13H), 7.50e7.52 (m, 2H); dC
(100 MHz, CDCl3) ꢀ1.0, ꢀ0.9, 14.0, 22.6, 26.0, 26.9, 31.8, 34.6, 35.5,
51.5, 65.5, 124.0, 126.7, 126.8, 127.8, 128.1, 128.3, 128.86, 128.93,
130.0, 132.76, 132.81, 132.9, 133.7, 129.6, 140.7, 160.4; dSe (76 MHz,
CDCl3) 315.7; nmax (neat) 3067, 3024, 2955, 2928, 2855, 1609, 1578,
1454, 1427, 1250, 1111, 837, 698 cmꢀ1; m/z (EI) 91 (98), 190 (100),
306 (99), 535 (1%, Mþ). HRMS (EI): Mþ, found 535.2179.
C31H41NSi80Se requires 535.2173.
4.5.5. (E)-2-[(tert-Butyldimethylsilyl)methylene]-1-phenyl-4-(phe-
nylselanyl)-N-propylbutan-1-amine (11be). Pale yellow oil, 65%
yield; dH (400 MHz, CDCl3) 0.02 (s, 3H), 0.03 (s, 3H), 0.88 (m, 9H),
0.88 (t, J¼7.3 Hz, 3H), 1.48 (sextd, J¼2.0, 7.3 Hz, 2H), 2.20e2.27 (m,
1H), 2.38e2.52 (m, 3H), 2.73e2.80 (m, 2H), 4.10 (s, 1H), 5.90 (s, 1H),
7.20e7.28 (m, 8H), 7.43e7.45 (m, 2H); dC (100 MHz, CDCl3) ꢀ4.3,
ꢀ4.2, 11.8, 17.1, 23.2, 26.6, 27.4, 35.0, 49.8, 69.6, 121.9, 126.9, 127.2,
127.6, 128.3, 129.0, 129.9, 133.2, 142.5, 158.1; dSe (76 MHz, CDCl3)
315.2; nmax (neat) 3059, 3024, 2955, 2928, 2855, 1612, 1458, 1250,
833, 733, 702 cmꢀ1; m/z (EI) 58 (78), 148 (100), 200 (46), 315 (20),
4.5.11. (E)-N-Benzyl-1,2-diphenyl-5-(phenylselanyl)pent-2-en-1-
amine (12dd). Mixture of regioisomers (11dd:12dd¼9:91). Pale
yellow oil, 49% yield; Major regioisomer; dH (400 MHz, CDCl3) 2.34
(q, J¼7.4 Hz, 2H), 2.89 (t, J¼7.4 Hz, 2H), 3.71e3.86 (m, 2H), 4.43 (s,
1H), 5.89 (t, J¼7.4 Hz, 1H), 6.79e6.81 (m, 2H), 7.16e7.34 (m, 18H);
dSe (76 MHz, CDCl3) 295.7; nmax (neat) 3059, 3024, 2928, 1578, 1493,
1477, 1454, 1119, 1072, 1026, 737, 698 cmꢀ1; m/z (EI) 91 (99), 196

4322
K. Shintaku et al. / Tetrahedron 69 (2013) 4311e4324
(100), 326 (28), 483 (7%, Mþ). HRMS (EI): Mþ, found 483.1460.
C30H29N80Se requires 483.1465.
22.6, 25.6, 31.7, 37.0, 72.2, 114.8, 128.1, 135.9, 156.5; nmax (neat) 3348,
3090, 2955, 2932, 2858,1566,1250, 906, 852, 768, 691 cmꢀ1; m/z (EI)
73 (79), 139 (12), 156 (70), 226 (4%, Mþ). HRMS (EI): Mþ, found
226.1757. C13H26OSi requires 226.1753.
4.5.12. (E)-N-Benzyl-2-benzylidene-1-phenyl-4-(phenylselanyl)bu-
tan-1-amine (11dd). Minor regioisomer; dH (400 MHz, CDCl3),
characteristic signals: 4.31 (s, 1H), 6.88 (s, 1H); dSe (76 MHz, CDCl3)
316.6.
4.6.3. (E)-2,2-Dimethyl-6-(phenylselanyl)-4-[(trimethylsilyl)methy-
lene]hexan-3-ol (9ac). Pale yellow oil, 69% yield; dH (400 MHz,
CDCl3) 0.16 (s, 9H), 0.90 (s, 9H), 1.55 (br s, 1H), 4.31 (s, 1H), 5.14 (d,
J¼11.2 Hz, 1H), 5.32 (d, J¼17.6 Hz, 1H), 5.79 (s, 1H), 6.60 (dd, J¼11.2,
17.6 Hz, 1H); dC (100 MHz, CDCl3) 0.3, 26.4, 35.5, 77.7, 115.2, 131.0,
138.0, 155.3; nmax (neat) 3472, 2955, 2905, 1558, 1477, 1362, 1250,
991, 841, 756, 691 cmꢀ1; m/z (EI) 75 (100), 140 (23), 156 (3), 212 (5%,
Mþ). HRMS (EI): Mþ, found 212.1599. C12H24OSi requires 212.1596.
4.5.13. (E)-1,2-Diphenyl-5-(phenylselanyl)-N-propylpent-2-en-1-
amine (12de). Mixture of regioisomers (11de:12de¼19:81). Pale
yellow oil, 43% yield; Major regioisomer; dH (400 MHz, CDCl3) 0.90
(t, J¼7.4 Hz, 3H), 1.40 (br s, 1H), 1.48e1.54 (m, 2H), 2.31 (q, J¼7.4 Hz,
2H), 2.47e2.68 (m, 2H), 2.88 (t, J¼7.4 Hz, 2H), 4.37 (s, 1H), 5.84 (t,
J¼7.4 Hz, 1H), 6.78e6.79 (m, 2H), 7.16e7.33 (m, 13H); dSe (76 MHz,
CDCl3) 296.3; nmax (neat) 3055, 3024, 2959, 2928, 2870, 1578, 1477,
1454, 1072, 1022, 737, 702 cmꢀ1; m/z (EI) 91 (58), 148 (100), 250
(49), 278 (48), 435 (33%, Mþ). HRMS (EI): Mþ, found 435.1475.
C26H29N80Se requires 435.1465.
4.6.4. (E)-2-[(tert-Butyldimethylsilyl)methylene]-1-phenylbut-3-en-
1-ol (9ba). Pale yellow oil, 94% yield; dH (270 MHz, CDCl3) 0.18 (s,
3H), 0.19 (s, 3H), 0.94 (s, 9H), 2.00 (br s, 1H), 5.10 (d, J¼13.5 Hz, 1H),
5.18 (d, J¼16.2 Hz, 1H), 5.55 (d, J¼2.7 Hz, 1H), 6.14 (s, 1H), 6.58 (dd,
J¼13.5, 16.2 Hz, 1H), 7.26e7.39 (m, 5H); dC (68 MHz, CDCl3) ꢀ4.0,
ꢀ3.9, 17.3, 26.5, 75.0, 116.3, 127.0, 127.7, 128.0, 128.5, 135.7, 142.5,
154.7; nmax (neat) 3402, 3063, 3028, 2951, 2855, 1566, 1470, 1250,
906, 779, 698 cmꢀ1; m/z (EI) 107 (52), 145 (46), 173 (98), 218 (100),
259 (4), 274 (3%, Mþ). HRMS (EI): Mþ, found 274.1757. C17H26OSi
requires 274.1753.
4.5.14. (E)-2-Benzylidene-1-phenyl-4-(phenylselanyl)-N-propylbu-
tan-1-amine (11de). Minor regioisomer; dH (400 MHz, CDCl3),
characteristic signals: 4.25 (s, 1H), 6.83 (s, 1H); dSe (76 MHz, CDCl3)
316.6.
4.5.15. (E)-N-Benzyl-4-phenyl-1-(phenylselanyl)dec-3-en-5-amine
(12df). Mixture of regioisomers (11df:12df¼14:86). Pale yellow oil
32% yield; Major regioisomer; dH (400 MHz, CDCl3) 0.85 (t, J¼7.0 Hz,
3H), 1.24e1.53 (m, 9H), 2.33 (q, J¼7.5 Hz, 2H), 2.86e2.94 (m, 3H),
3.86 (ABq, J¼13.2 Hz, 2H), 5.59 (t, J¼7.5 Hz, 1H), 7.07e7.41 (m, 15H);
dSe (76 MHz, CDCl3) 295.1; nmax (neat) 3059, 3024, 2928, 2855, 1578,
1492, 1454, 1072, 1022, 733, 698 cmꢀ1; m/z (EI) 91 (75), 190 (55),
248 (87), 320 (13), 406 (100), 477 (2%, Mþ). HRMS (EI): Mþ, found
477.1937. C26H29N80Se requires 477.1935.
4.6.5. (E)-3-[(tert-Butyldimethylsilyl)methylene]non-1-en-4-ol
(9bb). Mixture of regioisomers (9bb:10bb¼80:20). Pale yellow oil,
81% yield; Major regioisomer; dH (400 MHz, CDCl3) 0.13 (d, J¼7.1 Hz,
6H), 0.89 (t, J¼7.1 Hz, 3H), 0.91 (s, 9H), 1.26e1.72 (m, 9H), 4.51 (dd,
J¼4.1, 7.6 Hz, 1H), 5.16 (dt, J¼1.1, 11.4 Hz, 1H), 5.30 (d, J¼17.9 Hz, 1H),
5.88 (s, 1H), 6.58 (dd, J¼11.4, 17.9 Hz, 1H); nmax (neat) 3356, 3090,
2955, 2928, 2858, 1566, 1466, 1250, 907, 833, 779, 687 cmꢀ1; m/z
(EI) 141 (97), 194 (95), 211 (75), 268 (10%, Mþ). HRMS (EI): Mþ,
found 268.2220. C16H32OSi requires 268.2222.
4.5.16. (E)-N-Benzyl-3-benzylidene-1-(phenylselanyl)nonan-4-
amine (11df). Minor regioisomer; dH (400 MHz, CDCl3), character-
istic signals: 3.72 (ABq, J¼13.2 Hz, 1H), 6.48 (s, 1H); dSe (76 MHz,
CDCl3) 318.4.
4.6.6. (Z)-4-(tert-Butyldimethylsilyl)deca-1,3-dien-5-ol (10bb). Mi-
nor regioisomer; dH (400 MHz, CDCl3), characteristic signals: 0.15 (s,
3H), 0.23 (s, 3H), 0.93 (s, 9H), 4.25 (d, J¼8.3 Hz, 1H), 7.00 (d,
J¼11.2 Hz, 1H).
4.6. General procedure for oxidative deselenation of allylic
selenides
4.6.7. (E)-4-[(tert-Butyldimethylsilyl)methylene]-2,2-dimethylhex-5-
en-3-ol (9bc). Pale yellow oil, 92% yield; dH (400 MHz, CDCl3) 0.12
(s, 3H), 0.16 (s, 3H), 0.91 (s, 18H), 1.58 (br s, 1H), 4.37 (s, 1H), 5.14 (d,
J¼11.6 Hz, 1H), 5.33 (d, J¼17.6 Hz, 1H), 5.84 (s, 1H), 6.63 (dd, J¼11.6,
17.6 Hz, 1H); dC (100 MHz, CDCl3) ꢀ4.0, ꢀ3.8, 17.2, 26.47, 26.50, 35.7,
77.5, 115.0, 128.5, 138.3, 156.2; nmax (neat) 3472, 2955, 2858, 1558,
1466, 1362, 1254, 826 cmꢀ1; m/z (EI) 180 (60), 197 (46), 254 (1%,
Mþ). HRMS (EI): Mþ, found 254.2070. C15H30OSi requires 254.2066.
To a solution of allylic selenides (0.15 mmol) in THF (2 mL) was
added 10 equiv of H2O2 (30% in H2O) at 0 ꢁC. After stirring for 4 h at
this temperature, the reaction was quenched with satd NaHCO3 and
extracted with ether. The combined organic layers were washed
with brine, dried over MgSO4, concentrated, and purified by col-
umn chromatography on silica gel to afford conjugated dienes.
4.6.1. (E)-1-Phenyl-2-[(trimethylsilyl)methylene]but-3-en-1-ol
(9aa). Pale yellow oil, 98% yield; dH (400 MHz, CDCl3) 0.20 (s, 9H),
1.98 (br s, 1H), 5.10 (d, J¼11.2 Hz, 1H), 5.15 (d, J¼17.6 Hz, 1H), 5.51 (s,
1H), 6.12 (s, 1H), 6.56 (dd, J¼11.2, 17.6 Hz, 1H), 7.28e7.38 (m, 5H); dC
(100 MHz, CDCl3) 0.2, 74.9, 116.4, 127.0, 127.8, 128.5, 130.4, 135.4,
142.4, 153.9; nmax (neat) 3356, 3090, 3063, 3028, 2955, 2897, 1566,
1454, 1250, 988, 837, 768, 698 cmꢀ1; m/z (EI) 73 (100), 107 (63), 216
(9), 232 (17%, Mþ). HRMS (EI): Mþ, found 232.1280. C14H20OSi re-
quires 232.1283.
4.6.8. (E)-2-[(Dimethylphenylsilyl)methylene]-1-phenylbut-3-en-1-
ol (9ca). Pale yellow oil, 78% yield; dH (400 MHz, CDCl3) 0.45 (s, 6H),
2.02 (br s, 1H), 5.02 (d, J¼11.5 Hz,1H), 5.14 (d, J¼17.8 Hz, 1H), 5.54 (s,
1H), 6.28 (s, 1H), 6.48 (dd, J¼11.5, 17.8 Hz, 1H), 7.25e7.39 (m, 8H),
7.55e7.57 (m, 2H); dC (100 MHz, CDCl3) ꢀ0.68, ꢀ0.72, 74.9, 116.9,
127.0, 127.7, 127.9, 128.6, 129.0, 133.8, 135.4, 139.1, 142.3, 155.3; nmax
(neat) 3383, 3024, 2955, 2897, 1562, 1427, 1250, 1111, 910, 826, 729,
698 cmꢀ1; m/z (EI) 75 (100), 135 (100), 203 (62), 278 (3), 294 (2%,
Mþ). HRMS (EI): Mþ, found 294.1438. C19H22OSi requires 294.1440.
4.6.2. (E)-3-[(Trimethylsilyl)methylene]non-1-en-4-ol (9ab). Mixture
of regioisomers (9ab:10ab¼93:7). Colorless liquid, 75% yield; Minor
regioisomer (10ab) was not isolated by column chromatography on
silica gel; Major regioisomer; dH (400 MHz, CDCl3) 0.15 (s, 9H), 0.89
(t, J¼7.6 Hz, 3H), 1.25e1.51 (m, 7H), 1.63e1.70 (m, 2H), 4.46 (dd,
J¼3.9, 7.6 Hz, 1H), 5.16 (d, J¼11.2 Hz, 1H), 5.30 (d, J¼17.8 Hz, 1H), 5.85
(s, 1H), 6.57 (dd, J¼11.2, 17.8 Hz, 1H); dC (100 MHz, CDCl3) 0.01, 14.0,
4.6.9. (E)-3-[(Dimethylphenylsilyl)methylene]non-1-en-4-ol (9cb).
Mixture of regioisomers (9cb:10cb¼64:36). Pale yellow oil, 88%
yield; dH (400 MHz, CDCl3) 0.40 (s, 3H), 0.41 (s, 3H), 0.89 (t,
J¼7.0 Hz, 3H), 1.27e1.75 (m, 9H), 4.52 (dd, J¼3.8, 7.7 Hz, 1H), 5.09
(d, J¼11.5 Hz, 1H), 5.28 (d, J¼17.8 Hz, 1H), 6.00 (s, 1H), 6.49 (dd,
J¼11.5, 17.8 Hz, 1H), 7.34e7.36 (m, 3H), 7.52e7.54 (m, 2H); nmax
(neat) 3360, 3051, 2955, 2932, 2858, 1562, 1427, 1250, 1111, 818,

K. Shintaku et al. / Tetrahedron 69 (2013) 4311e4324
4323
775, 729, 702 cmꢀ1; m/z (EI) 135 (100), 217 (25), 288 (46%, Mþ).
1250, 907, 748, 698 cmꢀ1; m/z (EI) 91 (30), 196 (100), 321 (14%, Mþ).
HRMS (EI): Mþ, found 288.1906. C18H28OSi requires 288.1909.
HRMS (EI): Mþ, found 321.1915. C21H27NSi requires 321.1913.
4.6.10. (Z)-4-(Dimethylphenylsilyl)deca-1,3-dien-5-ol (10cb). Minor
regioisomer; dH (400 MHz, CDCl3) 0.46 (s, 6H), 0.87 (t, J¼7.0 Hz, 3H),
1.27e1.75 (m, 9H), 4.29 (dd, J¼3.9, 7.8 Hz, 1H), 5.10 (d, J¼10.0 Hz,
1H), 5.22 (dd, J¼1.7, 16.6 Hz, 1H), 6.48 (ddd, J¼10.0, 11.2, 16.6 Hz,
1H), 6.90 (d, J¼11.2 Hz, 1H), 7.34e7.36 (m, 3H), 7.52e7.54 (m, 2H).
4.6.18. (E)-1-Phenyl-N-propyl-2-[(trimethylsilyl)methylene]but-3-
en-1-amine (13ae). Mixture of regioisomers (13ae:14ae¼97:3).
Pale yellow oil, 93% yield; Minor regioisomer (14ae) was not iso-
lated by column chromatography on silica gel; Major regioisomer;
dH (400 MHz, CDCl3) 0.17 (s, 9H), 0.90 (t, J¼7.4 Hz, 3H), 1.50 (sextd,
J¼2.6, 7.4 Hz, 2H), 2.43e2.56 (m, 2H), 4.53 (s,1H), 5.06 (d, J¼11.2 Hz,
1H), 5.25 (d, J¼17.6 Hz, 1H), 6.04 (s, 1H), 6.54 (dd, J¼11.2, 17.6 Hz,
1H), 7.22e7.33 (m, 5H); dC (100 MHz, CDCl3) 0.3, 11.9, 23.3, 50.1,
65.0, 115.2, 126.9, 127.6, 128.3, 130.2, 136.8, 142.9, 153.8; nmax (neat)
3059, 3024, 2955, 1562, 1454, 1250, 907, 841, 752, 698 cmꢀ1; m/z
(EI) 73 (18), 106 (29), 148 (100), 273 (13%, Mþ). HRMS (EI): Mþ,
found 273.1915. C17H27NSi requires 273.1913.
4.6.11. (E)-4-[(Dimethylphenylsilyl)methylene]-2,2-dimethylhex-5-
en-3-ol (9cc). Pale yellow oil, 70% yield; dH (400 MHz, CDCl3) 0.41
(s, 3H), 0.42 (s, 3H), 0.93 (s, 9H), 1.58 (br s, 1H), 4.35 (s, 1H), 5.06 (d,
J¼11.2 Hz, 1H), 5.31 (d, J¼17.6 Hz, 1H), 5.95 (s, 1H), 6.52 (dd, J¼11.2,
17.6 Hz, 1H), 7.34e7.36 (m, 3H), 7.52e7.55 (m, 2H); dC (100 MHz,
CDCl3) ꢀ0.8, ꢀ0.6, 26.5, 35.7, 77.8, 115.7, 127.8, 128.4, 128.9, 133.7,
138.0, 139.3, 156.9; nmax (neat) 3472, 3051, 2955, 2905, 2870, 1728,
1558, 1427, 1362, 1250, 1111, 991, 814, 779, 702 cmꢀ1; m/z (EI) 135
(99), 140 (98), 203 (62), 217 (100), 274 (1%, Mþ). HRMS (EI): Mþ,
found 274.1749. C17H26OSi requires 274.1745.
4.6.19. (E)-N-Benzyl-3-[(trimethylsilyl)methylene]non-1-en-4-amine
(13af). Pale yellow oil, 89% yield; dH (400 MHz, CDCl3) 0.17 (s, 9H),
0.85 (t, J¼7.1 Hz, 3H), 1.19e1.57 (m, 9H), 3.43 (t, J¼7.1 Hz, 1H), 3.62
(ABq, J¼12.9 Hz, 2H), 5.12 (d, J¼11.2 Hz, 2H), 5.31 (d, J¼17.8 Hz, 1H),
5.77 (s, 1H), 6.61 (dd, J¼11.2, 17.8 Hz, 1H), 7.20e7.33 (m, 5H); dC
(100 MHz, CDCl3) 0.4, 14.0, 22.5, 26.0, 31.8, 36.0, 51.3, 60.6, 114.6,
126.7, 128.3, 137.3, 140.9, 155.5; nmax (neat) 3028, 2955, 2928, 2855,
1558, 1454, 1250, 853, 737, 698 cmꢀ1; m/z (EI) 91 (48), 190 (100),
244 (65), 315 (13%, Mþ). HRMS (EI): Mþ, found 315.2378. C20H33NSi
requires 315.2382.
4.6.12. (E)-1,2-Diphenylpenta-2,4-dien-1-ol (10da). Mixture of regi-
oisomers (9da:10da¼17:83). Pale yellow oil, 98% yield; Major
regioisomer; dH (400 MHz, CDCl3) 2.09 (br s, 1H), 5.09 (dd, J¼1.8,
10.8 Hz, 1H), 5.33 (dd, J¼1.8, 17.0 Hz, 1H), 5.51 (s,1H), 6.26 (dt, J¼10.8,
17.0 Hz, 1H), 6.52 (d, J¼10.8 Hz, 1H), 6.99e7.01 (m, 2H), 7.24e7.32 (m,
8H); nmax (neat) 3371, 3082, 3055, 3020, 2932, 2858, 1713, 1466, 999,
906, 702 cmꢀ1; m/z (EI) 105 (100), 129 (50), 236 (99%, Mþ). HRMS
(EI): Mþ, found 236.1209. C17H16O requires 236.1201.
4.6.20. (E)-N-Benzyl-2-[(tert-butyldimethylsilyl)methylene]-1-
phenylbut-3-en-1-amine (13bd). Pale yellow oil, 99% yield; dH
(400 MHz, CDCl3) 0.16 (s, 6H), 0.93 (s, 9H), 3.73 (ABq, J¼13.2 Hz,
2H), 4.62 (s, 1H), 5.03 (d, J¼11.2 Hz, 1H), 5.17 (d, J¼17.3 Hz, 1H), 6.21
(s, 1H), 6.56 (dd, J¼11.2, 17.3 Hz, 1H), 7.19e7.38 (m, 10H); dC
(100 MHz, CDCl3) ꢀ3.88, ꢀ3.86, 17.4, 26.6, 52.0, 64.3, 115.2, 126.9,
127.0, 127.6, 128.26, 128.35, 137.0, 140.5, 142.8, 154.0; nmax (neat)
3063, 3028, 2951, 2855, 1562, 1493, 1454, 1250, 907, 833, 737,
698 cmꢀ1; m/z (EI) 91 (80), 196 (100), 363 (21%, Mþ). HRMS (EI):
Mþ, found 363.2379. C24H33NSi requires 363.2382.
4.6.13. (E)-2-Benzylidene-1-phenylbut-3-en-1-ol (9da). Minor regi-
oisomer; dH (400 MHz, CDCl3), characteristic signals: 5.15 (d,
J¼11.5 Hz, 1H), 5.29 (d, J¼17.6 Hz, 1H), 5.67 (s, 1H), 6.71 (dd, J¼11.5,
17.6 Hz, 1H).
4.6.14. (E)-4-Phenyldeca-1,3-dien-5-ol (10db). Mixture of regioisom-
ers (9db:10db¼14:86). Pale yellow oil, 99% yield; Minor regioisomer
(9db) was not isolated by column chromatography on silica gel;
Major regioisomer; dH (400 MHz, CDCl3) 0.85 (t, J¼7.0 Hz, 3H),
1.19e1.51 (m, 8H),1.62 (br s,1H), 4.39 (t, J¼5.4 Hz,1H), 5.05 (dd, J¼2.0,
11.1, 1H), 5.29 (dd, J¼2.0, 16.5 Hz, 1H), 6.27 (dd, J¼11.1, 16.5 Hz, 1H),
6.35 (d, J¼11.1 Hz, 1H), 7.19e7.38 (m, 5H); nmax (neat) 3371, 3082,
3055, 3020, 2932, 2858, 1713, 1466, 999, 907, 702 cmꢀ1; m/z (EI) 99
(100), 129 (76), 159 (57), 230 (16%, Mþ). HRMS (EI): Mþ, found
230.1676. C16H22O requires 230.1671.
4.6.21. (E)-2-[(tert-Butyldimethylsilyl)methylene]-1-phenyl-N-pro-
pylbut-3-en-1-amine (13be). Pale yellow oil, 99% yield; dH (400 MHz,
CDCl3) 0.15 (s, 6H), 0.88 (t, J¼5.4 Hz, 3H), 0.91 (s, 9H), 1.51 (sextd,
J¼1.5, 7.6 Hz, 2H), 2.46e2.58 (m, 2H), 4.59 (s, 1H), 5.05 (d, J¼11.5 Hz,
1H), 5.25 (d, J¼17.8 Hz, 1H), 6.12 (s, 1H), 6.56 (dd, J¼11.5, 17.8 Hz, 1H),
7.22e7.36 (m, 5H); dC (100 MHz, CDCl3) ꢀ3.90, ꢀ3.87, 11.9, 17.4, 23.3,
26.6, 50.2, 65.1, 115.0, 126.9, 127.6, 127.9, 128.3, 137.2, 143.1, 154.2;
nmax (neat) 3063, 3024, 2955, 2928, 2855, 1562, 1462, 1250, 907, 833,
779, 698 cmꢀ1; m/z (EI) 148 (100), 200 (62), 286 (68), 315 (74%, Mþ).
HRMS (EI): Mþ, found 315.2390. C20H33NSi requires 315.2382.
4.6.15. (E)-2,2-Dimethyl-4-phenylhepta-4,6-dien-3-ol (10dc). Mix-
ture of regioisomers (9dc:10dc¼43:57). Pale yellow oil, 99% yield;
Major regioisomer; dH (400 MHz, CDCl3) 0.82 (s, 9H), 4.28 (s, 1H),
5.08 (d, J¼8.8, 1H), 5.32 (dd, J¼1.8, 16.0 Hz, 1H), 6.36e6.42 (m, 2H),
7.25e7.35 (m, 5H); nmax (neat) 3456, 3082, 3055, 3024, 2955, 2905,
2870, 1477, 1366, 1072, 1003, 910, 732 cmꢀ1; m/z (EI) 58 (100), 159
(59), 216 (10%, Mþ). HRMS (EI): Mþ, found 216.1513. C15H20O re-
quires 216.1514.
4.6.22. (E)-N-Benzyl-3-[(tert-butyldimethylsilyl)methylene]non-1-
en-4-amine (13bf). Mixture of regioisomers (13bf:14bf¼96:4). Pale
yellow oil, 80% yield; Minor regioisomer (14bf) was not isolated by
column chromatography on silica gel; Major regioisomer; dH
(400 MHz, CDCl3) 0.15 (s, 6H), 0.85 (t, J¼7.1 Hz, 3H), 0.92 (s, 9H),
1.21e1.56 (m, 9H), 3.49 (t, J¼6.0 Hz, 1H), 3.62 (ABq, J¼12.7 Hz, 2H),
5.10 (d, J¼11.2 Hz, 1H), 5.32 (d, J¼17.6 Hz, 1H), 5.83 (s, 1H), 6.63 (dd,
J¼11.2, 17.6 Hz, 1H), 7.12e7.30 (m, 5H); dC (100 MHz, CDCl3) ꢀ3.83,
ꢀ3.80, 14.0, 17.3, 22.6, 26.6, 31.9, 36.3, 51.4, 60.4, 114.3, 126.4, 126.8,
128.27, 128.30, 137.7, 140.9, 156.1; nmax (neat) 3063, 3028, 2955,
2928, 2855, 1562, 1462, 1250, 906, 829, 694 cmꢀ1; m/z (EI) 91 (22),
190 (100), 286 (47), 357 (12%, Mþ). HRMS (EI): Mþ, found 357.2845.
C23H39NSi requires 357.2852.
4.6.16. (E)-4-Benzylidene-2,2-dimethylhex-5-en-3-ol (9dc). Minor
regioisomer; dH (400 MHz, CDCl3), characteristic signals: 0.99 (s,
9H), 4.48 (s, 1H), 5.19 (d, J¼11.5 Hz, 1H), 5.43 (d, J¼17.9 Hz, 1H), 6.78
(dd, J¼11.5, 17.9 Hz, 1H).
4.6.17. (E)-N-Benzyl-1-phenyl-2-[(trimethylsilyl)methylene]but-3-
en-1-amine (13ad). Pale yellow oil, 85% yield; dH (400 MHz, CDCl3)
0.10 (s, 9H), 1.55 (br s, 1H), 3.63 (ABq, J¼13.1 Hz, 2H), 4.51 (s, 1H),
4.98 (d, J¼11.2 Hz, 1H), 5.13 (d, J¼17.6 Hz, 1H), 6.04 (s, 1H), 6.48 (dd,
J¼11.2, 17.6 Hz, 1H), 7.15e7.28 (m, 10H); dC (100 MHz, CDCl3) 0.4,
51.9, 64.2, 115.4, 126.9, 127.0, 127.7, 128.29, 128.33, 130.7, 136.6,
140.5, 142.7, 153.5; nmax (neat) 3063, 3028, 2955, 1562, 1493, 1454,
4.6.23. (E)-N-Benzyl-2-[(dimethylphenylsilyl)methylene]-1-phenylbut-
3-en-1-amine (13cd). Pale yellow oil, 63% yield; dH (400 MHz, CDCl3)
0.10 (s, 6H), 1.67 (br s, 1H), 3.73 (ABq, J¼13.1 Hz, 2H), 4.63 (s,1H), 4.97

4324
K. Shintaku et al. / Tetrahedron 69 (2013) 4311e4324
(d, J¼11.2 Hz, 1H), 5.19 (d, J¼17.6 Hz, 1H), 6.31 (s,1H), 6.48 (dd, J¼11.2,
17.6 Hz, 1H), 7.21e7.39 (m, 13H), 7.52e7.55 (m, 2H); dC (100 MHz,
CDCl3) ꢀ0.57, ꢀ0.54, 51.9, 64.2, 115.9, 127.0, 127.1, 127.7, 127.8, 128.1,
128.3, 128.4, 128.8, 133.8, 136.6, 139.4, 140.2, 142.5, 154.9; nmax (neat)
3063, 3024, 2955, 1562, 1493, 1454, 1427, 1250, 1111, 837, 729,
698 cmꢀ1; m/z (EI) 91 (42), 135 (17), 196 (100), 383 (11%, Mþ). HRMS
(EI): Mþ, found 383.2075. C26H29NSi requires 383.2069.
2H), 5.17 (d, J¼11.5 Hz, 1H), 5.45 (d, J¼18.1 Hz, 1H), 6.23e6.28 (m,
1H), 6.76 (dd, J¼11.5, 18.1 Hz, 1H), 7.16e7.36 (m, 10H); nmax (neat)
3059, 3028, 2928, 2855, 1600, 1493, 1454, 907, 698 cmꢀ1; m/z (EI) 91
(100), 190 (29), 248 (79), 319 (6%, Mþ). HRMS (EI): Mþ, found
319.2306. C23H29N requires 319.2300.
4.6.31. (E)-N-Benzyl-4-phenyldeca-1,3-dien-5-amine (13df). Minor
regioisomer; dH (400 MHz, CDCl3), characteristic signals: 3.32 (t,
J¼6.2 Hz, 1H), 3.84 (ABq, J¼13.3 Hz, 1H), 4.99e5.02 (m, 1H),
5.21e5.26 (m, 1H), 6.74 (s, 1H).
4.6.24. (E)-2-[(Dimethylphenylsilyl)methylene]-1-phenyl-N-pro-
pylbut-3-en-1-amine (13ce). Pale yellow oil, 99% yield; dH
(400 MHz, CDCl3) 0.42 (s, 3H), 0.43 (s, 3H), 0.95 (t, J¼7.4 Hz, 3H),
1.51 (sextd, J¼1.2, 7.6 Hz, 2H), 2.51e2.65 (m, 2H), 4.57 (s, 1H), 5.03
(d, J¼11.2 Hz, 1H), 5.30 (d, J¼17.8 Hz, 1H), 6.23 (s, 1H), 6.52 (dd,
J¼11.2, 17.8 Hz, 1H), 7.20e7.36 (m, 8H), 7.52e7.54 (m, 2H); dC
(100 MHz, CDCl3) ꢀ0.57, ꢀ0.54, 11.8, 23.3, 50.2, 65.2, 115.7, 127.0,
127.4, 127.6, 127.8, 128.3, 128.8, 133.8, 136.8, 139.5, 142.9, 155.4; nmax
(neat) 3067, 3024, 2959, 1562, 1454, 1427, 1250, 1111, 907, 833, 729,
698 cmꢀ1; m/z (EI) 135 (37), 148 (100), 335 (14%, Mþ). HRMS (EI):
Mþ, found 335.2067. C22H29NSi requires 335.2069.
Acknowledgements
This work was partially supported by Grant-in-Aids for Scientific
Research (C) from the Ministry of Education, Culture, Sports, Sci-
ence and Technology (MEXT) of Japan and by the Collaborative
Research Program of Institute for Chemical Research, Kyoto Uni-
versity (grant # 2012-9).
References and notes
4.6.25. (E)-N-Benzyl-3-[(dimethylphenylsilyl)methylene]non-1-en-
4-amine (13cf). Pale yellow oil, 76% yield; dH (400 MHz, CDCl3) 0.42
(s, 6H), 0.86 (t, J¼7.0 Hz, 3H), 1.22e1.58 (m, 9H), 3.50 (t, J¼6.5 Hz,
1H), 3.65 (ABq, J¼12.9 Hz, 2H), 5.04 (d, J¼11.2 Hz, 1H), 5.31 (d,
J¼16.8 Hz, 1H), 5.95 (s, 1H), 6.54 (dd, J¼11.2, 16.8 Hz, 1H), 7.22e7.35
(m, 8H), 7.54e7.56 (m, 2H); dC (100 MHz, CDCl3) ꢀ0.6, ꢀ0.5, 14.0,
22.6, 26.0, 31.8, 36.2, 51.4, 60.5, 115.1, 126.4, 126.8, 127.8, 128.3,
128.8, 133.8, 137.2, 139.7, 140.8, 157.1; nmax (neat) 3067, 3024, 2955,
2928, 2855, 1562, 1454, 1250, 1111, 841, 729, 698 cmꢀ1; m/z (EI) 91
(70), 190 (100), 306 (55), 377 (25%, Mþ). HRMS (EI): Mþ, found
377.2542. C25H35NSi requires 377.2539.
1. (a) Kulinkovich, O. G.; de Meijere, A. Chem. Rev. 2000, 100, 2789e2834; (b) Sato,
F.; Urabe, H.; Okamoto, S. Chem. Rev. 2000, 100, 2835e2886; (c) Sato, F.; Urabe,
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H.; Sato, F. Angew. Chem., Int. Ed. 2000, 39, 3290e3292; (g) Baum, O.; Quntar, A.
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Hirano, S.; Tanaka, R.; Urabe, H.; Sato, F. Org. Lett. 2004, 6, 727e729.
4.6.26. (E)-N-Benzyl-1,2-diphenylpenta-2,4-dien-1-amine
(14dd). Mixture of regioisomers (13dd:14dd¼9:91). Pale yellow oil,
79% yield; Major regioisomer; dH (400 MHz, CDCl3) 3.81 (ABq,
J¼13.4 Hz, 2H), 4.52 (s, 1H), 5.03 (dd, J¼1.8, 10.1 Hz, 1H), 5.30 (dd,
J¼1.8, 17.0 Hz, 1H), 6.27 (dt, J¼10.1, 17.0 Hz, 1H), 6.53 (d, J¼10.1 Hz,
1H), 7.21e7.36 (m, 5H); nmax (neat) 3082, 3059, 3024, 2831, 1701,
1601, 1493, 1454, 910, 702 cmꢀ1; m/z (EI) 91 (78), 196 (100), 234
(30), 325 (86%, Mþ). HRMS (EI): Mþ, found 325.1828. C24H23N re-
quires 325.1830.
3. (a) Gao, Y.; Harada, K.; Sato, F. Tetrahedron Lett. 1995, 36, 5913e5916; (b) Gao, Y.;
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Am. Chem. Soc. 1999, 121, 7342e7344; (b) Suzuki, D.; Urabe, H.; Sato, F. J. Am.
Chem. Soc. 2001, 123, 7925e7926 Reaction with nitriles; (c) Suzuki, D.; Nobe, Y.;
Watai, Y.; Tanaka, R.; Takayama, Y.; Sato, F.; Urabe, H. J. Am. Chem. Soc. 2005, 127,
7474e7479 Reaction with allenes see; (d) Tanaka, R.; Sasaki, M.; Sato, F.; Urabe,
H. Tetrahedron Lett. 2005, 46, 329e332; (e) Shimp, H. L.; Micalizio, G. C. Tet-
rahedron 2008, 64, 3437e3445 For a review; (f) Perez, L. J.; Micalizio, G. C.
Synthesis 2008, 627e648 Reaction with carbonates; (g) Wolan, A.; Cadoret, F.;
Six, Y. Tetrahedron 2009, 65, 7429e7439.
5. (a) Hill, J. E.; Balaich, G.; Fanwick, P. E.; Rothwell, I. P. Organometallics 1993, 12,
2911e2924; (b) Yamaguchi, S.; Jin, R.-Z.; Tamao, K.; Sato, F. J. Org. Chem. 1998,
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1710e1714; Angew. Chem., Int. Ed. 1999, 38, 1604e1607; (d) Morlender-Vais, N.;
Solodovnikova, N.; Marek, I. Chem. Commun. 2000, 1849e1850.
4.6.27. (E)-N-Benzyl-2-benzylidene-1-phenylbut-3-en-1-amine
(13dd). Minor regioisomer; dH (400 MHz, CDCl3), characteristic
signals: 4.73 (s, 1H), 5.10 (d, J¼11.2 Hz, 1H), 6.72 (dd, J¼11.2, 17.8 Hz,
1H), 6.99 (s, 1H).
6. (a) Paulmier, C. In Selenium Reagents and Intermediates in Organic Synthesis;
Baldwin, J. E., Ed.; Pergamon: Oxford, UK, 1986; (b) Krief, A.; Hevesi, L. In Or-
ganoselenium Chemistry; Liotta, D., Ed.; John Wiley & Sons: New York, NY, 1987;
(c) Krief, A.; Hevesi, L. Organoselenium Chemistry I; Springer: Berlin, Germany,
1988; (d) Organoselenium Chemistry; Wirth, T., Ed.; Springer: Berlin, Germany,
2000; (e) Nomoto, A.; Ogawa, A. In The Chemistry of Organic Selenium and
Tellurium Compounds; Rappoport, Z., Ed.; John Wiley & Sons: Chichester, UK,
4.6.28. (E)-1,2-Diphenyl-N-propylpenta-2,4-dien-1-amine
(14de). Mixture of regioisomers (13de:14de¼19:81). Pale yellow
oil, 68% yield; Major regioisomer; dH (400 MHz, CDCl3) 0.91 (t,
J¼7.3 Hz, 3H), 1.48 (br s, 1H), 1.50e1.57 (m, 2H), 2.50e2.68 (m, 2H),
4.47 (s, 1H), 5.02 (dd, J¼2.0, 10.0, 1H), 5.29 (dd, J¼2.0, 17.0 Hz, 1H),
6.22 (dt, J¼10.0, 17.0 Hz, 1H), 6.49 (d, J¼10.0 Hz, 1H), 6.90e6.93 (m,
2H), 7.18e7.34 (m, 8H); nmax (neat) 3059, 3024, 2957, 2870, 1601,
1493, 1450, 907, 745, 702 cmꢀ1; m/z (EI) 148 (82), 277 (100%, Mþ).
HRMS (EI): Mþ, found 277.1829. C20H23N requires 277.1830.
ꢀ
2012; Vol. 3, pp 623e688; (f) Mlochowski, J.; Lisiak, R.; Wojtowicz-Mlochow-
ska, H. In The Chemistry of Organic Selenium and Tellurium Compounds; Rap-
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10530e10535.
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3112e3120.
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7138e7139.
10. Alami, M.; Ferri, F.; Linstrumelle, G. Tetrahedron Lett. 1993, 34, 6403e6406.
11. The structure of allylic alcohols 7 and 8 was assigned by inspection of the
spinespin coupling of the vinyl proton (7: singlet, 8: triplet).
12. The structure of allylic amines 11 and 12 was assigned by inspection of the
spinespin coupling of the vinyl proton (11: singlet, 12: triplet).
13. The structure of cis-16 was assigned by the coupling constant between alkene
protons (cis-16: 13.8 Hz).
4.6.29. (E)-2-Benzylidene-1-phenyl-N-propylbut-3-en-1-amine
(13de). Minor regioisomer; dH (400 MHz, CDCl3), characteristic
signals: 4.67 (s, 1H), 5.11 (d, J¼11.5 Hz, 1H), 5.36 (d, J¼17.8 Hz, 1H),
6.71 (dd, J¼11.5, 17.8 Hz, 1H), 6.99 (s, 1H).
4.6.30. (E)-N-Benzyl-4-phenyldeca-1,3-dien-5-amine (14df). Mixture
of regioisomers (13df:14df¼14:86). Pale yellow oil, 73% yield; Major
regioisomer; dH (400 MHz, CDCl3) 0.86 (t, J¼7.0 Hz, 3H), 1.18e1.40
(m, 8H), 1.53 (br s, 1H), 3.57 (t, J¼6.5 Hz, 1H), 3.74 (ABq, J¼13.2 Hz,
14. Nakagawa, T.; Kasatkin, A.; Sato, F. Tetrahedron Lett. 1995, 36, 3207e3210.