Conjugate addition of vinylic organocuprates generated via transmetalation of phenylseleno-substituted vinylzirconates: Functionalization at the 4-position of enones

Article abstract of DOI:10.1002/hc.20720

Hydrozirconation of propargylic selenides (1) or 4-phenylseleno-1-butyne (2) with Cp₂ZrHCl, followed by in situ transmetalation to cuprate (Me₂Cu(CN)Li₂) and addition of enones, led to the formation of 1,4-adducts in good

Full text of DOI:10.1002/hc.20720

Heteroatom Chemistry
Volume 22, Number 3/4, 2011
Conjugate Addition of Vinylic Organocuprates
Generated via Transmetalation of
Phenylseleno-Substituted Vinylzirconates:
Functionalization at the 4-Position of Enones
Masahito Segi, Masahiro Suzuki, Kazuki Shintaku,
and Hajime Maeda
Division of Material Sciences, Graduate School of Natural Science and Technology, Kanazawa
University, Kakuma-machi, Kanazawa 920-1192, Japan
Received 14 December 2010; revised 6 February 2011
many metal derivatives in the transmetalation proce-
ABSTRACT: Hydrozirconation of propargylic se-
dure, organozirconium compounds have been used
lenides (1) or 4-phenylseleno-1-butyne (2) with
for generation of vinylic organocuprates [4–6] be-
Cp2ZrHCl, followed by in situ transmetalation to
cause alkenylzirconocenes are easily prepared by the
cuprate (Me2Cu(CN)Li2) and addition of enones, led
highly regio- and stereoselective hydrozirconation
to the formation of 1,4-adducts in good yields. The
of terminal alkynes with zirconocene hydride chlo-
adducts derived from 1 were subjected to oxidation
ride (Cp2ZrHCl, Schwartz reagent) [7–11]. On the
with H2 O2 to afford allylic alcohol derivatives via [2,3]
other hand, organoselenium chemistry has become
sigmatropic rearrangement of allylic selenides. On the
a very powerful tool in organic synthesis [12–14]. It
other hand, the oxidation of the products derived from
is noteworthy that compounds bearing the phenylse-
2 gave the corresponding ketones having a conjugated
leno (PhSe) group have easily handled nature. One of
diene moiety at the β-position via selenoxide elimi-
the most common and useful transformations of this
ꢀ
C
nation. 2011 Wiley Periodicals, Inc. Heteroatom Chem
group is its oxidative removal under mild conditions,
leading to olefins or allylic alcohols via selenoxide
elimination or [2,3] sigmatropic rearrangement, re-
22:545–552, 2011; View this article online at wileyonlineli-
brary.com. DOI 10.1002/hc.20720
spectively. In this study, we have investigated the
conjugate addition of vinylic organocuprates gener-
ated via transmetalation of vinylzirconates having a
phenylseleno group to enones, followed by function-
alization at the β-side chain based on organosele-
nium chemistry.
INTRODUCTION
Conjugate addition of organocuprates to α,
β-unsaturated carbonyl compounds is one of the
important and valuable synthetic processes in or-
ganic chemistry [1]. Especially, the consistently effi-
cient 1,4-addition of functionalized organocuprates
to enones has been achieved utilizing a transmetala-
tion strategy for the cuprate formation [2,3]. Among
RESULTS AND DISCUSSION
Dedicated to Professor Kin-ya Akiba on the occasion of his 75th
birthday.
Correspondence to: M. Segi; e-mail: segi@t.kanazawa-u.ac.jp.
2011 Wiley Periodicals, Inc.
c
ꢀ
545

546 Segi et al.
The vinylzirconates were easily prepared in situ from
terminal alkynes 1 and 2 using Schwartz reagent.
First, propargylic selenides 1 were employed as start-
ing alkynes. After the hydrozirconation of phenyl
propargyl selenide 1a with Cp2ZrHCl in THF at
room temperature for 15 min, 1 equiv of MeLi and
Me2Cu(CN)Li2 (generated from 2 MeLi + CuCN in
THF at −78◦C) in that order were added to the above
mixture at −78◦C. The treatment of the resulting re-
action mixture with 2-cyclohexen-1-one at this tem-
perature afforded the desired 1,4-adduct 3aa with E
configuration in 73% yield [Eq. (1)]. The structure
of the obtained product was determined by nuclear
magnetic resonance (NMR), infrared (IR), and mass
1
spectrometry (MS) spectra. The H NMR spectrum
SCHEME 1
of 3aa showed two olefinic protons at δ 5.55 and 5.23
as a doublet–triplet and a doublet–doublet, respec-
tively, having a large vicinal coupling (J = 15.1 Hz)
between their protons, which indicates E configura-
tion as shown in [Eq. (1)].
geometry. The subsequent conjugate addition to cy-
clohexenone, followed by proton quenching, leads to
the formation of the 1,4-adduct (3aa) with complete
E configuration.
The obtained 1,4-adducts 3 contain an allylic se-
lenide moiety at the β-side chain. They were oxi-
dized by H2O2 in the presence of pyridine to give
allylic alcohol derivatives 4 as a mixture of diastere-
omers in good to excellent yields via [2,3] sigmat-
ropic rearrangement of the corresponding allylic se-
lenoxides. The results are shown in Table 2. In the
case of five-membered ring ketones, the rearrange-
ment proceeded with high diastereoselectivity, but it
was not determined whether the major isomer was
trans or cis from NMR spectral analysis in all cases.
In addition, when R was n-C7H15 in Table 2, the dou-
ble bond formed during the rearrangement showed
a complete preference for the E configuration.
The hydrozirconation of 2 with Cp2ZrHCl, fol-
lowed by in situ transmetalation to Me2Cu(CN)Li2
and addition of enones, resulted in the formation of
1,4-adducts 5 having a homoallylic selenide moiety
at the β-position in excellent yields. The results are
shown in Table 3. Furthermore, all of these obtained
products have E geometry on the double bond.
Oxidation of the above products (5b and 5d) by
H2O2 in tetrahydrofuran (THF) afforded the corre-
sponding ketones 6b and 6d having a conjugated
diene part at the β- position in good yields via se-
lenoxide elimination (Scheme 2). The products were
characterized by NMR and MS data.
Several examples of these conjugate additions
using propargylic selenide derivatives 1 as starting
alkynes are illustrated in Table 1. This conjugate
addition did not proceed at all in the absence of
cuprates. Therefore, these satisfactory yields of 1,4-
adducts imply that transmetalation from zirconium
to copper at the terminal carbon occurs efficiently
in this one-pot process. When the alkyne 1b having
a stereogenic center was used as a starting mate-
rial, a mixture of diastereoisomers (ca. 1:1) was ob-
tained. However, unambiguous structural evidence
for the diastereomers did not come from NMR spec-
tral analysis (entries 2, 4, and 6).
The intermediates in this one-pot sequence are
shown in Scheme 1. Hydrozirconation of terminal
alkynes (1a) with Cp2ZrHCl proceeds with an excel-
lent regio- and stereochemical control to afford only
terminal zirconocene intermediate I. The resulting
vinylzirconocene I reacts with 1 equiv of MeLi to
give the corresponding methylzirconocene interme-
diate II, which are subsequently subjected to trans-
metalation reaction by the addition of a cooled so-
lution of Me2Cu(CN)Li2 to yield presumably vinylic
cyanocupurate III with the retention of double bond
In conclusion, a simple and useful method
for functionalization at 4-position of enones has
been developed by conjugate addition of vinylic
organocuprates generated via transmetalation of
vinylzirconates having a phenylseleno group to
enones, followed by oxidative deselenation.
Heteroatom Chemistry DOI 10.1002/hc

Conjugate Addition of Vinylic Organocuprates Generated via Transmetalation of Phenylseleno-Substituted Vinylzirconates 547
TABLE 1 Conjugate Addition of Vinylic Cuprates Generated via Transmetalation of Vinylzirconates Derived from Terminal
Alkynes
Entry
1
Enone
O
Alkyne
Product
Yield (%)a
73
O
O
1a
3aa
SePh
76b
67
3ab
3ba
2
3
1b
1a
SePh
n-C7H15
O
O
SePh
O
60b
4
1b
3bb
SePh
n-C7H15
O
5
6
3ca
3cb
78
1a
1b
SePh
O
O
SePh
54b
n-C7H15
aIsolated yield, chromatographically pure materials.
bMixture of diastereomers.
EXPERIMENTAL
Column chromatography was conducted by us-
ing Fuji Silysia Chemical silica gel BW-127ZH. THF
was distilled from sodium benzophenone ketyl un-
der nitrogen. CH2Cl2 was dried over calcium hydride
and distilled under nitrogen. Ethanol was distilled
1H, 13C, and 77Se NMR spectra were recorded on
JEOL JNM-FX-100 (1H, 99.6 MHz) and JNM-GX-400
(1H; 399.7 MHz, 13C; 100.4 MHz, and 77Se; 76.2 MHz,
respectively) spectrometers. Chemical shifts were re-
ported in ppm downfield from tetramethylsilane as
an internal standard. IR spectra were obtained on a
JASCO A-202 spectrometer. Mass spectra (EI) were
recorded on a Hitachi M-80 mass spectrometer.
˚
from calcium hydride and stored over 4 A molecu-
lar sieves. Other reagents were commercially avail-
able and used without further purification. All reac-
tions were performed under argon atmosphere with
flame-dried glassware using a vacuum pump unless
otherwise described.
Synthesis of Phenyl Propargyl Selenide 1a
To a stirred solution of diphenyl diselenide (4.71 g,
15.0 mmol) and sodium formaldehydesulfoxylate
dihydrate (Rongalit) (2.31 g, 15 mmol) in EtOH
(50 mL), a solution of sodium hydroxide (1.80 g,
45 mmol) in H2O (5 mL) was added. After the solu-
tion was stirred for 15 min at 50◦C, the oil bath was
replaced by an ice bath. Propargyl bromide (3.60 g,
30 mmol) was added and the reaction mixture was
SCHEME 2
Heteroatom Chemistry DOI 10.1002/hc

548 Segi et al.
TABLE 2 Oxidation of Allylic Selenides
stirred for 3 h at 0◦C. The reaction was quenched
with 1 N HCl and extracted with ether. The combined
organic layers were washed with saturated NaHCO3
followed by brine, dried over MgSO4, and concen-
trated. The residue was distilled under reduced pres-
sure (74–75◦C/0.5 mmHg) to give phenyl propargyl
selenide 1a (4.12 g, 92% yield) [15].
bined organic layers were washed with brine, dried
over MgSO4, and concentrated. The residue was dis-
tilled under reduced pressure (48–50◦C/0.5 mmHg)
to give 1-decyn-3-ol (2.72 g, 88% yield).
To a solution of 1-decyn-3-ol (2.7 g, 17 mmol)
and pyridine (135 mg, 0.17 mmol) in diethyl ether
(30 mL), phosphorus tribromide (2.16 g, 8.0 mmol)
was added dropwise at room temperature. After the
solution was stirred for 12 h at this temperature fol-
lowed by 2 h of additional stirring at reflux, the re-
action was quenched with H2O and extracted with
ether. The combined organic layers were washed
with brine, dried over MgSO4, and concentrated. The
residue was distilled under reduced pressure (30–
31◦C/0.5 mmHg) to give 3-bromo-1-decyne (1.13 g,
31% yield).
Synthesis of 3-Phenylseleno-1-decyne 1b
To a THF solution of ethynylmagnesium bromide
(0.5 M solution in THF, 40 mL, 20 mmol), 1-octanal
(2.56 g, 20 mmol) in THF (5 mL) was added drop-
wise at 0◦C. After stirring for 1 h at room tempera-
ture, the reaction was quenched with 1 N HCl. The
reaction mixture was extracted with ether. The com-
Heteroatom Chemistry DOI 10.1002/hc

Conjugate Addition of Vinylic Organocuprates Generated via Transmetalation of Phenylseleno-Substituted Vinylzirconates 549
TABLE 3 Hydroziconation, Transmetalation, and Conjugate Addition Using 2 in One-Pot Procedure
To a stirred solution of diphenyl diselenide
(1.57 g, 5.0 mmol) and sodium formaldehydesulfoxy-
late dihydrate (Rongalit) (1.3 g, 5.0 mmol) in EtOH
(20 mL), a solution of sodium hydroxide (0.60 g,
15 mmol) in H2O (5 mL) was added. After the so-
lution was stirred for 15 min at 50◦C, 3-bromo-1-
decyne (1.09 g, 5.0 mmol) was added and the re-
action mixture was further stirred for 3 h at 0◦C.
The reaction was quenched with 1 N HCl and ex-
tracted with ether. The combined organic layers
were washed with saturated NaHCO3 followed by
brine, dried over MgSO4, and concentrated. The
residue was distilled under reduced pressure (88–
90◦C/0.5 mmHg) to give 3-phenylseleno-1-decyne 1b
(1.89 g, 52% yield).
added dropwise at 0◦C. After the solution was stirred
for 20 min, the reaction was quenched with H2O and
extracted with ether. The combined organic layers
were washed with brine, dried over MgSO4, and con-
centrated. The residue was distilled under reduced
pressure (75–76◦C / 0.3 mm Hg) to give 3-butyn-1-yl
mesylate (4.0 g, 85% yield).
To a solution of diphenyl diselenide (4.24 g,
13.5 mmol) and sodium formaldehydesulfoxylate di-
hydrate (Rongalit) (3.51 g, 13.5 mmol) in EtOH
(50 mL), a solution of sodium hydroxide (1.62 g,
40.5 mmol) in H2O (10 mL) was added. After the so-
lution was stirred for 15 min at 50◦C, 3-butyn-1-yl
mesylate (4.0 g, 27 mmol) was added and the reac-
tion mixture was further stirred for 15 min at this
temperature. The reaction was quenched with 1 N
HCl and extracted with ether. The combined organic
layers were washed with saturated NaHCO3 followed
by brine, dried over MgSO4, and concentrated. The
residue was distilled under reduced pressure (83–
84◦C/0.5 mmHg) to give 4-phenylseleno-1-butyne 2
(3.2 g, 56% yield).
Synthesis of 4-Phenylseleno-1-butyne 2
To a solution of 3-butyn-1-ol (1.55 g, 22.1 mmol) and
triethylamine (3.52 g, 34.8 mmol) in CH2Cl2 (30 mL),
methanesulfonyl chloride (5.09 g, 44.4 mmol) was
Heteroatom Chemistry DOI 10.1002/hc

550 Segi et al.
3.46 (d, J = 7.6 Hz, 2H), 5.27 (dd, J = 7.6, 15.1 Hz,
1H), 5.61 (td, J = 15.1, 7.2 Hz, 1H), 7.2–7.5 (m,
5H); 13C NMR (100 MHz, CDCl3): δ (ppm) 27.9, 29.4,
37.9, 39.2, 44.5, 126.0, 127.3, 128.8, 129.4, 134.1,
134.8, 212.5; IR (neat, cm−1): ν 3050, 2950, 1740
(C O), 1575, 960; MS m/z (%): 280 (M+, 64), 158
(56), 123 (59), 95 (86), 67 (100), 41 (36). HRMS (EI)
Calcd for C14H16OSe: 280.0366, Found: 280.0371.
General Procedure for Conjugate Addition of
Vinylic Organocuprates to Various Enones
To a 25 mL of round-bottomed flask, Cp2ZrHCl
(0.26 g, 1.0 mmol) was added and was degassed un-
der high vacuum with an argon purge. A solution of
phenylseleno-substituted alkyne 1 or 2 (1.0 mmol)
in THF (5 mL) was added and the reaction mixture
was stirred for 15 min at room temperature. The re-
action was cooled to −78◦C and MeLi (1 M solution
in Et2O, 1.0 mL, 1.0 mmol) was added dropwise. Af-
ter stirring for 15 min at −78◦C, Me2Cu(CN)Li2 (1 M
solution in THF, 1.0 mL, 1.0 mmol) prepared from
CuCN and 2 equiv of MeLi in another flask [6] was
added dropwise and the solution was further stirred
for 30 min at this temperature. An enone (0.5 mmol)
was added to the reaction mixture. After stirring for
1 h at −78◦C, the reaction was warmed up to 0◦C
and quenched with 1 N HCl and extracted with ether.
The combined organic layers were washed with satu-
rated NaHCO3 followed by brine, dried over MgSO4,
concentrated, and purified by column chromatogra-
phy on silica gel to afford 1,4-adducts 3 or 5.
(E)-3-[3-(Phenylselanyl)dec-1-enyl]cyclopentanone
1
3bb. Yield = 60% yield, oil, H NMR (400 MHz,
CDCl3): major adduct: δ (ppm) 0.88 (t, 3H), 1.1–2.3
(m, 18H), 2.67 (m, 1H), 3.70 (td, J = 6.1, 8.8 Hz,
1H), 5.01 (dd, J = 7.1, 15.0 Hz, 1H), 5.42 (dd, J =
6.1, 15.0 Hz, 1H), 7.2–7.5 (m, 5H); minor adduct:
δ (ppm) 0.88 (t, 3H), 1.10–2.30 (m, 18H), 2.67 (m,
1H), 3.69 (td, J = 6.1, 8.8 Hz, 1H), 5.02 (dd, J =
7.1, 15.0 Hz, 1H), 5.43 (dd, J = 6.1, 15.0 Hz, 1H),
7.20–7.50 (m, 5H).
(E)-5-Methyl-8-(phenylselanyl)oct-6-en-3-one 3ca.
Yield = 78% yield, oil, 1H NMR (400 MHz, CDCl3): δ
(ppm) 0.89 (d, 3H), 1.05 (t, 3H), 2.24 (q, 2H), 2.32 (d,
2H), 2.63 (sep, 1H), 3.44 (d, J = 7.6 Hz, 2H), 5.26 (dd,
J = 7.3, 15.3 Hz, 1H), 5.54 (td, J = 15.3, 7.6 Hz, 1H),
7.2–7.5 (m, 5H); 13C NMR (100 MHz, CDCl3): δ (ppm)
7.62, 20.0, 29.9, 32.1, 36.5, 49.2, 124.7, 127.1, 128.8,
129.8, 133.8, 137.6, 210.5; IR (neat, cm−1): ν 2980,
2930, 1715 (C O), 1580, 1480, 1440, 970, 750, 690;
MS m/z (%): 296 (M+, 0.1), 157 (11), 139 (75), 121
(9), 77 (8), 57 (100). HRMS (EI) Calcd for C15H20OSe:
296.0679, Found: 296.0676.
(E)-3-[3-(Phenylselanyl)prop-1-enyl]cyclohexa-
none 3aa. Yield = 73% yield, oil, 1H NMR (400
MHz, CDCl3): δ (ppm) 1.2–2.4 (m, 11H), 3.45 (d, J
= 7.6 Hz, 2H), 5.23 (dd, J = 6.7, 15.1 Hz, 1H), 5.55
(td, J = 15.1, 7.6 Hz, 1H), 7.2–7.5 (m, 5H); 13C NMR
(100 MHz, CDCl3): δ (ppm) 24.8, 29.8, 31.1, 41.1,
41.1, 47.2, 125.5, 127.3, 128.8, 128.8, 134.1, 135.8,
210.7; 77Se NMR (76 MHz, CDCl3): δ (ppm) 355.2; IR
(neat, cm−1): ν 3080, 2940, 1710 (C O), 1580, 965,
740, 690; MS m/z (%): 294 (M+, 5), 157 (24), 137
(85), 95 (47), 67 (90), 55 (100). HRMS (EI) Calcd for
C15H18OSe: 294.0523, Found: 294.0520.
(E)-5-Methyl-8-(phenylselanyl)pentadec-6-en-3-
one 3cb. Yield = 54% yield, oil, 1H NMR (400 MHz,
CDCl3): major adduct: δ (ppm) 0.85 (d, 3H), 0.88
(t, 3H), 1.00 (t, 3H), 1.2–1.8 (m, 12H), 2.16 (d, 2H),
2.30 (q, 2H), 2.57 (sep, 1H), 3.66 (td, J = 7.3 Hz,
1H), 4.99 (dd, J = 9.8 Hz, 1H), 5.33 (dd, J = 7.3,
9.8 Hz, 1H), 7.2–7.5 (m, 5H); minor adduct: δ (ppm)
0.85 (d, 3H), 0.88 (t, 3H), 1.00 (t, 3H), 1.2–1.8 (m,
12H), 2.16 (d, 2H), 2.30 (q, 2H), 2.57 (sep, 1H), 3.67
(td, J = 7.1 Hz, 1H), 5.06 (dd, J = 9.5 Hz, 1H), 5.35
(dd, J = 7.1, 9.5 Hz, 1H), 7.2–7.5 (m, 5H); IR (neat,
cm−1): ν 2950, 2900, 2860, 1715 (C O), 1455, 1380,
1120, 1020, 965, 740, 695.
(E)-3-[3-(Phenylselanyl)dec-1-enyl]cyclohexanone
1
3ab. Yield = 76% yield, oil, H NMR (400 MHz,
CDCl3): major adduct: δ (ppm) 1.2–2.3 (m, 21H),
3.66 (td, J = 15.1, 7.6 Hz, 1H), 4.99 (dd, J = 7.0,
15.1 Hz, 1H), 5.35 (dd, J = 6.7, 15.1 Hz, 1H), 7.2–7.5
(m, 5H); minor adduct: δ (ppm) 1.2–2.3 (m, 21H),
3.66 (td, J = 15.1, 7.6 Hz, 1H), 4.99 (dd, J = 7.0,
15.1 Hz, 1H), 5.38 (dd, J = 6.7, 15.1 Hz, 1H), 7.2–7.5
(m, 5H); IR (neat, cm−1): ν 2950, 2850, 1710 (C O),
1580, 1480, 1435, 1220, 960, 910, 740, 690; MS m/z
(%): 392 (M+, 15), 312 (3), 235 (85), 217 (44), 177
(13), 157 (23), 123 (100), 97 (100), 67 (38), 55 (35).
HRMS (EI) Calcd for C22H32OSe: 392.1618, Found:
392.1618.
(E)-3-[4-(Phenylselanyl)but-1-enyl]cyclohexanone
5a. Yield = 95% yield, oil, 1H NMR (400 MHz,
CDCl3): δ (ppm) 1.4–2.5 (m, 11H), 2.92 (t, 2H), 5.43
(ABq, 2H), 7.2–7.5 (m, 5H); 13C NMR (100 MHz,
CDCl3): δ (ppm) 24.7, 27.2, 31.1, 33.0, 41.1, 41.1,
47.2, 126.6, 127.9, 128.8, 130.1, 132.4, 134.6, 210.9;
MS m/z (%): 308 (M+, 31), 171 (20), 151 (68), 133
(E)-3-[3-(Phenylselanyl)prop-1-enyl]cyclopenta-
none 3ba (Lit. [16]). Yield = 67% yield, oil, 1H
NMR (400 MHz, CDCl3): δ (ppm) 1.4–2.7 (m, 9H),
Heteroatom Chemistry DOI 10.1002/hc

Conjugate Addition of Vinylic Organocuprates Generated via Transmetalation of Phenylseleno-Substituted Vinylzirconates 551
(14), 107 (25), 91 (89), 55 (96), 39 (36). HRMS (EI)
Calcd for C16H20OSe: 308.0679, Found: 308.0681.
product: m/z (%) 154 (M+, 0.3), 136 (5), 98 (100),
69 (61), 41 (64); minor product: m/z (%) 154 (M+,
0.05), 136 (6), 98 (100), 69 (63), 41 (65). HRMS (EI)
Calcd for C9H14O2: 154.0994, Found: 154.0996.
Trans-(E)-4-Phenyl-3-[4-(phenylselanyl)but-1-enyl]
1
cyclohexane 5b. Yield = 67% yield, oil, H NMR
(100 MHz, CDCl3): δ (ppm) 1.3–2.5 (m, 11H), 2.63
(t, 1H), 5.17 (ABq, 2H), 7.1–7.5 (m, 10H); MS m/z
(%): 384 (M+, 29), 227 (60), 200 (28), 169 (28), 123
(41), 91 (100), 55(8).
(E)-3-(1-Hydroxydec-2-enyl)cyclohexanone 4ab.
1
Yield = 94% yield, oil, H NMR (100 MHz, CDCl3):
major product: δ (ppm) 0.88 (dt, 3H), 1.2–2.3 (m,
21H), 3.8–4.0 (m, 1H), 5.43 (dd, J = 6.6, 15.4 Hz,
1H), 5.69 (dt, J = 5.3, 15.4 Hz, 1H); minor product:
δ (ppm) 0.88 (dt, 3H), 1.2–2.3 (m, 21H), 3.8–4.0 (m,
1H), 5.41 (dd, J = 6.1, 15.4 Hz, 1H), 5.69 (dt, J = 5.3,
15.4 Hz, 1H); MS: major product: m/z (%) 252 (M+,
0.1), 234 (14), 179 (4), 155 (15), 123 (21), 98 (100),
81 (44), 57 (31), 41 (40); minor product: m/z (%) 252
(M+, 0.1), 234 (16), 179 (4), 155 (15), 123 (24), 98
(100), 81 (46), 55 (35), 41 (43).
(E)-3-[4-(Phenylselanyl)but-1-enyl]cyclopentanone
5c. Yield = 87% yield, oil, 1H NMR (100 MHz,
CDCl3): δ (ppm) 1.6–2.5 (m, 11H), 2.94 (t, 2H), 5.50
(ABq, 2H), 7.2–7.5 (m, 5H); MS m/z (%): 294 (M+,
100), 157 (24), 137 (85), 119 (14), 95 (47), 67 (90),
55 (100), 41 (38). HRMS (EI) Calcd for C15H18OSe:
294.0523, Found: 294.0520.
(E)-4-Phenyl-8-(phenylselanyl)oct-5-en-2-one 5d.
3-(1-Hydroxyprop-2-enyl)cyclopentanone
4ba.
1
Yield = 82% yield, oil, H NMR (400 MHz, CDCl3):
1
Yield = 70% yield, oil, H NMR (400 MHz, CDCl3):
major product: δ (ppm) 1.7–2.4 (m, 8H), 4.09 (brs,
1H), 5.20 (dd, J = 1.0, 10.2 Hz, 1H), 5.28 (dd, J =
1.0, 17.1 Hz, 1H), 5.89 (ddd, J = 6.3, 10.2, 17.1 Hz,
1H); MS: major product: m/z (%) 140 (M+, 2), 112
(4), 83 (100), 55 (65), 39 (13). HRMS (EI) Calcd for
C8H12O2: 140.0837, Found: 140.0835.
δ (ppm) 2.04 (s, 3H), 2.37 (q, J = 6.6 Hz, 2H), 2.77
(d, J = 7.1 Hz, 2H), 2.88 (t, J = 6.6 Hz, 2H), 3.84
(q, J = 7.1 Hz, 1H), 5.42 (td, J = 15.3, 6.6 Hz, 1H),
5.60 (dd, J = 15.3, 7.1 Hz, 1H), 7.1–7.5 (m, 10H); 13
C
NMR (100 MHz, CDCl3): δ (ppm) 27.28, 30.67, 33.13,
43.66, 49.49, 126.52, 126.77, 127.54, 128.58, 129.02,
130.29, 132.66, 134.04, 143.26, 207.03; MS m/z (%):
358 (M+, 10), 315 (12), 171 (28), 143 (88), 91 (100),
51 (10).
(E)-3-(1-Hydroxydec-2-enyl)cyclopentanone 4bb.
1
Yield = 92% yield, oil, H NMR (100 MHz, CDCl3):
major product: δ (ppm) 0.88 (t, 3H), 1.2–2.4 (m,
20H), 4.00 (brs, 1H), 5.45 (dd, J = 6.4, 15.4 Hz, 1H),
5.72 (dt, J = 6.1, 15.4 Hz, 1H); MS: major product:
m/z (%) 238 (M+, 1), 220 (34), 155 (59), 135 (21), 95
(100), 79 (73), 57 (50), 41 (49).
General Procedure for Oxidative Deselenation of
Allylic Selenide
To a solution of selenide 3 (0.20 mmol) and pyridine
(0.40 mmol) in CH2Cl2(5 mL), H2O2 (2.0 mmol) was
added at 0◦C. After stirring for 40 min at this tem-
perature, the reaction was quenched with H2O and
extracted with ether. The combined organic layers
were washed with brine, dried over MgSO4, concen-
trated, and purified by column chromatography on
silica gel to afford an allylic alcohol 4.
6-Hydroxy-5-methyloct-7-en-3-one 4ca. Yield =
1
72% yield, oil, H NMR (100 MHz, CDCl3): major
product: δ (ppm) 1.4–2.5 (m, 10H), 3.99 (brt, J =
6.1 Hz, 1H), 5.21 (dt, J = 1.2, 17.1 Hz, 1H), 5.28
(dd, J = 6.4, 15.4 Hz, 1H), 5.85 (ddd, J = 6.4, 10.5,
17.1 Hz, 1H); minor product: δ (ppm) 1.4–2.5 (m,
10H), 4.05 (brt, J = 5.1 Hz, 1H), 5.21 (dt, J = 1.2,
17.1 Hz, 1H), 5.28 (dd, J = 6.4, 15.4 Hz, 1H), 5.85
(ddd, J = 6.4, 10.5, 17.1 Hz, 1H); MS m/z (%): 156
(M+, 0.01), 138 (26), 109 (9), 85 (29), 57 (100), 41
(49).
3-(1-Hydroxyprop-2-enyl)cyclohexanone
4aa.
1
Yield = 68% yield, oil, H NMR (400 MHz, CDCl3):
major product: δ (ppm) 1.4–2.5 (m, 10H), 3.99 (brt,
J = 6.1 Hz, 1H), 5.21 (dt, J = 1.2, 17.1 Hz, 1H),
5.28 (dt, J = 1.2, 10.5 Hz, 1H), 5.85 (ddd, J= 10.5,
17.1 Hz, 2H); minor product: δ (ppm) 1.4–2.5 (m,
10H), 4.05 (brt, J = 5.1 Hz, 1H), 5.21 (dt, J = 1.2,
17.1 Hz, 1H), 5.28 (dt, J = 1.2, 10.5 Hz, 1H), 5.85
(ddd, J= 10.5, 17.1 Hz, 2H); 13C NMR (100 MHz,
CDCl3): major product: δ (ppm) 75.9, 116.3, 116.4,
138.7, 212.1; minor product: δ (ppm) 76.0, 116.3,
116.4, 138.6, 211.9; IR (neat, cm−1): ν 3450 (OH),
2940, 1700 (C O), 1640, 1420, 990, 910; MS: major
(E)-6-Hydroxy-5-methylpentadec-7-en-3-one 4cb.
1
Yield = 93% yield, oil, H NMR (100 MHz, CDCl3):
major product: δ (ppm) 0.7–2.8 (m, 28H), 3.8–4.1
(m, 1H), 5.40 (dd, J = 6.2, 15.4 Hz, 1H), 5.67 (dt, J
= 6.1, 15.4 Hz, 1H); minor product: δ (ppm) 0.7–2.8
(m, 28H), 3.8–4.1 (m, 1H), 5.34 (dd, J = 7.5, 15.4 Hz,
1H), 5.67 (dt, J = 6.1, 15.4 Hz, 1H); MS m/z (%): 236
Heteroatom Chemistry DOI 10.1002/hc

552 Segi et al.
(M+-H2O, 100), 165 (44), 138 (41), 109 (75), 81 (40),
55 (46).
(dd, J = 0.5, 17.1 Hz, 1H), 5.81 (dd, J = 7.1, 15.4 Hz,
1H), 6.01 (dd, J = 10.3, 15.4 Hz, 1H), 6.27 (dt, J
= 17.1, 10.3 Hz, 1H), 7.1–7.5 (m, 5H); MS m/z (%):
200 (M+, 5), 142 (100), 115 (67), 77 (41). HRMS (EI)
Calcd for C14H16O: 200.1201, Found: 200.1198.
General Procedure for Oxidative Deselenation of
Homoallylic Selenide
To a solution of selenide 5 (0.14 mmol) in
THF(5 mL), H2O2 (1.4 mmol) was added at 0◦C and
stirred for 5 min. Then the reaction was warmed up
to room temperature. After stirring for 1 h, the re-
action was quenched with H2O and extracted with
ether. The combined organic layers were washed
with brine, dried over MgSO4, concentrated, and pu-
rified by column chromatography on silica gel to af-
ford the diene 6.
REFERENCES
[1] Lipshutz, B. H.; Sengupta, S. Org React 1992, 41, 135.
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Trans-(E)-3-(Buta-1,3-dienyl)-4-phenylcyclohexa-
none 6b. Yield = 70% yield, oil, 1H NMR (100
MHz, CDCl3): δ (ppm) 1.2–2.8 (m, 8H), 4.89 (dd,
J = 1.4, 9.3 Hz 1H), 5.02 (dd, J = 1.4, 16.8 Hz, 1H),
5.38 (dd, J = 6.4, 15.4 Hz, 1H), 5.82 (dd, J = 10.3,
15.4 Hz, 1H), 6.09 (ddd, J = 9.3, 10.3, 16.8 Hz, 1H),
7.1–7.5 (m, 1H); MS m/z (%): 226 (M+, 19), 168 (3),
141 (3), 122 (18), 104 (100), 79 (23).
(E)-4-Phenylocta-5,7-dien-2-one 6d. Yield
=
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Am Chem Soc 1981, 103, 3112.
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3790.
1
78% yield, oil, H NMR (100 MHz, CDCl3): δ (ppm)
2.07 (s, 3H), 2.85 (d, J = 7.1 Hz 2H), 3.94 (q, J =
7.1 Hz, 1H), 5.00 (dd, J = 0.5, 10.3 Hz, 1H), 5.11
Heteroatom Chemistry DOI 10.1002/hc