One-pot synthesis of heterocyclic compounds initiated by chemoselective addition to β-acyl substituted unsaturated aldehydes with nucleophilic tin complexes

Article abstract of DOI:10.1016/j.jorganchem.2006.03.043

β-Acyl substituted unsaturated aldehydes 1 were revealed to be good precursors for the synthesis of various heterocyclic compounds by the combination with tin nucleophiles. Various 2-monosubstituted pyrroles were prepared in an one-pot procedure via the reductive amination of formyl groups of 1 by using Bu₂SnIH-HMPA complex. One-pot synthesis of heterocycles was carried out initiated by chemoselective reduction of 1 with Bu₃SnH-HMPA complex and the subsequent reaction with heterocumulenes. Furthermore, the one-pot synthesis of nitrogen heterocyclic compounds accompanying chemo-, regio- and diastereoselective carbon-carbon bond formation in side chain moieties was effectively accomplished initiated by the regio- and diastereoselective allylation of the formyl group of 1 with allylic tin species.

Full text of DOI:10.1016/j.jorganchem.2006.03.043

Journal of Organometallic Chemistry 692 (2007) 604–619
www.elsevier.com/locate/jorganchem
One-pot synthesis of heterocyclic compounds initiated by
chemoselective addition to b-acyl substituted unsaturated
aldehydes with nucleophilic tin complexes
*
Ikuya Shibata , Hirofumi Kato, Makoto Yasuda, Akio Baba
Department of Applied Chemistry, Graduate School of Engineering, Research Center for Environmental Preservation,
Osaka University, 2-1 Yamadaoka, Suita, Osaka 565-0871, Japan
Received 15 February 2006; received in revised form 13 March 2006; accepted 20 March 2006
Available online 30 August 2006
Abstract
b-Acyl substituted unsaturated aldehydes 1 were revealed to be good precursors for the synthesis of various heterocyclic compounds
by the combination with tin nucleophiles. Various 2-monosubstituted pyrroles were prepared in an one-pot procedure via the reductive
amination of formyl groups of 1 by using Bu2SnIH–HMPA complex. One-pot synthesis of heterocycles was carried out initiated by
chemoselective reduction of 1 with Bu3SnH–HMPA complex and the subsequent reaction with heterocumulenes. Furthermore, the
one-pot synthesis of nitrogen heterocyclic compounds accompanying chemo-, regio- and diastereoselective carbon–carbon bond forma-
tion in side chain moieties was effectively accomplished initiated by the regio- and diastereoselective allylation of the formyl group of 1
with allylic tin species.
Ó 2006 Elsevier B.V. All rights reserved.
Keywords: Heterocycle; Reductive amination; Reduction; Allylation; Tin hydride; Allylic tin
1. Introduction
2. Results and discussion
Tin–heteroatom bonds can be easily generated by the
addition of organotin nucleophiles to carbonyl compounds
[1]. The reduction of carbonyl compounds by tributyltin
hydride (Bu3SnH) is a well-known method [2]. Although
the reactions proceed under mild and neutral conditions,
the resulting tin alkoxides have been scarcely used for
further transformation in which most tin–oxygen bonds
are hydrolyzed to alcohols. However, tin–oxygen and –
nitrogen bonds bear high nucleophilicity. In some cases,
their nucleophilicity is higher than that of the correspond-
ing free alcohols and amines [3]. Herein we report the one-
pot synthesis of heterocycles initiated by the chemoselective
addition of bifunctional compounds 1. The generated tin–
heteroatom bonds worked as key intermediates (Scheme 1).
2.1. One-pot synthesis of 2-monosubstituted pyrroles by
reductive amination
We have been developing the unique reactivities of the
halogen-substituted tin hydride systems such as Bu2SnIH
and Bu2SnClH–HMPA which promote effective reduction
of imines [4]. In particular, Bu2SnClH–HMPA affords
effective reductive amination to give a wide range of sec-
ondary and tertiary amines in one-pot procedures [5]. Pyr-
roles are important heterocycles broadly used in materials
science [6] and found in naturally occurring and biologi-
cally important molecules [7]. Accordingly, substantial
attention has been paid to develop efficient methods for
the synthesis of pyrroles, most known methods are for
forming 2,5-di- or polysubstituted pyrroles. Convenient
methods have scarcely reported for the construction of
2-monosubstituted pyrrole ring [8]. Herein a novel, and
*
Corresponding author. Tel.: +81 6 6879 7386; fax: +81 6 6879 7387.
E-mail address: shibata@chem.eng.osaka-u.ac.jp (I. Shibata).
0022-328X/$ - see front matter Ó 2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.jorganchem.2006.03.043

I. Shibata et al. / Journal of Organometallic Chemistry 692 (2007) 604–619
605
Nu
O
Sn Nu
R
R
H
"N" source
O
O
N
1
Sn
Scheme 1. Reaction concept for synthesis of heterocycles.
Bu2SnIH-HMPA
CHO
R
R
N
Ar
2
ArNH2
+
O
1
Scheme 2.
efficient method for construction of 2-monosubstituted
pyrroles was developed via the reductive amination by di-
butyliodotin hydride (Bu2SnIH)–HMPA system (Scheme
2) [9].
for the cyclization because chlorotin derivative, Bu2Sn-
ClH–HMPA, gave no pyrrole 2a at all where only 3a was
obtained under the same conditions (entry 4). Various aro-
matic amines were applicable to give pyrroles 2b–d in
one-pot procedures by the reductive amination of 1 using
Bu2SnIH–HMPA system followed by heating at 80 °C
(entries 5–7). In the case of 1b, pyrrole 2e was also obtained
(entry 8). Enal having aromatic ketone 1c was also reactive
to give the corresponding pyrroles 2f–h where reductive
amination was carried out at À40 °C (entries 9–11).
As shown in Table 1, first, it was found that enal 1a in
the presence of iodotin hydride in THF at 0 °C for 2 h
underwent reductive amination with p-chloroaniline to give
secondary amine 3a in 74% yield (entry 1). Although no
cyclization occurred, this result indicates that reductive
amination was carried out effectively without affecting the
remaining enone functionality in 1a. Chloro-substituent
on nitrogen aromatic ring was not reduced. After the
reductive amination, heating the mixture at 80 °C for 2 h
afforded pyrrole 2a in 22% yield with 60% of 3a (entry
2). In this case, 1,4-dioxane was used as a solvent to heat
the reaction mixture at 80 °C. Noteworthy is that under
the same conditions, pyrrole 2a was obtained in 81% yield
in the presence of an equimolar amount of HMPA (entry
3), in which non-cyclized product 3a was not obtained at
all. The iodo-substituent on the tin center was essential
A plausible reaction course is indicated in Scheme 3. Ini-
tially, reductive amination occurs by mixing Bu2SnIH–
HMPA with starting substrate 1 and an aromatic amine.
It is cleared that halogenotin hydride bears high imine-
selectivity because formyl and enone groups of 1 were
not reduced at all. In the next stage, the resulting tin–nitro-
gen bond adds to the remaining ketone moiety in 1 by heat-
ing. At the last stage, the elimination of tin hydroxide gives
pyrroles 2. The reaction was carried out in a one-pot pro-
cedure hence no intermediates were isolated. The substitu-
Table 1
One-pot synthesis of 2-monosubtituted pyrroles 2 (1 mmol of 1, 1 mmol of ArNH2, 1 mmol of tin hydride, 1 mmol of HMPA, 1 mL of solvent)
Ar
N
Ar
R
Sn
R
CHO
Tin Hydride
Conditions1
R
N
H
N
Ar
+
ArNH2
R
O
Conditions 2
O
1
O
2
3
Entry
R
Ar
Tin hydride
Solvent
Conditions 1
Conditions 2
Product and yield (%)
1
2
3
4
5
6
7
8
9
n-C8H17 (1a)
p-ClC6H4
Bu2SnIH
Bu2SnIH
THF
0 °C, 2 h
0 °C, 2 h
0 °C, 2 h
0 °C, 2 h
0 °C, 2 h
0 °C, 2 h
0 °C, 2 h
0 °C, 2 h
À40 °C, 2 h
À40 °C, 2 h
À40 °C, 2 h
0 °C, 2 h
3a 74
2a 22, 3a 60
2a 81
3a 98
2b 54
2c 60
2d 66
2e 60
2f 46
Dioxane
Dioxane
Dioxane
Dioxane
Dioxane
Dioxane
THF
THF
THF
THF
80 °C, 2 h
80 °C, 2 h
80 °C, 2 h
80 °C, 2 h
80 °C, 2 h
80 °C, 2 h
60 °C, 2 h
60 °C, 2 h
60 °C, 2 h
60 °C, 2 h
Bu2SnIH–HMPA
Bu2SnClH–HMPA
Bu2SnIH–HMPA
Bu2SnIH–HMPA
Bu2SnIH–HMPA
Bu2SnIH–HMPA
Bu2SnIH–HMPA
Bu2SnIH–HMPA
Bu2SnIH–HMPA
Ph
p-Tol
p-MeOC6H4
p-ClC6H4
p-ClC6H4
Ph
PhCH2CH2CH2 (1b)
Ph (1c)
10
11
2g 41
2h 49
p-MeOC6H4

606
I. Shibata et al. / Journal of Organometallic Chemistry 692 (2007) 604–619
Bu2SnIH-HMPA
CHO
R
ArNH2
+
R
N
O
1
Ar
2
- H2O
-SnOH
H
SnO
H
H
R
N
R
NAr
O
Ar
I
Bu
H
Sn
Bu
HMPA
O
H
H
H
H
H
I
O
R
H
Ar
Bu
H
Ar
Bu
R
N
Ar
N
N
Bu
O
R
R
N
Sn
HMPA
I
I
Sn
H
Sn
O
Bu
Sn
Bu
Ts
Bu
HMPA
HMPA
B
A
Scheme 3. A plausible reaction mechanism.
ent and ligand in the tin complex play important roles for
the synthesis of pyrroles. Bu2SnIH–HMPA is a trigonal
bipyramidal structure in which iodine substituent occupy
apical position [10]. The Sn–halogen bond is responsible
for high imine-selectivity, which promotes the formation
of an iminium ion A. As a result, electrophilicity of imine
is increased [4,5]. The activated imine thus formed would
be reduced more rapidly than any other functionalities
such as starting formyl and enone moieties. After the
imine-selective reduction, tin–nitrogen bond is formed.
High coordination of tin is important for the intramolecu-
lar addition. Namely, in the pentavalent tin amide B, the
tin–nitrogen bond occupying the apical position bears ade-
quate nucleophilicity to the remaining carbonyl groups
[11]. It seems that dibutylchlorotin amide moiety
(Bu2ClSnN–) does not have enough nucleophilicity to
cause cyclization because of the electron-withdrawing char-
acter of Cl substituent (entry 4).
atom nucleophiles were generated by the combination of
heterocumulenes (Scheme 4).
For the selective reduction of the formyl groups of 1, the
choice of reducing agents is important, because of coexis-
tence reactive functionalities of enones. As shown in
Table 2, use of conventional agents such as LiAlH4 and
NaBH4 resulted in complex reactions (entries 1–3). Tribu-
tyltin hydride (Bu3SnH) itself bears little reducing ability
(entry 4). The Bu3SnH reaction catalyzed by Lewis acid
[13] gave only 4a, though in moderate yields (entries 5
and 6). We had already developed Bu3SnH–HMPA to
effect chemoselective reduction of formyl groups under
mild conditions [14], and here Bu3SnH–HMPA was found
to reduce the formyl group of 1a in the highest yield (entry
7). Dibutylchlorotin hydride (Bu2ClSnH) complex [15] also
gave good yield of 4a (entry 8). In these cases, other prod-
ucts than 4a–d were not obtained and starting 1a was
recovered. This would be because of the decomposition
of tin hydrides.
2.2. One-pot synthesis of heterocycles initiated by
chemoselective reduction
As shown in Scheme 5, we next tried to prepare hetero-
cycles through initiation by tin hydride reduction in one-
pot procedure. Thus, after the chemoselective reduction
of the formyl group of 1, the generated tin–oxygen bond
of C was allowed to react with an isocyanate [16]. The
resulting tin–nitrogen bond of D successively adds to the
enone moiety in conjugate fashion to give 2-oxazolidinones
Next, the one-pot synthesis of heterocycles was carried
out initiated by the chemoselective reduction of the formyl
groups of bifunctional compounds 1 [12]. The generated
tin–oxygen bonds worked as key intermediates. Hetero-
H
H
O
Sn
H
R
O
R
R
O
Sn
H
O
N
Sn
O
O
1
Scheme 4. Reaction concept for synthesis of heterocycles.

I. Shibata et al. / Journal of Organometallic Chemistry 692 (2007) 604–619
607
Table 2
Chemoselective reduction of formyl group of 1a. (1 mmol of MH, 1 mmol of 1a, 1 mL of THF)
n-C8H17
n-C8H17
n-C8H17
OH
OH
OH
O
OH
OH
4a
4c
4b
4d
M H
n-C8H17
CHO
O
THF
n-C8H17
1a
OH
O
Entry
Reducing agent (MÀH)
Conditions
Product and yield (%)
1
2
3
4
5
6
7
8
DIBAL (1 mmol)
NaBH4 (1 mmol)
LiAlH4 (1 mmol)
Bu3SnH (1 mmol)
Bu3SnH (1 mmol)–ZnCl2 (0.1 mmol)
Bu3SnH (1 mmol)–MgBr2 (0.1 mmol)
Bu3SnH–HMPA (1 mmol)
0 °C, 5 h
rt, 1.5 h
0 °C, 1 h
rt, 23 h
rt, 23 h
rt, 14 h
rt, 3 h
4a 25, 4b 31
4d 61
4b 33, 4c 12
Trace
4a 40
4a 35
4a 56
4a 51
Bu2ClSnH–HMPA (1 mmol)
rt, 3 h
(1 mmol)
Sn-H
HMPA (1 mmol)
HMPA
n-C8H17
CHO
n-C8H17
Sn
O
O
THF (1 mL), 60 °C, 2 h
O
C
1a (1 mmol)
n-C8H17
n-C8H17
nBuN C O
O
H+
O
nBu
(0.8 mmol)
O
N
O
N
O
Sn
60 °C,
1~3 h
0 °C, 0.5 h
nBu
5a
O
HMPA
D
Bu2ClSnH
Bu3SnH
37%
84%
Sn-H=
Scheme 5.
5. In the tin hydride initiated reductions presented here, use
of dibutylchlorotin hydride system (Bu2ClSnH–HMPA)
and the subsequent treatment with BuN@C@O gave the
desired 2-oxazolidone 5a in only 37% yield, although the
initial reduction of the formyl group proceeded effectively
(see Table 2, entry 8). In contrast, the reduction of 1 with
tributyltin nucleophile (Bu3SnH–HMPA) and subsequent
treatment with BuN@C@O afforded 2-oxazolidones 5a in
a good yield (84%). 2-Oxazolidones are important biologi-
cally active compounds and precursors of b-amino alcohols
[17].
The role of the Sn–N bond of D is clearly important
because linear compound 6 which bears no tin moiety did
not afford intramolecular conjugate addition under the
same conditions (Scheme 6).
Bu3SnN moieties have fundamentally higher nucleophi-
licity than ClBu2SnN moieties because of the presence of
the electron-withdrawing Cl substituent in the latter case.
Hence, Bu3SnN moieties worked effectively in the pre-
sented conjugate addition. HMPA also plays an important
role in the conjugate addition besides the chemoselective
reduction of the formyl group in 1, in the generation of
nucleophilic pentacoordinate tin amides D [11]. It is clear
that no intramolecular conjugate addition takes place in
the absence of HMPA, because the ZnCl2-catalyzed
Bu3SnH reduction (Table 2, entry 5) and the subsequent
reaction with BuN@C@O at 60 °C for 2 h gave only the
linear compound 6. As shown in Table 3, various 2-oxaz-
olidones 5 were prepared by Bu3SnH–HMPA. Aliphatic,
allylic, secondary alkyl and aromatic isocyanates were
reactive towards 1a, giving the corresponding 2-oxazoli-
dones 5a–f in good to excellent yields (entries 1–6). Use
of substrates 1c, d having aromatic ketone moieties also
gave 2-oxazolidone 5h and 5i (entries 8 and 9).
The advantage of this method includes the potential to
use other heterocumulenes instead of isocyanates, giving a
variety of heterocycles. Use of phenyl isothiocyanate affor-
ded oxazolidin-2-thione 7 (Scheme 7). In this case, it was
known that tin–oxygen bond should add across the C@S
bond of isothiocyanates to give E because strong affinity
of tin to sulfur atom [16b]. The subsequent intramolecular
conjugate addition occurs from the terminal imino-nitrogen

608
I. Shibata et al. / Journal of Organometallic Chemistry 692 (2007) 604–619
O
HMPA
THF, 60 °C, 2 h
n-C8H17
no cyclization
O
NHnBu
O
6
Scheme 6.
Table 3
Synthesis of 2-oxazolidones (1 mmol of 1, 1 mmol of Bu3SnH–HMPA, 0.8 mmol of isocyanate, 1 mL of THF)
R1
Bu3SnH
HMPA
THF
60 °C, 2 h
R1
CHO
O
R2
R2N C O
H+
N
O
0 °C, 30 min
then 60 °C, 1 h
O
1
O
5
Entry
R1 (1)
R2
Bu
Product and yield (%)
1
2
3
4
5
6
7
8
9
n-C8H17 (1a)
5a
5b
5c
5d
5e
5f
84
73
75
70
87
85
56
38
42
H2C@CHCH2
ClCH2CH2
PhCH2
(CH3)2CH
Ph
Bu
Bu
Bu
Ph(CH2)3 (1b)
Ph (1c)
p-ClC6H4 (1d)
5g
5h
5i
atom. The use of CO2 as a heterocumulene did not afford
cyclic products plausibly because of lower reactivity of
tin–oxygen bond than Sn–N bonds in the conjugate
addition.
diketene occurred at the acyl carbon–oxygen bond [19].
After isomerization to the stable tin enolate H, the intra-
molecular conjugate addition took place.
As shown in Scheme 8, use of diphenylketene afforded
the c-lactone 8 through the intramolecular conjugate addi-
tion of tin enolate F. The conjugate addition occurred
through C-alkylation of tin enolate. This result is in con-
trast to our previous intramolecular reaction with alkyl
halides to cause O-alkylation [18].
Electrophiles other than heterocumulenes were also
applicable (Scheme 9). An electrophilic alkene reacted with
the Sn–O bond of C to give intermediate G, and intramo-
lecular addition proceeded to give cyclic ether 9 in a one-
pot procedure. When C was treated with diketene, the a-
acyl-c-lactone 10 was obtained, so the ring cleavage of
2.3. One-pot synthesis of nitrogen heterocycles initiated by
regio- and diastereoselective carbon–carbon bond formation
Next, a one-pot synthesis of nitrogen heterocyclic com-
pounds was carried out initiated by the allylation of the
formyl group of bifunctional carbonyl compounds 1
[20]. The generated tin–oxygen bonds worked as key
intermediates to prepare various heterocyclic compounds
accompanying chemo-, regio- and diastereoselective car-
bon–carbon bond formation in the side chain moieties.
Allylic tributyltins bear low reactivities toward carbonyl
groups. To achieve effective allylation, representative
Bu3SnH-HMPA
n-C8H17
n-C8H17
(1 mmol)
CHO
OSnBu3
O
60 °C, 2 h
O
C
HMPA
1a (1 mmol)
n-C8H17
n-C8H17
PhN C S
(0.8 mmol)
O
H+
O
O
PhN
N
O
0 °C, 0.5 h
60 °C, 2 h
Ph
S
Bu3Sn
S
7
HMPA
E
76%
Scheme 7.

I. Shibata et al. / Journal of Organometallic Chemistry 692 (2007) 604–619
609
Bu3SnH-HMPA
(1 mmol)
n-C8H17
n-C8H17
CHO
OSnBu3
HMPA
O
O
60 °C, 2 h
C
1a (1 mmol)
n-C8H17
n-C8H17
Ph2C C O
(0.8 mmol)
O
O
Ph
Ph
Ph
-78 °C to rt, 12 h
then H3O+
O
O
Ph
Bu3Sn
O
O
47%
8
HMPA
F
Scheme 8.
n-C8H17
n-C8H17
n-C8H17
CHO
1a
O
O
O
O
NC
NC
Sn
Ph
O
CN
Bu3SnH
HMPA
G
CN
HMPA
60 °C, 2 h
Ph
9
78%
Ph
CN
0 °C, 30 min,
then 60 °C, 1 h
(dr = 40 : 60)
n-C8H17
OSnBu3
HMPA
CN
O
C
0 °C, 30 min,
then 60 °C, 1 h
O
O
O
n-C8H17
n-C8H17
n-C8H17
O
O
Me
O
O
Me
O
O
O
SnO
SnO
HMPA
O
H
O
HMPA
72%
10
Scheme 9.
Lewis acids such as TiCl4 and BF3 Æ OEt2 have been used
as activators of carbonyl substrates [21]. However, these
conventional Lewis acids did not afford chemoselective
allylation of the formyl groups of bifunctional substrates
1 because of their instability to acids. We fortunately
found here that allylic chlorodibutyltin (11) system [22]
effectively reacted with the formyl group of substrate 1
without any strong Lewis acids. The allylation was highly
chemoselective to the formyl group where the enone moi-
ety of 1a did not react at all. As shown in Table 4, after
the allylation, the successive reaction with an isocyanate
followed by heating afforded 4,5-trans-disubstituted-2-
oxazolidinones 12a and 12b selectively (entries 3 and 4).
The chloro substituents on the tin center are essential
because allyltributyltin (11a) was not reactive at all (entry
1). In addition, HMPA is essential to cause the cyclization
to give 12 because only linear adduct 13 was obtained in
the absence of HMPA (entry 2). The reaction course to 12
is explained as shown in the equation of Table 4. After
the chemoselective allylation of the formyl group, the gen-
erated tin–oxygen bond of I reacts with an isocyanate
spontaneously. As a result, an adduct J is formed. The
resulting tin–nitrogen bond successively adds to the enone
moieties of 1 in a fashion of conjugate addition to give
2-oxazolidinones 12 in a one-pot procedure. HMPA plays
an important role for the conjugate addition of the stan-
nylcarbamate J where HMPA coordinates to the tin cen-
ter to form pentacoordinate tin amide species, increasing
their nucleophilicity [11]. The intramolecular conjugate
addition did not take place at all in the absence of
HMPA. The activating effect of HMPA to silicon species
was also discussed [23].
[ClBu2Sn]N– nucleophiles work well here in comparison
with the reaction involving Bu2SnClH-reduction (Scheme
5). The reason is not clear yet, however, allylic substituent
would work well to orientate ClBu2SnN– group causing
cyclization. In the 2-oxazolidinones 12, 4,5-trans-disubsti-
tuted isomers predominated. The trans selectivity is
explained in terms of 1, 3-allylic strain in the intramolecu-
lar addition (Scheme 10).
Next, we applied crotyltin reagents in the initial carbon–
carbon bond formation. Crotylmetalation of the carbonyl
functionality incurs problems of regio- and diastereoselec-
tivities. A chloro substituent on the tin center is easily
introduced by the redistribution of crotyltributyltin (14)
with Bu2SnCl2 (Scheme 11) [24]. The redistribution pro-

610
I. Shibata et al. / Journal of Organometallic Chemistry 692 (2007) 604–619
Table 4
One-pot synthesis of 2-oxazolidinones (1 mmol of 1, 1 mmol of 11, 1 mmol of HMPA, 1 mmol of isocyanate, 1 mL of THF)
Sn
R1
CHO
R2N=C=O
0 °C, 1 h
R1
, HMPA
THF, rt, 20 h
11
OSn
O
1
O
HMPA
I
R1
O
R1
R2
O
O
N
H
O
O
O
R1
N
O
60 °C, 1 h
then H2O
R2
Sn
N
O
R2
O
HMPA
J
12
13
Entry
R1
R2
Ph
Sn (11)
Product and yield (%)
1
2
3
4
n-C8H17 (1a)
Bu3Sn (11a)
Bu2ClSn (11b)
11b
No reaction
13a 99 (without HMPA)
12a 81 (trans:cis = 91:9)
12b 54 (trans:cis = 100:0)
p-ClC6H4 (1d)
Ts
11b
ceeds by the initial formation of chlorodibutyl (1-methylal-
lyl)tin K through the reaction at the terminal c-carbon of
14, and the subsequent isomerization takes place to give
(Z)-crotyldibutylchlorotin L. It has been reported that
(Z)-isomers L are formed irrespective of the starting E/Z-
crotyltin 14 [25]. Generated allylic tins K and L both work
as nucleophiles to aldehydes, and here we controlled the
reaction species by the order of the addition of Bu2SnCl2,
determining a/c regioselectivity of the products.
Initially, crotyltributyltin 14, Bu2SnCl2, HMPA and the
enone 1 were heated in one-portion at 60 °C for 3 h. The
subsequent addition of RN@C@O at 0 °C followed by
heating gave 4,5-trans-substituted 2-oxazolidones 15a–c
which include Z-crotyl and carbonylmethyl substituents
on the rings (Scheme 12).
As shown in Scheme 13, it is considered that the Z-crotyl
substituent in 15 is derived from the in situ generated chloro-
dibutyl(1-methylallyl)tin K which adds to the formyl group
of 1 at the terminal c-carbon. This regioselectivity is con-
firmed by quenching the mixture of the crotylation product
of the carbonyl substrates, where Z-homocrotyl alcohols 16
were obtained. The stereoselectivity of the reactions
between K and 1 is consistent with a six-membered, chair-
like, cyclic transition state in which a-methyl substituent
adopts a pseudo-axial position. The (Z)-preference is
thought to be due to the steric congestion between the
a-methyl group and the tin ligands in the transition state
[26].
On the contrary, when crotyltributyltin 14 and n-
Bu2SnCl2 were preheated at 60 °C for 2 h, the subsequent
R2
O
R2
O
O
N
N
R2
Sn
Sn
O
O
12
O
N
H
H
H
H
R1
SnO
H
H
R1
O
H
H
O
R1
H
trans-isomer
Scheme 10.
Me
Me
Bu3Sn
Me
Bu2ClSn
H
(E)- and (Z)-14
Bu2SnCl
Me
- Bu3SnCl
SnClBu2
H
L
K
+
H
Bu2SnCl2
H
Scheme 11.

I. Shibata et al. / Journal of Organometallic Chemistry 692 (2007) 604–619
611
Me
O
R1
R1
Bu2SnCl2
H
R2N
0 °C, 1 h
C O
HMPA
O
R2
O
1
N
O
60 °C, 0.5 h
THF, 60 °C, 3 h
+
Me
O
Bu3Sn
(Z)-14
R1= n-C8H17
R1= n-C8H17
R1= p-ClC6H4
R2= Ts
R2= nBu
R2= Ts
(1a)
(1a)
(1c)
15a 62% (ds = 100%)
15b 75% (ds = 100%)
15c 70% (ds = 100%)
Scheme 12.
HMPA
O
HMPA
Me
R1
H
g
a
SnClBu2
H
R1
SnClBu2
H
Bu3Sn
O
HMPA
O
- Bu3SnCl
Me
H
O
14
O
K
R1
Me
+
Bu2SnCl2
O
1
Me
HMPA
R2
O
R1
Bu2ClSn
R1
N
HMPA
O
O
R2
H
N
O
SnClBu2
O
R1
O
R2N C
O
O
H
15
O
OH
Me
R1
MeOH
Me
O
Me
16
Scheme 13.
reaction with 1 followed by the addition to an isocyanate
afforded 4,5-trans-disubstituted-2-oxazolidones 17a–c
which include carbonylmethyl- and 1-methylallyl groups
on the ring (Scheme 14).
The regioselectivity to introduce a 1-methylallyl group
on the ring of 17 is derived from the initial reaction of
the in situ generated (Z)-crotyldibutylchlorotin L through
preferential isomerization from K by preheating at 60 °C
for 2 h. In addition, it is noted that high diastereoselectivity
in the side chain, 1-methylallyl substituent, was obtained.
The same diastereoisomers of 17 predominated irre-
spective of the E/Z-stereochemistry of 14. This diastere-
oselectivity is derived from the crotylation step. Thus,
quenching the solution of crotylation of 1 gave the corre-
sponding homoallylic alcohols 18 with high syn selectivi-
ties from both E- and Z-crotyltins 14 (Scheme 15). As
O
Me
R1
Me
R1
H
Bu3Sn
R2N
C
O
THF
O
O
HMPA
1
14
R2
N
O
rt to 60 °C, 1 h
35 °C, 6 h
60 °C, 2 h
O
Bu2SnCl2
R1= n-C8H17
R1= n-C8H17
R1= p-ClC6H4
R2= Ts
R2= nBu
R2= Ts
(E)-2c
17a 96% (ds = 82%)
17b 96% (ds = 82%)
17c 62% (ds = 85%)
(1a)
(1a)
(E)-2c
(Z)-2c
(1d)
Scheme 14.

612
I. Shibata et al. / Journal of Organometallic Chemistry 692 (2007) 604–619
O
OH
n-C8H17
H
n-C8H17
1a
O
HMPA
THF
Bu2SnCl2
Bu3Sn
(E)-14
Me
Me
O
Me
35°C, 6 h
60 °C, 2 h
18a 83% syn: anti= 83 : 17
Cl
O
Cl
OH
H
O
0 °C, 2 h
1d
THF
HMPA
Bu3Sn
(Z)-14
Bu2SnCl2
O
Me
60 °C, 2 h
18b 77% syn: anti= 82 : 18
Scheme 15.
O
R1
O
Me
H
Me
α
O
1
HMPA
γ
Bu2ClSn
35 °C, 6 h
Sn
H
L
HMPA
OH
R1
Bu2ClSn
R1
MeOH
O
O
O
Me
18
Me
HMPA
R2
O
R2N C O
R1
Me
Bu2ClSn N
O
R1
H
O
R2
N
O
O
H
17
O
Me
Scheme 16.
described in Scheme 11, (Z)-crotyltin L is formed by the
redistribution of 14 with Bu2SnCl2 irrespective of the E/
Z-stereochemistry of 14, reacting with the formyl group
of 1 at the terminal c-carbon. As shown in Scheme 16,
the crotylation of the (Z)-isomer L proceeds through a
six-membered chair-like transition state, affording syn
adducts predominantly [27].
a variety of heterocycles was established initiated by
chemoselective reduction of enals 1.
4. Experimental
4.1. Instrumentation
4.1.1. General procedures
3. Conclusion
IR spectra were recorded on a Horiba FT-720 spectrom-
eter. All the 1H and 13C spectra of the products were
recorded with a JEOL JNM-GSX-270 (270 and 67 MHz,
respectively) in deuteriochloroform (CDCl3) containing
0.03% (w/v) of tetramethylsilane. Mass spectra were
recorded on a JEOL JMS-DS-303. Column chromatogra-
phy was performed by using Fuji Davison gel FL-
100DX. Preparative TLC was carried out on Wakogel B-
In conclusion, various 2-monosubstituted pyrroles
could be prepared in a one-pot procedure by the imine-
selective reduction of in situ formed bifunctional sub-
strates bearing imine and enone functionalities. One-pot
synthesis of nitrogen heterocyclic compounds was
initiated by chemoselective allylation of 1. Regio- and dia-
stereoselective carbon–carbon bond formation was estab-
lished in the side chain of the rings. One-pot synthesis of
1
5F silica gel. Yields were determined by H NMR using
internal standards.

I. Shibata et al. / Journal of Organometallic Chemistry 692 (2007) 604–619
613
4.2. Materials
on silica-gel column (FL100-DX (Fuji silysia)). Elution
with hexane removed other unknown by-products and
elution hexane/EtOAc = 7/3 gave 1c as a pure form
(see Scheme 17).
Dibutyltin dihydride was prepared by dibutyltin
dichloride (Bu2SnCl2) with LiAlH4 [28]. Dibutyltin
diiodide (Bu2SnI2) was prepared according to described
method [29]. Dibutyltin halide hydrides (Bu2SnXH) were
synthesized in situ by the redistribution reaction between
Bu2SnH2 and Bu2SnX2 (X=Cl, I) [30]. Allyltributyltin
(11a) was prepared by the reaction of tributyltin chloride
(Bu3SnCl) with the corresponding allylic Grignard
reagents [31]. Allyldibutylchlorotin was synthesized by
the redistribution reaction between Bu2SnCl2 and diallyl-
dibutyltin (11b). THF was freshly distilled from sodium
benzophenone ketyl. Crotyltributyltin (E)-14 [32] and
(Z)-14 [33] were prepared by known methods. For the
preparation of (E)-14, starting substrate, crotyl chloride,
was used as sterically (E)-pure form which was provided
by the reduction of commercially available (E)-crotylal-
dehyde with LiAlH4 and subsequent chlorination of the
(E)-crotyl alcohol with PCl3. Substrates 1a and 1b were
prepared according to reported methods starting from
the alkylation of furan [34]. Substrates 1c, 1d were pre-
pared by our original method via Wittig reaction as
follows.
4.2.1.1. (E)-4-Oxo-4-phenyl-but-2-enal (1c). Colorless
1
wax; IR 1697, 1670 cmÀ1; H NMR (CDCl3) d 6.99 (dd,
J = 7.32 and 15.62 Hz, 1H), 7.53–8.00 (m, 5H), 7.72 (d,
J = 15.62 Hz, 1H), 9.99 (d, J = 7.32 Hz, 1H); 13C NMR
(CDCl3) d 128.86, 129.01, 134.14, 136.24, 139.14, 142.04,
189.75, 192.74; HRMS calcd for C10H8O2 160.054; found
160.0528.
4.3. Typical experimental procedure to prepare pyrrole (2)
To a dry nitrogen-filled 10-mL round-bottomed flask
containing dibutyltin dihydride (Bu2SnH2, 0.166 g,
0.5 mmol) in 1,4-dioxane (1 mL) was added dibutyltin dii-
odide (Bu2SnI2, 0.243 g, 0.5 mmol) and HMPA (0.180 g,
1 mmol) at rt. After stirring at rt for 10 min, the resulting
solution of dibutyliodotin hydride (Bu2SnIH, 1 mmol)
was cooled to 0 °C. Carbonyl substrate 1a (0.196 g,
1 mmol), and p-chloroaniline (0.128 g) were added succes-
sively, and stirring was continued at 0 °C for 2 h. The IR
absorption band of Sn–H (1850 cmÀ1) disappeared, which
indicated the formation of stannylamide(II). The mixture
was heated to 80 °C and stirred for 2 h. The reaction was
quenched by MeOH (0.5 mL), and the residue was chro-
matographed on silica-gel column (FL100-DX (Fuji sily-
sia)). Elution with hexane gave pyrrole 2a (0.234 g, 81%).
4.2.1. Synthesis of (E)-4-oxo-4-phenyl-but-2-enal (1c)
To a dry nitrogen-filled 300-mL round-bottomed flask
containing Ph3P (33.11 g, 126.23 mmol) in CHCl3
(150 mL) was added 2-bromo-propiophenone (25.1 g,
126 mmol) at rt. After stirring at rt for 4 h, 500 mL of
ether was added to form white precipitates. After separa-
tion, the resulting white precipitate was added to 1 L
water containing Na2CO3 (101 g), which was stirred at
rt for 15 h. Ylide was obtained as a white solid which
was filtered and dried. To a dry nitrogen-filled 300-mL
round-bottomed flask containing 40 wt% glyoxal (145 g,
1 mol) in dichloromethane (100 mL) was added a CH2Cl2
solution of the ylide (38.0 g, 100 mmol) dropwise at rt
for 1 h. The solution was stirred overnight at rt and
poured into a mixture of ether and water with vigorous
stirring. The resulting white solid (Ph3PO) was filtered
off. Ether layer was separated, and the aqueous layer
was extracted with ether. The combined ether solution
was dried over MgSO4 and concentrated to give an oil.
Purification was performed by column chromatography
4.3.1. 1-(4-Chlorophenyl)-2-octyl-1H-pyrrole (2a)
Colorless wax; IR 1596, 1496 cmÀ1; 1H NMR (CDCl3) d
0.86 (t, J = 6.83 Hz, 3H), 1.21–1.30 (m, 10H), 1.44–1.55
(m, 2H), 2.49 (t, J = 7.81 Hz, 2H), 6.04–6.06 (m, 1H),
6.21 (t, J = 2.93 Hz, 1H), 6.67–6.69 (m, 1H), 7.22 (d,
J = 8.79 Hz, 2H), 7.39 (d, J = 8.79 Hz, 2H); 13C NMR
(CDCl3) d 14.08, 22.63, 26.65, 29.13, 29.27, 29.30, 31.57,
31.80, 107.10, 108.26, 121.30, 127.30, 129.18, 132.77,
134.21, 139.06; HRMS calcd for C18H24NCl 289.1597;
found 289.1597.
4.3.2. 2-Octyl-1-phenyl-1H-pyrrole (2b)
1
Colorless wax; IR 1516 cmÀ1; H NMR (CDCl3) d 0.86
(t, J = 6.83 Hz, 3H), 1.21–1.30 (m, 10H), 1.45–1.56 (m,
Ph
Ph
Ph
+
Na2CO3
Br-
Br
PPh3
PPh3
O
PPh3
PPh3
+
CHCl3
O
O
O
H
O
Ph
O
Ph
+
H
CH2Cl2
O
O
H
1c
Scheme 17.

614
I. Shibata et al. / Journal of Organometallic Chemistry 692 (2007) 604–619
2H), 2.52 (t, J = 7.81 Hz, 2H), 6.05–6.07 (m, 1H), 6.21 (t,
J = 2.93 Hz, 1H), 6.72–6.73 (m, 1H), 7.27–7.45 (m, 5H);
13C NMR (CDCl3) d 14.03, 22.60, 26.67, 29.11 (d), 29.25,
29.30, 31.79, 106.69, 107.84, 121.34, 126.09, 126.89,
128.93, 134.16, 140.50; HRMS calcd for C18H25N
255.1987; found 255.1993.
0.5 h. The IR absorption band of NCO (2200 cmÀ1) disap-
peared, which indicated the formation of stannylcarbamate
adduct (II). The mixture was heated to 60 °C and stirred
for 1 h. The reaction was quenched by MeOH (0.5 mL),
and the residue was chromatographed on silica-gel column
(FL100-DX (Fuji silysia)). By-products such as organotin
compounds were removed by eluting with hexane. Subse-
quent elution with EtOAc gave 2-oxazolidonone 5a
(0.199 g, 84% based on BuN@C@O).
4.3.3. 2-Octyl-1-p-tolyl-1H-pyrrole (2c)
1
Colorless wax; IR 1520 cmÀ1; H NMR (CDCl3) d 0.86
(t, J = 6.83 Hz, 3H), 1.21–1.30 (m, 10H), 1.45–1.55 (m,
2H), 2.40 (s, 3H), 2.50 (t, J = 7.81 Hz, 2H), 6.03–6.05 (m,
1H), 6.19 (t, J = 2.93 Hz, 1H), 6.69–6.71 (m, 1H), 7.15–
7.24 (m, 4H); 13C NMR (CDCl3) d 14.05, 20.98, 22.62,
26.65, 29.11, 29.14, 29.28, 29.31, 31.81, 106.38, 107.59,
121.40, 125.97, 129.53, 134.28, 136.71, 137.97; HRMS
calcd for C19H27N 269.2144; found 269.2148.
4.4.1. 3-Butyl-4-(2-oxo-decyl)-oxazolidin-2-one (5a)
Colorless wax; IR (neat) 2927, 1751, 1712 cmÀ1 1H
;
NMR (270 MHz, CDCl3, 25 °C) d 0.85–0.96 (m, 6H,
2CH3), 1.21–1.60 (m, 16H, CH2), 2.45 (t, 2H, J = 7.3 Hz,
C@OCH2), 2.61 (dd, 1H, J = 9.3 and 18.1 Hz, one of
C@OCH2), 2.88–2.96 (m, 1H, one of NCH2), 3.01 (dd,
1H, J = 3.9 and 18.1 Hz, one of C@OCH2), 3.37–3.50
(m, 1H, one of NCH2), 3.84 (dd, 1H, J = 5.9 and 8.8 Hz,
one of OCH2), 4.12–4.22 (m, 1H, CHN), 4.52 (dd, 1H,
J = 8.3 and 8.8 Hz, one of CH2O); 13C NMR (67.9 MHz,
CDCl3, 25 °C) d 13.45, 13.83, 19.66, 22.38, 22.39, 28.85,
28.90, 29.08, 29.19, 31.56, 41.61, 43.02, 45.22, 50.64,
67.89, 157.73, 207.93; HRMS calcd for C17H31NO3
297.2304, found 297.2298.
4.3.4. 1-(4-Methoxy-phenyl)-2-octyl-1H-pyrrole (2d)
Colorless wax; IR 1500 cmÀ1 1H NMR (CDCl3) d
;
0.86 (t, J = 6.83 Hz, 3H), 1.21–1.30 (m, 10H), 1.44–1.54
(m, 2H), 2.46 (t, J = 7.81 Hz, 2H), 3.85 (s, 3H), 6.01–
6.03 (m, 1H), 6.18 (t, J = 2.93 Hz, 1H), 6.67–6.69 (m,
1H), 6.92–7.22 (m, 4H); 13C NMR (CDCl3) d 14.06,
22.63, 26.59, 29.14, 29.30, 29.34, 29.68, 31.82, 55.45,
106.11, 107.42, 114.07, 121.57, 127.42, 133.51, 134.54,
158.53; HRMS calcd for C19H27NO 285.2093; found
285.2086.
4.4.2. 3-Allyl-4-(2-oxo-decyl)-oxazolidin-2-one (5b)
Colorless wax; IR (neat) 2927, 1751, 1712 cmÀ1
;
1H
NMR (270 MHz, CDCl3, 25 °C)
d
0.88 (t, 3H,
4.3.5. 1-(4-Chloro-phenyl)-2-(3-phenyl-propyl)-1H-pyrrole
(2e)
J = 6.8 Hz, CH3), 1.11–1.56 (m, 12H, CH2), 2.42 (t, 2H,
J = 7.3 Hz, C@OCH2), 2.58 (dd, 1H, J = 9.8 and
18.1 Hz, one of C@OCH2), 3.01 (dd, 1H, J = 3.9 and
18.1 Hz, one of C@OCH2), 3.63 (dd, 1H, J = 6.8
and 15.6 Hz, one of C@CCH2), 3.87 (dd, 1H, J = 6.3
and 8.8 Hz, one of CH2O), 4.06 (dd, 1H, J = 5.4 and
15.6 Hz, one of C@CCH2), 4.12–4.33 (m, 1H, one of
CH2N), 4.57 (t, 1H, J = 8.8 Hz, one of CH2O), 5.08–5.29
(m, 2H, C@CH2), 5.68–5.85 (m, 1H, CH@CH2); 13C
NMR (67.9 MHz, CDCl3, 25 °C) d 13.78, 22.30, 23.25,
28.77, 28.78, 28.99, 31.47, 42.79, 44.82, 45.10, 50.78,
67.96, 118.12, 132.04, 157.58, 207.79; HRMS calcd for
C16H27NO3 281.1991, found 281.1988.
Colorless wax; IR 1496 cmÀ1; 1H NMR (CDCl3) d 1.75–
1.87 (m, 2H), 2.51–2.59 (m, 4H), 6.06–6.09 (m, 1H), 6.18–
6.21 (m, 1H), 6.66–6.68 (m, 1H), 7.050–7.352 (m, 9H); 13C
NMR (CDCl3) d 26.09, 30.67, 35.29, 107.39, 108.32,
121.46, 125.71, 127.19, 128.25, 128.31, 129.20, 132.76,
133.49, 138.87, 141.86; HRMS calcd for C19H18NCl
295.1128; found 295.1125.
4.3.6. 1-(4-Chloro-phenyl)-2-phenyl-1H-pyrrole (2f)
Colorless wax; IR 1600, 1492 cmÀ1; 1H NMR (CDCl3) d
6.35–6.38 (m, 1H), 6.42–6.44 (m, 1H), 6.90–6.91 (m, 1H),
7.09 (d, J = 8.40 Hz, 2H), 7.13–7.24 (m, 5H), 7.28 (d,
J = 8.40 Hz, 2H); 13C NMR (CDCl3) d 109.60, 110.99,
124.16, 126.49, 126.76, 128.18, 128.32, 129.13, 132.19,
132.59, 133.79, 139.01; HRMS calcd for C16H12NCl
253.0658; found 253.0653.
4.4.3. 3-(2-Chloro-ethyl)-4-(2-oxo-decyl)-oxazolidin-2-one
(5c)
Colorless wax; IR (neat) 2931, 1754, 1712 cmÀ1
;
1H
NMR (270 MHz, CDCl3, 25 °C)
d
0.88 (t, 3H,
J = 6.4 Hz, CH3), 1.22–1.58 (m, 12H, CH2), 2.47 (t, 2H,
J = 7.3 Hz, C@OCH2), 2.69 (dd, 1H, J = 8.8 and
18.1 Hz, one of C@OCH2), 3.13 (dd, 1H, J = 4.4 and
18.1 Hz, one of C@OCH2), 3.30–3.44 (m, 1H, one of
CH2N), 3.64–3.76 (m, 3H, CH2Cl and one of CH2N),
3.91 (dd, 1H, J = 6.3 and 8.8 Hz, one of CH2O), 4.26–
4.39 (m, 1H, CHN), 4.58 (t, 1H, J = 8.8 Hz, one of
CH2O); 13C NMR (67.9 MHz, CDCl3, 25 °C) d 13.91,
22.45, 23.46, 28.92, 28.96, 29.13, 31.62, 41.31, 43.05,
44.15, 45.59, 51.64, 68.31, 157.47, 207.91; HRMS calcd
for C15H26ClNO3 303.1601, found 303.1609.
4.4. Representative procedure for the preparation of
2-oxazolidinone initiated by chemoselective reduction
To a dry nitrogen-filled 10-mL round-bottomed flask
containing triibutyltin hydride (0.291 g, 1 mmol) in THF
(1 mL) was added and HMPA (0.180 g, 1 mmol) at rt. To
the resulting solution was added carbonyl substrate (1a)
(0.196 g, 1 mmol), and stirred at 60 °C for 2 h. The reaction
mixture was cooled to 0 °C. To this mixture was added
butyl isocyanate (0.0975 g, 0.8 mmol) and stirred for

I. Shibata et al. / Journal of Organometallic Chemistry 692 (2007) 604–619
615
4.4.4. 3-Benzyl-4-(2-oxo-decyl)-oxazolidin-2-one (5d)
Colorless wax; IR (neat) 2927, 1758, 1712 cmÀ1 1H
;
Ph); 13C NMR (67.9 MHz, CDCl3, 25 °C) d 13.50, 19.62,
24.60, 29.14, 34.70, 41.56, 42.02, 45.21, 50.52, 67.87,
125.76, 128.45, 128.58, 140.90, 157.75, 207.48; HRMS
calcd for C18H25NO3 303.1834, found 303.1834.
NMR (270 MHz, CDCl3, 25 °C)
d
0.88 (t, 3H,
J = 6.8 Hz, CH3), 1.08–1.48 (m, 12H, CH2), 2.24 (t, 2H,
J = 8.3 Hz, C@OCH2), 2.50 (dd, 1H, J = 9.3 and
18.1 Hz, one of C@OCH2), 2.87 (dd, 1H, J = 3.9 and
18.1 Hz, one of C@OCH2), 3.87 (dd, 1H, J = 6.6 and
8.6 Hz, one of CH2O), 3.97–4.11 (m, 1H, CHN), 4.21 (d,
1H, J = 15.7 Hz, one of CH2Ph), 4.54 (t, 1H, J = 8.6 Hz,
one of CH2O), 4.21 (d, 1H, J = 15.7 Hz, one of CH2Ph),
7.20–7.83 (m, 5H, Ph); 13C NMR (67.9 MHz, CDCl3,
25 °C) d 13.99, 22.53, 23.41, 28.94, 29.18, 29.29, 31.67,
42.97, 45.33, 46.49, 50.82, 68.16, 127.77, 127.92, 127.77,
128.78, 158.31, 207.84; HRMS calcd for C20H29NO3
331.2147, found 331.2136.
4.4.8. 3-Butyl-4-(2-oxo-2-phenyl-ethyl)-oxazolidin-2-one
(5h)
Colorless wax; IR (neat) 2958, 1747, 1678 cmÀ1
;
1H
NMR (270 MHz, CDCl3, 25 °C)
d
0.93 (t, 3H,
J = 7.3 Hz, CH3), 1.26–1.61 (m, 4H, CH2), 2.96–3.06 (m,
1H, one of NCH2), 3.14 (dd, 1H, J = 9.3 and 17.6 Hz,
one of C@OCH2), 3.45–3.55 (m, 1H, one of NCH2), 3.55
(dd, 1H, J = 3.9 and 17.6 Hz, one of C@OCH2), 3.95
(dd, 1H, J = 5.9 and 8.8 Hz, one of OCH2), 4.32–4.43
(m, 1H, CHN), 4.63 (t, 1H, J = 8.8 Hz, one of OCH2),
7.49–7.94 (m, 5H, Ph); 13C NMR (67.9 MHz, CDCl3,
25 °C) d 13.64, 19.80, 29.34, 41.51, 41.81, 51.22, 68.23,
127.91, 128.81, 133.93, 137.22, 157.95, 196.93; HRMS
calcd for C15H19NO3 261.1365, found 261.1368.
4.4.5. 3-Isopropyl-4-(2-oxo-decyl)-oxazolidin-2-one (5e)
Colorless wax; IR (neat) 2927, 1751, 1712 cmÀ1 1H
;
NMR (270 MHz, CDCl3, 25 °C)
d
0.81 (t, 3H,
J = 6.8 Hz, CH3), 1.03–1.29 (m, 18H, CH2 and
CH(CH3)2), 2.37 (t, 2H, J = 7.3 Hz, C@OCH2), 2.65 (dd,
1H, J = 10.3 and 18.6 Hz, one of C@OCH2), 2.92 (dd,
1H, J = 3.4 and 18.6 Hz, one of C@OCH2), 3.71–3.85
(m, 2H, one of CH2O and CHMe2), 4.10–4.19 (m, 1H,
CHN), 4.41 (t, 1H, J = 8.8 Hz, one of CH2O); 13C NMR
(67.9 MHz, CDCl3, 25 °C) d 13.99, 19.19, 21.32, 22.52,
23.51, 28.98, 29.01, 29.19, 31.67, 43.21, 45.85, 47.31,
50.32, 68.35, 157.29, 208.33; HRMS calcd for C16H29NO3
283.2147, found 283.2136.
4.4.9. 3-Butyl-4-[2-(4-chloro-phenyl)-2-oxo-ethyl]-
oxazolidin-2-one (5i)
Colorless wax; IR (neat) 2958, 1747, 1681 cmÀ1
;
1H
NMR (270 MHz, CDCl3, 25 °C)
d
0.94 (t, 3H,
J = 7.3 Hz, CH3), 1.22–1.61 (m, 4H, 2CH2), 2.94–3.05
(m, 1H, one of NCH2), 3.13 (dd, 1H, J = 9.3 and
18.1 Hz, one of C@OCH2), 3.46–3.57 (m, 1H, one of
NCH2), 3.52 (dd, 1H, J = 3.4 and 18.1 Hz, one of
C@OCH2), 3.95 (dd, 1H, J = 5.4 and 8.8 Hz, one of
OCH2), 4.33–4.42 (m, 1H, CHN), 4.63 (t, 1H, J = 8.8 Hz,
one of OCH2), 7.47 (d, 2H, J = 8.3 Hz, arom), 7.90 (d,
2H, J = 8.3 Hz, arom); 13C NMR (67.9 MHz, CDCl3,
25 °C) d 13.63, 19.81, 29.34, 41.47, 41.81, 51.13, 68.14,
129.17, 129.33, 134.21, 140.47, 157.89, 195.74; HRMS
calcd for C15H18ClNO3 295.0975, found 295.0976.
4.4.6. 3-(4-Phenyl)-4-(2-oxo-decyl)-oxazolidin-2-one (5f)
Colorless wax; IR (neat) 2927, 1758, 1709, 755 cmÀ1; 1H
NMR (270 MHz, CDCl3, 25 °C) d 0.87 (t, 3H, J = 6.8 Hz,
CH3), 1.17–1.55 (m, 12H, CH2), 2.32 (t, 2H, J = 7.3 Hz,
C@OCH2), 2.65 (dd, 1H, J = 9.8 and 18.1 Hz, one
of C@OCH2), 2.97 (dd, 1H, J = 2.9 and 18.1 Hz, one of
C@OCH2), 4.01 (dd, 1H, J = 5.4 and 8.8 Hz, one of
CH2O), 4.67 (dd, 1H, J = 8.3 and 8.8 Hz, one of CH2O),
4.75–4.85 (m, 1H, CHN), 7.14–7.41 (m, 5H, arom); 13C
NMR (67.9 MHz, CDCl3, 25 °C) d 13.81, 22.34, 23.26,
28.80(d), 28.99, 31.50, 42.87, 44.68, 52.16, 67.67, 121.68,
125.22, 129.06, 136.05, 155.29, 208.13; HRMS calcd for
C21H27NO3 317.1991, found 317.1991.
4.4.10. 1-(3-Phenyl-2-thioxo-oxazolidin-4-yl)-decan-2-one
(7)
1
Mp 80 °C; IR (neat) 2927, 1743, 1700 cmÀ1; H NMR
(270 MHz, CDCl3, 25 °C) d 0.87 (t, 3H, J = 7.3 Hz,
CH3), 1.16–1.53 (m, 12H, CH2), 2.20–2.40 (m, 2H,
C@OCH2), 2.71 (dd, 1H, J = 9.8 and 18.1 Hz, one of
C@OCH2), 2.85 (dd, 1H, J = 3.4 and 18.1 Hz, one
of C@OCH2), 4.24 (dd, 1H, J = 6.8 and 9.3 Hz, one of
CH2O), 4.73–4.85 (m, 1H, CHN), 5.01 (t, 1H, J = 9.3 Hz,
one of CH2O), 7.14–7.55 (m, 5H, arom); 13C NMR
(67.9 MHz, CDCl3, 25 °C) d 14.05, 22.56, 23.41, 28.99(d),
29.19, 31.71, 43.00, 45.51, 58.56, 72.91, 121.91, 128.54,
129.62, 136.85, 187.70, 207.51; HRMS calcd for
C19H27NOsS 333.1762, found 333.1755. Anal. Calc. for
C19H27NOsS: C, 68.43; H, 8.16; N, 4.20. Found: C,
68.20; H, 7.96; N, 4.14.
4.4.7. 3-Butyl-4-(2-oxo-5-phenylpentyl)-oxazolidin-2-one
(5g)
Colorless wax; IR (neat) 2931, 1751, 1712 cmÀ1
;
1H
NMR (270 MHz, CDCl3, 25 °C)
d
0.92 (t, 3H,
J = 7.2 Hz, CH3), 1.24–1.38 (m, 2H, CH2), 1.41–1.54 (m,
2H, CH2), 1.91 (tt, 2H, J = 7.3 and 7.4 Hz, CH2CH2Ph),
2.43 (t, 2H, J = 7.3 Hz, C@OCH2CH2), 2.53 (dd, 1H,
J = 9.4 and 18.8 Hz, one of C@OCH2), 2.61 (t, 2H,
J = 7.4 Hz, PhCH2), 2.88 (m, 1H, one of NCH2), 2.90
(dd, 1H, J = 3.9 and 18.8 Hz, one of C@OCH2), 3.37–
3.45 (m, 1H, one of NCH2), 3.78 (dd, 1H, J = 6.0 and
8.9 Hz, one of OCH2), 4.06–4.16 (m, 1H, CHN), 4.48 (t,
1H, J = 8.9 and 8.9 Hz, one of CH2O); 7.12–7.31 (m, 5H,
4.4.11. 4-(2-Oxo-decyl)-3,3-diphenyl-dihydro-furan-2-one
(8)
Bp 190 °C/0.1 mmHg; IR (neat) 2923, 1778, 1712 cmÀ1
;
1H NMR (270 MHz, CDCl3, 25 °C) d 0.87 (t, 3H,

616
I. Shibata et al. / Journal of Organometallic Chemistry 692 (2007) 604–619
J = 6.9 Hz, CH3), 1.16–1.52 (m, 12H, CH2), 2.04 (dd, 1H,
J = 10.4 and 18.3 Hz, one of C@OCH2), 2.24 (t, 2H,
J = 7.4 Hz, C@OCH2), 2.48 (dd, 1H, J = 3.5 and 18.3 Hz,
one of C@OCH2), 3.84–3.92 (m, 2H, one of CH2O and
CHN), 4.66 (dd, 1H, J = 5.9 and 8.4 Hz, one of CH2O),
7.05–7.50 (m, 10H, Ph); 13C NMR (67.9 MHz, CDCl3,
25 °C) d 14.07, 22.60, 23.53, 29.03, 29.11, 29.24, 31.78,
38.44, 42.58, 43.14, 58.59, 69.83, 127.42, 127.90, 128.10,
128.45, 128.56, 128.62, 138.72, 139.18, 177.11, 208.63;
HRMS calcd for C26H32O3 392.2351, found 392.2356.
with EtOAc gave 2-oxazolidonone (12a) (0.273 g, 81%).
The stereochemistry of the major diastereoisomer of 12a
was determined by NOE. As for product 12b, the structure
was indicated by X-ray analysis.
4.5.1. 5-Allyl-4-(2-oxo-decyl)-3-phenyl-oxazolidin-2-one
(12a)
Bp 135 °C/0.1 mmHg; IR (neat) 2927, 1758, 1712,
759 cmÀ1 1H NMR (CDCl3) d 0.90 (t, 3H, J = 6.4 Hz,
;
CH3), 1.28–1.57 (m, 12H, CH2), 2.34 (t, 2H, J = 7.3 Hz,
C@OCH2), 2.55–2.70 (m, 2H, CH2C@C), 2.73 (dd, 1H,
J = 9.8 and 18.1 Hz, one of C@OCH2), 2.92 (dd, 1H,
J = 3.0 and 18.1 Hz, one of C@OCH2), 4.30 (ddd,
J = 3.0, 3.2 and 9.0 Hz, 1H, CHO), 4.55 (ddd, 1H,
J = 3.0, 3.2 and 9.8 Hz, CHN), 5.20–5.33 (m, 2H, allyl
C@CH2), 5.81–5.96 (m, 1H, allyl CH@C), 7.15–7.46 (m,
5H, arom); 13C NMR (CDCl3) d 14.07, 22.61, 23.48,
29.04(d), 29.25, 31.74, 38.77, 43.39, 44.70, 56.16, 78.51,
119.87, 121.40, 125.28, 129.36, 131.09, 136.22, 154.62,
208.57; HRMS calcd for C22H31NO3 357.2304, found
357.2309 (see Scheme 18).
4.4.12. 4-(2-Oxo-decyl)-2-phenyl-dihydrofuran-3,3-
dicarbonitrile (9)
(Major isomer) colorless wax; IR (neat) 2923, 1708 cmÀ1
;
1H NMR (270 MHz, CDCl3, 25 °C) d 0.88 (t, 3H,
J = 6.8 Hz, CH3), 1.18–1.62 (m, 12H, CH2), 2.45–2.53 (m,
2H, C@OCH2), 2.87 (dd, 1H, J = 9.3 and 18.1 Hz, one of
C@OCH2), 3.15 (dd, 1H, J = 3.5 and 18.1 Hz, one of
C@OCH2), 3.39–3.48 (m, 1H, CCH), 3.85 (dd, 1H, J = 8.3
and 9.3 Hz, one of CH2O), 4.54 (t, 1H, J = 9.3 Hz, one of
CH2O), 5.18 (s, 1H, CH), 7.38–7.54 (m, 5H, Ph); 13C
NMR (67.9 MHz, CDCl3, 25 °C) d 14.00, 22.53, 23.57,
29.01 (d), 29.19, 31.68, 42.67, 43.13, 45.29, 46.91, 71.68,
86.55, 113.21, 126.06, 128.72, 129.98, 132.79, 206.95; HRMS
calcd for C22H28N2O2 352.2151, found 352.2145.
4.5.2. 5-Allyl-4-[2-(4-chloro-phenyl)-2-oxo-ethyl]-3-
(toluene-4-sulfonyl)-oxazolidin-2-one (12b)
Mp 183 °C; IR (neat) 3070, 1778, 1677, 1168, 663 cmÀ1
;
1H NMR (CDCl3) d 2.47 (s, 3H, CH3), 2.44–2.51 (m, 2H,
C@CCH2), 3.47 (dd, 1H, J = 10.3 and 18.1 Hz, one of
C@OCH2), 3.96 (dd, 1H, J = 2.4 and 18.1 Hz, one of
C@OCH2), 4.34 (td, 1H, J = 2.4 and 4.9 Hz, 1H, CHO),
4.57 (td, 1H, J = 2.4 and 10.3 Hz, 1H, CHN), 4.92–5.16
(m, 2H, allyl C@CH2), 5.45–5.60 (m, 1H, allyl CH@C),
7.38 (d, 2H, J = 8.3 Hz, arom), 7.49 (d, 2H, J = 8.3 Hz,
arom), 7.89 (d, 2H, J = 8.3 Hz, arom), 7.94 (d, 2H,
J = 8.3 Hz, arom); 13C NMR (CDCl3) d 21.74, 38.25,
43.72, 57.09, 79.72, 120.76, 123.37, 129.26, 129.44,
129.65, 129.81, 134.01, 134.57, 140.67, 145.86, 151.36,
195.77; HRMS calcd for C21H20ClNO5S 433.0751, found
(CI) 434.0834. Anal. Calc. for C21H20ClNO5S: C, 58.13;
H, 4.65; N, 3.23. Found: C, 58.16; H, 4.68; N, 3.22.
4.4.13. 3-Acetyl-4-(2-oxo-decyl)-dihydro-furan-2-one (10)
Colorless wax; IR (neat) 1774, 1716, 1643 cmÀ1 1H
;
NMR (270 MHz, CDCl3, 25 °C) d 0.88 (t, 3H, J = 6.8 Hz,
CH3), 1.18–1.60 (m, 12H, CH2), 2.28 (s, 3H, C@OCH3),
2.34–2.79 (m, 4H, C@OCH2), 3.26–3.40 (m, 1H, ring
CH), 3.48 (d, 1H, J = 7.8 Hz, CHAc), 3.91 (t, 1H,
J = 8.5 Hz, one of CH2O), 4.61 (t, 1H, J = 8.5 Hz, one of
CH2O); 13C NMR (67.9 MHz, CDCl3, 25 °C) d 13.91,
22.47, 23.51, 28.93, 28.98, 29.14, 29.48, 31.62, 32.77,
42.73, 44.32, 58.08. 71.59, 171.89, 200.05, 208.51; HRMS
calcd for C16H26O4 282.1831, found 282.1823.
4.5. Representative procedure for the preparation
of 2-oxazolidinone initiated by allylation
4.6. Representative procedure for the preparation of
2-oxazolidinone (15c) initiated by crotylation
To a dry nitrogen-filled 10-mL round-bottomed flask
containing diallyldibutyltin (0.166 g, 0.5 mmol) in THF
(1 mL) was added dibutyltin dichloride (0.151 g, 0.5 mmol)
and HMPA (0.180 g, 1 mmol) at rt. After stirring at rt for
10 min, to the resulting solution of allyldibutylchlorotin
(11b) (1 mmol) was added carbonyl substrate (1a)
(0.196 g, 1 mmol), and stirred at rt for 20 h. The reaction
mixture was cooled to 0 °C. To this mixture was added
phenyl isocyanate (0.119 g, 1 mmol) and stirred for 1 h.
The IR absorption band of NCO (2200 cmÀ1) disappeared,
which indicated the formation of stannylcarbamate adduct
J. The mixture was heated to 60 °C and stirred for 1 h. The
reaction was quenched by MeOH (0.5 mL), and the residue
was chromatographed on silica-gel column (FL100-DX
(Fuji silysia)). By-products such as organotin compounds
were removed by eluting with hexane. Subsequent elution
To a dry nitrogen-filled 10 mL round-bottomed flask
containing crotyltributyltin (Z)-14 (0.345 g, 1 mmol), car-
nOe study of 12a
O
2.9%
Ph
Ha
O
Ha
O
N
Hc
Oct
H
2.61%Hb
Hd He
8.35%
Scheme 18.

I. Shibata et al. / Journal of Organometallic Chemistry 692 (2007) 604–619
617
bonyl substrate (1b) (0.195 g, 1 mmol) in THF (1 mL) were
4.6.3. 5-But-2-enyl-4-[2-(4-chloro-phenyl)-2-oxo-ethyl]-3-
(toluene-4-sulfonyl)-oxazolidin-2-one (15c)
added dibutyltin dichloride (Bu2SnCl2) (0.303 g, 1 mmol)
and HMPA (0.180 g, 1 mmol) at rt. After stirring at
60 °C for 3 h, the reaction mixture was cooled to 0 °C.
To this mixture was added tosyl isocyanate (0.197 g,
1 mmol) and stirred for 1 h. IR absorption band of NCO
(2200 cmÀ1) had disappeared, which indicated the forma-
tion of stannylcarbamate adduct. The mixture was warmed
to 60 °C and stirred for 0.5 h. The reaction was quenched
by MeOH (0.5 mL), and the residue was chromatographed
on silica-gel column (FL100-DX (Fuji silysia)). By-prod-
ucts such as organotin compounds were removed by elut-
ing with hexane. Subsequent elusion with EtOAc gave 5-
(Z)-crotyl substituted 2-oxazolidonone 15c (0.312 g,
70%). Further purification of 15c was performed by recrys-
tallization. The structure of crystalline product 15c was
indicated by X-ray analysis. Conjugate addition using
other substrates were performed in a similar manner. Spec-
tral data of products obtained are listed from the following
pages.
Mp 160 °C; IR (neat) 3023, 1774, 1673, 1168, 810 cmÀ1
;
1H NMR (CDCl3) d 1.57 (d, 3H, J = 6.8 Hz, C@CCH3),
2.47 (s, 3H, CH3), 2.47–2.52 (m, 2H, CH2), 3.47 (dd, 1H,
J = 10.7 and 18.1 Hz, one of C@OCH2), 3.97 (dd, 1H,
J = 3.0 and 18.1 Hz, one of C@OCH2), 4.34 (td, 1H,
J = 3.0 and 7.8 Hz, CHO), 4.53 (td, 1H, J = 3.0 and
10.7 Hz, CHN), 5.07–5.17 (m, 1H, C@CH), 5.32–5.44 (m,
1H, CH@C), 7.37 (d, 2H, J = 8.3 Hz, arom), 7.48 (d, 2H,
J = 8.3 Hz, arom), 7.90 (d, 2H, J = 8.3 Hz, arom), 7.93 (d,
2H, J = 8.3 Hz, arom); 13C NMR (CDCl3) d 13.01, 21.72,
31.24, 43.87, 57.21, 80.30, 120.82, 128.33, 129.21, 129.44,
129.75, 129.91, 134.04, 134.62, 140.60, 145.79, 151.38,
195.82; HRMS calcd for C22H22ClNO5S 447.0907, found
(CI) 448.0985; Anal. Calc. for C22H22ClNO5S: C, 58.99;
H, 4.95; N, 3.13. Found: C, 58.79; H, 4.92; N, 3.19.
4.7. Representative procedure for the preparation of
2-oxazolidinone (17c) initiated by 1-methylallylation
4.6.1. 5-But-2-enyl-4-(2-oxo-decyl)-3-(toluene-4-sulfonyl)-
oxazolidin-2-one (15a)
To a dry nitrogen-filled 10-mL round-bottomed flask
containing crotylbutyltin (Z)-12c (0.345 g, 1 mmol) in
THF (1 mL) was added dibutyltin dichloride (Bu2SnCl2)
(0.303 g, 1 mmol) at rt. After stirring at 60 °C for 2 h, the
reaction mixture was cooled to rt (35 °C) and carbonyl sub-
strate (1b) (0.195 g, 1 mmol) and HMPA (0.180 g, 1 mmol)
were added. To this mixture was added tosyl isocyanate
(0.197 g, 1 mmol). The IR absorption band of NCO
(2200 cmÀ1) disappeared, which indicated the formation of
stannylcarbamate adduct. The mixture was warmed to
60 °C and stirring was continued for 1 h. The reaction was
quenched by MeOH, and the residue was chromatographed
on silica-gel column (FL100-DX (Fuji silysia)). Removal of
by-products such as organotin compounds was performed
by eluting with hexane. Subsequent elution with EtOAc gave
2-oxazolidonone 17c (0.277 g, 62%). Diastereomer ratio was
Bp 150 °C/0.1 mmHg; IR (neat) 2927, 1785, 1712, 1173,
1
759 cmÀ1; H NMR (CDCl3) d 0.88 (t, 3H, J = 6.8 Hz,
CH3), 1.23–2.53 (m, 12H, CH2), 1.56 (d, 1H, J = 6.9 Hz,
CH3), 2.46 (s, 3H, arom-CH3), 2.35–2.52 (m, 4H, C@CCH2
and C@OCH2C7), 2.93 (dd, 1H, J = 10.4 and 18.3 Hz, one
of C@OCH2), 3.41 (dd, 1H, J = 3.0 and 18.3 Hz, one of
C@OCH2), 4.22 (td, 1H, J = 4.9 and 3.0 Hz, CHO), 4.34
(td, 1H, J = 3.0 and 10.4 Hz, CHN), 5.06–5.16 (m, 1H,
C@CH), 5.34–5.46 (m, 1H, CH@C), 7.36 (d, 2H,
J = 8.3 Hz, arom), 7.91 (d, 2H, J = 8.3 Hz, arom); 13C
NMR (CDCl3) d 12.99, 14.07, 21.67, 22.60, 23.48, 29.05,
29.05, 29.27, 31.16, 31.75, 43.04, 47.35, 56.76, 80.32,
120.89, 128.30, 129.72, 129.79, 134.65, 145.69, 151.41,
208.32; HRMS calcd for C24H35NO5S 449.2236, found
449.2240. Anal. Calc. for C24H35NO5S: C, 64.11; H, 7.85;
N, 3.12. Found: C, 64.31; H, 7.7, N, 3.02.
1
determined by H NMR. Further purification of the main
diastereo isomer of 17 c was performed by recrystallization.
The structure of the crystalline product was indicated by X-
ray analysis. Conjugate 1-methylallylation using other sub-
strates was performed in a similar manner. Spectral data of
products obtained are listed in the following pages.
4.6.2. 5-But-2-enyl-3-butyl-4-(2-oxo-decyl)-oxazolidin-2-
one (15b)
Colorless wax; IR (neat) 2958, 1751, 1712, 1427 cmÀ1
;
1H NMR (CDCl3) d 0.88 (t, 3H, J = 6.8 Hz, CH3), 0.93
(t, 3H, J = 6.8 Hz, CH3), 1.23–1.58 (m, 16H, CH2), 1.67
(d, 3H, J = 6.8 Hz, CH3), 2.43 (t, 2H, J = 7.3 Hz,
C7CH2C@O), 2.49–2.54 (m, 2H, C@CCH2), 2.60 (dd, 1H,
J = 8.8 and 18.1 Hz, one of C@OCH2), 2.79–2.87 (m,
1H, one of NCH2), 2.87 (dd, 1H, J = 5.0 and 18.1 Hz,
one of C@OCH2), 3.40–3.55 (m, 1H, one of NCH2), 3.86
(ddd, 1H, J = 5.0, 5.6 and 8.8 Hz, CHN), 4.10 (td,
J = 3.4 and 5.6 Hz 1H, CHO), 5.38–5.50 (m, 1H, C@CH),
5.62–5.75 (m, 1H, CH@C); 13C NMR (CDCl3) d 13.11,
13.70, 14.08, 19.88, 22.62, 23.58, 29.08, 29.11, 29.30,
29.39, 31.71, 31.77, 41.60, 43.55, 45.36, 54.58, 79.17,
122.80, 128.49, 157.18, 208.32; HRMS calcd for
C21H37NO3 351.2773, found 351.2764.
4.7.1. 5-(1-Methyl-allyl)-4-(2-oxo-decyl)-3-(toluene-4-
sulfonyl)-oxazolidin-2-one (17a)
Mp 160 °C; IR (neat) 2927, 1786, 1712, 1172, 667 cmÀ1
;
1H NMR (CDCl3) major isomer d 0.88 (t, 3H, J = 6.9 Hz,
CH3), 0.94 (d, 3H, J = 6.9 Hz, CH3), 1.24–1.61 (m, 12H,
CH2), 2.46 (s, 3H, CH3), 2.33–2.51 (m, 3H, CHMe and
C7CH2C@O), 2.95 (dd, 1H, J = 8.9 and 17.8 Hz, one of
C@OCH2), 3.28 (dd, 1H, J = 3.0 and 17.8 Hz, one of
C@OCH2), 4.07 (dd, 1H, J = 3.0 and 5.5 Hz, CHO), 4.45
(td, 1H, J = 3.0 and 8.9 Hz, CHN), 4.92–5.06 (m, 2H, allyl
C@CH2), 5.54 (ddd, 1H, J = 7.8, 10.4, and 16.8 Hz, allyl
C@CH), 7.37 (d, 2H, J = 8.3 Hz, arom), 7.90 (d, 2H,
J = 8.3 Hz, arom); 13C NMR (CDCl3) d 14.02, 14.05,

618
I. Shibata et al. / Journal of Organometallic Chemistry 692 (2007) 604–619
(e) M. Pereyre, P.J. Quintard, A. Rahm, in: Tin in Organic Synthesis,
Butterworth, London, 1987.
[2] I. Shibata, A. Baba, Curr. Org. Chem. 6 (2002) 665.
[3] E.W. Abel, D.A. Armitage, D.B. Brady, Trans. Faraday Soc. 62
(1966) 3459.
21.68, 22.60, 23.40, 29.03, 29.04, 29.27, 31.75, 41.91, 43.17,
46.89, 55.24, 83.05, 117.71, 128.27, 129.62, 134.69, 136.67,
145.72, 151.39, 207.70; HRMS calcd for C24H35NO5S
449.2236, found 449.0985.
[4] I. Shibata, T. Moriuchi-Kawakami, D. Tanizawa, T. Suwa
E. Sugiyama, H. Matsuda, A. Baba, J. Org. Chem. 63 (1998)
383.
[5] T. Suwa, E. Sugiyama, I. Shibata, A. Baba, Synlett (2000) 556.
[6] For example, see: C.-F. Lee, L.-M. Yang, T.-Y. Hwu, A.-S. Feng
J.-C. Tseng, T.-Y. Luh, J. Am. Chem. Soc. 122 (2000) 4992, and
references therein.
4.7.2. 3-Butyl-5-(1-methyl-allyl)-4-(2-oxo-decyl)-
oxazolidin-2-one (17b)
Colorless wax; IR (neat) 2927, 1780, 1712, 1172,
1
732 cmÀ1; H NMR (CDCl3) major isomer d 0.88 (t, 3H,
J = 6.8 Hz, CH3), 0.93 (t, 3H, J = 7.3 Hz, CH3), 1.10 (d,
3H, J = 6.8 Hz, CH3), 1.24–1.65 (m, 16H, CH2), 2.43 (t,
2H, J = 7.3 Hz, C@OCH2C7), 2.41–2.53 (m, 1H, CHMe),
2.59 (dd, 1H, J = 7.3 and 18.1 Hz, one of C@OCH2),
2.76–2.83 (m, 1H, one of NCH2), 2.81 (dd, 1H, J = 4.9
and 18.1 Hz, one of C@OCH2), 3.41–3.51 (m, 1H, one of
NCH2), 3.90–3.94 (m, 1H), 3.96–4.02 (m, 1H), 5.07–5.23
(m, 2H, allyl C@CH2), 5.67–5.80 (m, 1H, allyl CH@C);
13C NMR (CDCl3) d 13.68, 14.06, 14.60, 19.90, 22.60,
23.61, 29.07(d), 29.28, 29.37, 31.76, 41.73, 42.15, 43.61,
45.75, 53.04, 82.10, 116.96, 137.91, 157.21, 207.95; HRMS
calcd for C21H37NO3 351.2773, found 351.2772.
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4.7.3. 4-[2-(4-Chloro-phenyl)-2-oxo-ethyl]-5-(1-methyl-
allyl)-3-(toluene-4-sulfonyl)-oxazolidin-2-one (17c)
Mp 139 °C; IR (neat) 2977, 1774, 1681, 1365, 667 cmÀ1
;
1H NMR (CDCl3) major isomer d 0.96 (d, 3H, J = 6.8 Hz,
CH3), 2.35–2.42 (m, 1H, CHMe), 2.46 (s, 3H, CH3), 3.48
(dd, 1H, J = 9.8 and 17.6 Hz, one of C@OCH2), 3.83
(dd, 1H, J = 3.0 and 17.6 Hz, one of C@OCH2), 4.18
(dd, 1H, J = 2.4 and 5.9 Hz, CHO), 4.61 (td, 1H, J = 3.0
and 9.8 Hz, CHN), 4.90–5.06 (m, 2H, arom C@CH2),
5.51–5.64 (m, 1H, arom CH@C), 7.35 (d, 2H, J = 8.3 Hz,
arom), 7.48 (d, 2H, J = 8.3 Hz, arom), 7.89 (d, 2H,
J = 8.3 Hz, arom), 7.93 (d, 2H, J = 8.3 Hz, arom); 13C
NMR (CDCl3) d 13.85, 21.54, 41.80, 42.99, 55.52, 82.70,
117.63, 128.05, 128.95, 129.35, 129.65, 134.04, 134.54,
136.50, 140.18, 145.64, 151.29, 195.17; HRMS calcd for
C22H22ClNO5S 447.0907, found (CI) 448.0988; Anal. Calc.
for C22H22ClNO5S: C, 58.99; H, 4.95; N, 3.13. Found: C,
58.78; H, 4.89; N, 3.11.
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Acknowledgments
This work was supported by Grant-in-Aid for Scientific
Research on Priority Areas (No. 14078101, ‘‘Reaction
Control of Dynamic Complexes’’) from Ministry of Educa-
tion, Culture, Sports, Science and Technology, Japan, and
The Sumitomo Foundation (050932).
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