3-Bromopropenyl methyl carbonate: A new reagent for the α-hydroxy allylation reaction of aldehydes in water

Article abstract of DOI:10.1055/s-2005-872144

3-Bromopropenyl methyl carbonate reacts smoothly with aldehydes in the presence of zinc in a mixture of saturated aqueous NH₄Cl and THF (9:1). Monoprotected alk-1-en-3,4-diols are formed in high yields and in short reaction times. The reaction

Full text of DOI:10.1055/s-2005-872144

SPECIAL TOPIC
2609
3-Bromopropenyl Methyl Carbonate: A New Reagent for the a-Hydroxy
Allylation Reaction of Aldehydes in Water
a
M
-Hydroxy
A
llylation
a
r
A
ldehyd
c
es in Wate
o
r
Lombardo,* Filippo Pasi, Caterina Tiberi, Claudio Trombini*
Dipartimento di Chimica ‘G. Ciamician’, Università di Bologna, via Selmi 2, 40126 Bologna, Italy
Fax +39(051)2099456; E-mail: marco.lombardo@unibo.it ; E-mail: claudio.trombini@unibo.it
Received 13 June 2005
while aromatic or a,b-unsaturated aldehydes led to syn-
adducts.
Abstract: 3-Bromopropenyl methyl carbonate reacts smoothly
with aldehydes in the presence of zinc in a mixture of saturated
aqueous NH Cl and THF (9:1). Monoprotected alk-1-en-3,4-diols
4
are formed in high yields and in short reaction times. The reaction
is diastereoselective, saturated aldehydes afford anti-adducts, while
a,b-unsaturated and aromatic aldehydes preferentially give the syn-
isomers. Very simple conditions for the conversion of intermediate
monocarbonate derivatives of alk-1-en-3,4-diols to cyclic carbon-
ates are also reported.
Scheme 1
Key words: zinc, 3-bromopropenyl carbonates, heterosubstituted
allyl zinc complexes, water as solvent, monoprotected alk-1-en-3,4-
diols
The reaction of 1 with metallic zinc in saturated aqueous
ammonium chloride solutions is very rapid at room tem-
perature, and if an aldehyde is present, the corresponding
diols 2 are obtained in very good yields (60–90%) after
hydrolysis and purification by flash chromatography. Hy-
drolysis of the intermediate ester functionality to free alk-
Twenty years have passed since the seminal work of
Pétrier and Luche on the allylation of aldehydes in aque-
ous media using organozinc reagents formed in situ. Al-
lylic bromides were reacted in a Barbier-type protocol,
1
-en-3,4-diols 2 is advisable, owing to the occurrence of
both intramolecular (Path a, Scheme 2) and intermolecu-
lar (Path b, Scheme 2) transesterification reactions in-
volving the intermediate alkoxide 3, leading to a number
of adducts, as outlined in Scheme 2.
using a mixture of saturated aqueous NH Cl and THF as
4
the solvent and zinc as the metal, to give homoallylic al-
cohols in almost quantitative yields (> 95%) and short re-
1
action times (30–45 min). In 2001 the Presidential Green
Chemistry Challenge Award (academic category) was
won by Li for his important contribution in the field of
Grignard/Barbier reactions using allylic halides and indi-
2
um in water and in air. In recent times water as a solvent
or co-solvent for organometallic chemistry has been thor-
3
oughly investigated and expanded, for example, in palla-
4
dium-catalyzed cross-coupling reactions and in Lewis
5
acid promoted processes. Water, the archetypical green
solvent, is not only low cost, non-toxic, and a safer sol-
6
vent, compared with commonly used organic solvents,
but often affords different results such as increased reac-
tions rates, for example in pericyclic cycloadditions, or
7
modified selectivities.
We recently proposed a new protocol for the a-hydroxy
allylation of carbonyl compounds in aqueous solvents,
using 3-bromopropenyl acetate 1 as the precursor of a
heterosubstituted allylic organometallic species, thus
opening a route to alk-1-en-3,4-diols 2 (Scheme 1). The
diastereochemical outcome of this reaction was unprece- In principle, the desired monoprotected product 6 could
9
dented among alternative hydroxyallylation reagents; in- be obtained in high yields if quenching of the intermediate
Scheme 2
8
deed, saturated aldehydes mainly afforded anti-adducts zinc alkoxide 3 with water (Path c) is faster than the trans-
esterification processes (Paths b and c). The idea of low-
ering the carbonyl electrophilicity led us to explore the
reactivity of 3-bromopropenyl carbonate 10 as a new pre-
cursor of heterosubstituted allylic organometallic species.
-Bromopropenyl methyl carbonate (10) can be obtained
SYNTHESIS 2005, No. 15, pp 2609–2614
x
x.
x
x
.
2
0
0
5
Advanced online publication: 04.08.2005
DOI: 10.1055/s-2005-872144; Art ID: C04005SS
Georg Thieme Verlag Stuttgart · New York
3
©

2
610
M. Lombardo et al.
SPECIAL TOPIC
in good yield, as a 65:35 mixture of Z/E-isomers, by radi- Further trends in chromatographic properties were ob-
1
0
11
cal bromination
Scheme 3).
of allyl methyl carbonate (9)
served in this work, which are useful for anticipating syn/
anti or cis/trans stereorelationships in 11 and 12, respec-
tively. For example, trans-12 has a higher R on silica with
(
f
respect to cis-12 and GC retention times of trans-12 are
always lower than retention times of cis-12.
As reported in Table 1, the same stereochemical prefer-
ence displayed by 3-bromopropenyl acetate (1) was ob-
served using carbonate 10. Again, while aliphatic
aldehydes give anti-adducts with good diastereoselectivi-
Scheme 3
We were delighted by the observation that the reaction of ty, aromatic and a,b-unsaturated aldehydes furnished syn-
0 (1.2 equiv) with aldehydes in saturated aqueous NH Cl adducts, generally with lower levels of diastereoselctivity.
1
4
and THF (9:1) using a slight excess of zinc (1.5 equiv) This behavior, peculiar to 3-halopropenyl esters and car-
proceeded smoothly affording the monoprotected adducts bonates, is ascribed to the presence of a C=O group on the
1
room temperature (Scheme 4, Table 1).
1 in high yields as the sole products, after 45 minutes at oxygen substituent; a theoretical study on the reaction
mechanism will be published in due course.
When we tried to purify 11 by flash-chromatography on
silica we observed the cyclization of 12 to 1,3-dioxol-
anones, to variable extents, depending on the nature of the
R group (Scheme 5).
Scheme 4
Table 1 Zinc Mediated a-Hydroxy Allylation of Aldehydes with 10
a
b
Entry
R in RCHO
11, Yield (%)
anti-11/syn-11
95:5
c
1
2
3
4
5
6
7
8
9
Cyclohexyl-
1-Methylethyl-
2-Methypropyl-
2-Phenylethyl-
Nonyl-
11a, 92
c
11b, 92
95:5
11c, 86
11d, 85
11e, 95
11f, 95
11g, 93
11h, 98
11i, 91
70:30
75:25
90:10
Scheme 5
Phenyl-
30:70
In particular: i) when R is a secondary aliphatic alkyl
group (Table 1, entries 1, 2), compounds 11 are quite sta-
ble on silica gel and can be isolated in high yields simply
by flash chromatography; ii) when R is a primary aliphatic
alkyl group (Table 1, entries 3–5) only partial cyclization
to 12 is observed; and iii) extensive cyclization occurs
when R is aromatic or unsaturated (Table 1, entries 6–10).
This general trend can be easily explained considering: i)
the relative bulkiness of R group and ii) the fact that cy-
clization of anti-11 affords sterically crowded cis-12,
while syn-11 gives the less sterically congested trans-12.
1-Naphthyl-
4-Methoxyphenyl-
4-Fluorophenyl-
40:60
12:88
30:70
1
0
(E)-2-Phenylethenyl- 11j, 88
25:75
a
1
Yields determined by H NMR spectroscopy and GC-MS of the
crude reaction mixtures.
b
1
Diastereomeric ratio determined by H spectroscopy and GC-MS of
the crude reaction mixtures.
c
Isolated yields.
A frequently used trick to purify products sensitive to the
Diasteroselectivity was determined by H NMR spectros- acidity of silica gel involves the addition of a small
1
copy after conversion of 11 into the corresponding diols 2 amount of Et
N (1–3%) to the eluent. To our surprise, the
N increased the rate of cyclization, inde-
3
by basic hydrolysis (K CO , MeOH–H O, 4:1). As report- presence of Et
2
3
2
3
1
2
8b
ed by Jiang et al. and later on confirmed by us, the pendently of the nature of the R group. So we developed
chemical shift of the homoallylic proton (H-4) in syn-2 al- a very easy procedure for the complete cyclization of 11
ways resonates 0.1–0.3 ppm upfield from that of anti-2. to 12, promoted by Et
Moreover, we observed that GC retention times of syn-11 action mixture containing 11 was stirred with Et
N adsorbed onto SiO
: the crude re-
N/SiO
O for two hours at room temperature, the solvent
was removed, and the solid residue was chromatographed
Table 2).
3
2
3
2
are always less than those of anti-11.
in Et
2
(
Synthesis 2005, No. 15, 2609–2614 © Thieme Stuttgart · New York

SPECIAL TOPIC
a-Hydroxy Allylation Reaction of Aldehydes in Water
2611
Table 2 Cyclization to 1,3-Dioxolanones 12 Promoted by Et N/
3
agents were commercially available and were used without further
purification, unless otherwise stated.
SiO2
a
a
Entry
11
trans-12, Yield (%)
cis-12, Yield (%)
cis-12a, 88
cis-12b, 82
cis-12c, 56
cis-12d, 59
cis-12e, 72
cis-12f, 32
cis-12g, 35
cis-12h, 15
cis-12i, 26
cis-12j, 24
3-Bromopropenyl Methyl Carbonate (10)
AIBN (0.328 g, 2 mmol) was added to a mixture of freshly purified
1
2
3
4
5
6
7
8
9
11a
11b
11c
11d
11e
11f
11g
11h
11i
trans-12a, 5
10
NBS (3.56 g, 20 mmol) and allyl methyl carbonate (2.73 mL, 24
mmol) in CCl (100 mL). The heterogeneous solution was rapidly
4
trans-12b, 5
brought to reflux (2–3 min) and stirred for 2 h at 80–90 °C. After
cooling to r.t., the solution was filtered, and the organic solvent was
evaporated at reduced pressure. The residue was rapidly chromato-
graphed through a short pad of silica (cyclohexane–EtOAc, 9:1) and
trans-12c, 21
trans-12d, 22
trans-12e, 10
trans-12f, 61
trans-12g, 50
trans-12h, 83
trans-12i, 62
trans-12j, 58
1
0 was further purified by distillation under vacuum (bp 45–55 °C,
–2
ca. 3 × 10 mmHg) to afford 2.73 g (14 mmol, 70%) of the title
compound as a 65:35 mixture of Z and E isomers.
(
Z)-10
H NMR (300 MHz, CDCl ): d = 3.89 (s, 3 H), 4.07 (dt, J = 1.0, 8.6
1
3
Hz, 2 H), 5.24 (dt, J = 6.1, 8.6 Hz, 1 H), 7.00 (dt, J = 1.0, 6.1 Hz, 1
H).
1
3
C NMR (75 MHz, CDCl ): d = 22.9, 55.4, 111.4, 138.4, 152.8.
3
10
11j
GC-MS (70 eV): m/z (%) = 55 (19), 59 (61), 71 (69), 115 (100), 119
(3), 121 (3), 194 (1), 196 (1).
a
Yields, determined after purification by flash-chromatography on
silica gel, refer to the two-step sequence – formation of 11 and cy-
clization to 12.
(
E)-10
H NMR (300 MHz, CDCl ): d = 3.78 (s, 3 H), 3.98 (dt, J = 1.0, 8.6
1
3
Hz, 2 H), 5.73 (dt, J = 8.6, 12.2 Hz, 1 H), 7.24 (dt, J = 1.2, 12.2 Hz,
1
H).
In conclusion, we have reported a simple and very effi-
cient procedure for the synthesis of monoprotected alk-1-
en-3,4-diols 11 in an aqueous medium. The most impor-
tant advantages of this procedure with respect to that pre-
viously reported, based on ester 1, are: i) the preparation
of 10 does not require the use of highly toxic acrolein; ii)
1
3
C NMR (75 MHz, CDCl ): d = 27.8, 55.1, 109.6, 140.6, 152.6.
3
GC-MS (70 eV): m/z (%) = 55 (16), 59 (80), 71 (68), 115 (100), 119
3), 121 (3), 194 (1), 196 (1).
(
4
-Hydroxy-3-propenyl Methyl Carbonates (11); General Proce-
dure
-Bromopropenyl methyl carbonate (10; 0.145 mL, 1.2 mmol) and
e.g., 10 can be stored under an inert atmosphere at room Zn (0.098 g, 1.5 mmol) were sequentially added to a solution of the
temperature for several months without appreciable de- aldehyde (1 mmol) in sat. aq NH Cl–THF (9:1, 5 mL); the hetero-
1
0 is noticeably more stable and easier to store than 1;
3
4
geneous solution was vigorously stirred at 20 ± 3 °C for 45 min. The
aqueous phase was extracted with Et O, the combined organic phas-
2
composition; and iii) the organozinc complex derived
from 10 proved to be more reactive than the correspond-
ing organometallic species derived from 1, as confirmed
on the one hand as the isolated yields (Table 2) are sys-
tematically 5–15% higher than those previously reported
es were dried (Na SO ), and concentrated at reduced pressure. The
4
2
1
crude mixture so obtained was analyzed by H NMR and GC-MS.
Both 11a and 11b can be purified by flash chromatography on silica
without significant decomposition; all other products were subject-
8
b
using 1, and on the other hand by the successful a-hy- ed to cyclization to 12 without prior purification.
droxyallylation of 4-fluorobenzaldehyde (Table 2, entry
anti-1-Cyclohexyl-1-hydroxybut-3-en-2-yl Methyl Carbonate
(anti-11a)
9
same experimental conditions, using 1.
), which conversely undergoes decomposition under the
8
b
1
H NMR (300 MHz, CDCl ): d = 0.94–1.32 (m, 6 H), 1.51–2.05 (m,
3
Finally, the use of the carbonate functionality could in 5 H), 3.56 (br dd, J = ca. 4.0, 7.6 Hz, 1 H), 3.80 (s, 3 H), 5.18 (ddt,
principle allow us to modulate the reactivity of 3-bro- J = 0.9, 4.0, 7.4 Hz, 1 H), 5.40 (ddd, J = 0.9, 1.5, 10.5 Hz, 1 H), 5.45
(
1
ddd, J = 0.9, 1.5, 17.4 Hz, 1 H), 5.95 (ddd, J = 7.4, 10.5, 17.4 Hz,
H).
mopropenyl carbonates, as well as the stability of the final
adducts; for example the stability of open chain adducts
GC-MS (70 eV): m/z (%) = 55 (100), 65 (44), 81 (30), 119 (3), 134
2), 197 (1).
1
1 can be increased by using tert-butyl carbonates instead
of a methyl carbonate, or, conversely, the spontaneous in
situ formation of cyclic carbonates 12 could be achieved Anal. calcd for C12
(
H O (228.14): C, 63.14; H, 8.83. Found: C,
20 4
6
3.75; H, 8.77.
by using an RO group which is a better leaving group than
the methoxy group. Work aimed at exploring the further
potential of carbonates is in progress.
anti-4-Hydroxy-5-methylhex-1-en-3-yl Methyl Carbonate (anti-
1b)
1
1
H NMR (300 MHz, CDCl ): d = 0.96 (d, J = 6.6 Hz, 3 H), 1.01 (d,
3
1
13
H and C NMR spectra were recorded on a Varian Inova 300 and
J = 6.6 Hz, 3 H), 1.59–1.86 (m, 1 H), 3.51 (dd, J = 4.3, 7.3 Hz, 1 H),
3
.80 (s, 3 H), 5.15 (dd, J = 4.3, 7.4 Hz, 1 H), 5.40 (dt, J = 1.0, 10.3
Hz, 1 H), 5.45 (dt, J = 1.0, 17.5 Hz, 1 H), 5.95 (ddd, J = 7.4, 10.3,
7.5 Hz, 1 H).
on a Varian Gemini 2000; chemical shifts are reported in ppm rela-
tive to TMS. GC analyses were performed with a HP5890 II instru-
ment (HP-5MS cross-linked 5% phenylmethyl silicone glass
capillary column, 0.25–mm film thickness) coupled to a HP5971
quadrupole mass detector. Melting points are uncorrected. All re-
1
GC-MS (70 eV): m/z (%) = 55 (100), 69 (30), 79 (6), 97 (2), 157 (1).
Synthesis 2005, No. 15, 2609–2614 © Thieme Stuttgart · New York

2
612
M. Lombardo et al.
SPECIAL TOPIC
Anal. calcd for C H O (188.12): C, 57.43; H, 8.57. Found: C,
9
Anal. calcd for C H O (156.18): C, 61.52; H, 7.74. Found: C,
8
16
4
12
3
5
7.94; H, 8.61.
60.91, H, 7.80.
1,3-Dioxolan-2-ones (12); General Procedure
Et N/SiO was prepared by simply stirring silica gel (25 g) with
4,5-trans-4-(2-Methylpropyl)-5-ethenyl-1,3-dioxolan-2-one
(4,5-trans-12c)
3
2
1
Et N (5 mL, 3.6 g, 36 mmol) in Et O at r.t. for 1 h. The solvent was
3
H NMR (200 MHz, CDCl ): d = 0.97 (d, J = 6.6 Hz, 3 H), 0.99 (d,
3
2
completely removed under reduced pressure to give 27.5 g of silica
ca. 0.9 mmol Et N/1 g SiO ). The crude reaction mixture contain-
ing 11 was stirred with Et N/SiO (1.5 g) in Et O (10 mL) for 2 h at
r.t., the solvent was evaporated under reduced pressure and products
were purified by flash chromatography on silica (cyclohexane–
EtOAc, 9:1).
J = 6.6 Hz, 3 H), 1.40–1.60 (m, 1 H), 1.66–1.98 (m, 2 H), 4.37 (ddd,
J = 4.0, 7.7, 9.2 Hz, 1 H), 4.60 (br tt, J = ca. 1.0, 7.7 Hz, 1 H), 5.44
(dt, J = 1.0, 10.3 Hz, 1 H), 5.50 (dt, J = 1.0, 17.3 Hz, 1 H), 5.89
(ddd, J = 7.0, 10.3, 17.3 Hz, 1 H).
(
3
2
3
2
2
13
C NMR (75 MHz, CDCl ): d = 21.9, 22.8, 24.8, 80.6, 83.1, 121.4,
3
1
31.9, 154.3.
GC-MS (70 eV): m/z (%) = 55 (61), 57 (30), 69 (100), 93 (4), 98 (5),
11 (2), 115 (1).
Anal. calcd for C H O (170.21): C, 63.51; H, 8.29. Found: C,
4
1
,5-trans-4-Cyclohexyl-5-ethenyl-1,3-dioxolan-2-one (4,5-trans-
2a)
1
1
H NMR (200 MHz, CDCl ): d = 0.77–1.43 (m, 6 H), 1.52–1.99 (m,
3
9
14
3
5
5
(
H), 4.09 (t, J = 6.6 Hz, 1 H), 4.79 (br tt, J = ca. 1.0, 6.8 Hz, 1 H),
.38 (dt, J = 1.0, 10.3 Hz, 1 H), 5.44 (dt, J = 1.0, 17.2 Hz, 1 H), 5.87
ddd, J = 7.0, 10.3, 17.2 Hz, 1 H).
6
3.50; H, 8.23.
4,5-cis-4-(2-Methylpropyl)-5-ethenyl-1,3-dioxolan-2-one (4,5-
cis-12c)
1
3
C NMR (50 MHz, CDCl ): d = 25.2, 25.4, 26.0, 27.6, 27.7, 41.0,
3
1
H NMR (300 MHz, CDCl ): d = 0.95 (d, J = 6.6 Hz, 3 H), 0.98 (d,
3
8
0.3, 85.5, 120.6, 133.1, 154.4.
GC-MS (70 eV): m/z (%) = 55 (64), 67 (31), 79 (12), 81 (42), 95
100), 109 (3), 119 (10), 134 (8), 196 (1).
Anal. calcd for C H O (196.24): C, 67.32; H, 8.22. Found: C,
J = 6.6 Hz, 3 H), 1.29 (ddd, J = 3.4, 8.4, 14.4 Hz, 1 H), 1.64 (ddd,
J = 5.1, 10.5, 14.4 Hz, 1 H), 1.77–1.88 (m, 1 H), 4.80 (ddd, J = 3.4,
7
J = 1.0, 10.5 Hz, 1 H), 5.49 (dt, J = 1.0, 17.4 Hz, 1 H), 5.84 (ddd,
J = 7.1, 10.5, 17.4 Hz, 1 H).
(
.6, 10.5 Hz, 1 H), 5.08 (br tt, J = ca. 1.0, 7.4 Hz, 1 H), 5.46 (dt,
11
16
3
6
6.93; H, 8.15.
1
3
C NMR (50 MHz, CDCl ): d = 21.4, 23.0, 24.7, 38.5, 78.3, 80.0,
3
4
,5-cis-4-Cyclohexyl-5-ethenyl-1,3-dioxolan-2-one (4,5-cis-12a)
H NMR (200 MHz, CDCl ): d = 0.88–1.43 (m, 5 H), 1.48–1.88 (m,
1
21.3, 129.5, 154.4.
1
3
GC-MS (70 eV): m/z (%) = 55 (68), 57 (30), 69 (100), 93 (5), 98 (5),
11 (4), 115 (1).
6
1
H), 4.38 (dd, J = 7.2, 8.9 Hz, 1 H), 5.05 (br tt, J = ca. 0.7, 7.3 Hz,
H), 5.48 (dt, J = 1.0, 10.3 Hz, 1 H), 5.49 (dt, J = 1.0, 17.2 Hz, 1
H), 5.94 (ddd, J = 7.4, 10.3, 17.2 Hz, 1 H).
1
Anal. calcd for C H O (170.21): C, 63.51; H, 8.29. Found: C,
14
9
3
1
3
63.22; H, 8.22.
C NMR (75 MHz, CDCl ): d = 24.9, 25.0, 25.8, 27.9, 28.6, 37.1,
3
8
0.1, 83.8, 121.8, 129.1, 154.5.
4,5-trans-4-(2-Phenylethyl)-5-ethenyl-1,3-dioxolan-2-one (4,5-
trans-12d)
GC-MS (70 eV): m/z (%) = 55 (67), 79 (15), 81 (44), 95 (100), 109
6), 134 (5).
(
1
H NMR (300 MHz, CDCl ): d = 1.97–2.07 (m, 1 H), 2.07–2.19 (m,
3
Anal. calcd for C H O (196.24): C, 67.32; H, 8.22. Found: C,
16
1 H), 2.75 (dt, J = 8.3, 14.1 Hz, 1 H), 2.89 (ddd, J = 5.6, 9.3, 14.1
Hz, 1 H), 4.31 (ddd, J = 4.4, 7.6, 12.0 Hz, 1 H), 4.66 (br dt, J = ca.
11
3
6
6.86; H, 8.28.
1.0, 7.3 Hz, 1 H), 5.42 (dt, J = 1.0, 10.6 Hz, 1 H), 5.47 (dt, J = 1.0,
17.4 Hz, 1 H), 5.84 (ddd, J = 7.4, 10.6, 17.4 Hz, 1 H), 7.17–7.37 (m,
5 H).
4
,5-trans-4-(1-Methylethyl)-5-ethenyl-1,3-dioxolan-2-one (4,5-
trans-12b)
1
H NMR (300 MHz, CDCl ): d = 0.99 (d, J = 6.8 Hz, 3 H), 1.04 (d,
3
13
C NMR (50 MHz, CDCl ): d = 30.9, 34.6, 80.8, 82.6, 121.4,
3
J = 6.8 Hz, 3 H), 1.99 (dhept, J = 6.8 Hz, 1 H), 4.09 (t, J = 6.7 Hz,
1
5
1
26.4, 128.3, 128.6, 131.8, 139.7, 154.1.
H), 4.76 (tt, J = 1.0, 6.8 Hz, 1 H), 5.40 (dt, J = 1.0, 10.3 Hz, 1 H),
.47 (dt, J = 1.0, 17.2 Hz, 1 H), 5.88 (ddd, J = 6.9, 10.3, 17.2 Hz, 1
GC-MS (70 eV): m/z (%) = 55 (15), 65 (15), 70 (18), 77 (12) 83
(
(
35), 91 (100), 105 (13), 117 (15), 141 (5), 149 (7), 156 (28), 218
1).
H).
1
3
C NMR (75 MHz, CDCl ): d = 17.2, 17.3, 31.5, 80.3, 86.1, 120.7,
3
Anal. calcd for C H O (218.25): C, 71.54; H, 6.47. Found: C,
3
1
33.1, 154.3.
13 14
7
1.75; H, 6.41.
GC-MS (70 eV): m/z (%) = 56 (100), 69 (54), 73 (48), 79 (10), 84
9), 97 (4), 101 (3).
(
4
12d)
,5-cis-4-(2-Phenylethyl)-5-ethenyl-1,3-dioxolan-2-one (4,5-cis-
Anal. calcd for C H O (156.18): C, 61.52; H, 7.74. Found: C,
12
8
3
1
6
1.39; H, 7.69.
H NMR (300 MHz, CDCl ): d = 1.75–1.88 (m, 1 H), 1.94–2.09 (m,
3
1
Hz, 1 H), 4.69 (ddd, J = 3.7, 7.8, 10.5 Hz, 1 H), 5.08 (br dt, J = ca.
1.0, 7.3 Hz, 1 H), 5.46 (dt, J = 1.0, 10.5 Hz, 1 H), 5.50 (dt, J = 1.0,
17.1 Hz, 1 H), 5.84 (ddd, J = 7.0, 10.5, 17.1 Hz, 1 H), 7.17–7.37 (m,
5 H).
H), 2.71 (dt, J = 8.2, 13.9 Hz, 1 H), 2.90 (ddd, J = 4.8, 9.1, 13.9
4
1
,5-cis-4-(1-Methylethyl)-5-ethenyl-1,3-dioxolan-2-one (4,5-cis-
2b)
1
H NMR (300 MHz, CDCl ): d = 0.92 (d, J = 6.7 Hz, 3 H), 1.09 (d,
3
J = 6.7 Hz, 3 H), 1.96 (dhept, J = 6.7, 8.7 Hz, 1 H), 4.32 (dd, J = 7.2,
8
1
1
.7 Hz, 1 H), 5.05 (br tt, J = ca. 1.0, 7.2 Hz, 1 H), 5.48 (dt, J = 1.0,
0.5 Hz, 1 H), 5.52 (dt, J = 1.0, 17.7 Hz, 1 H), 5.93 (ddd, J = 7.1,
0.5, 17.7 Hz, 1 H).
13
C NMR (50 MHz, CDCl ): d = 31.4, 31.8, 78.6, 79.8, 121.5,
3
1
26.4, 128.4, 128.6, 129.2, 139.9, 154.2.
GC-MS (70 eV): m/z (%) = 55 (10), 65 (19), 70 (36), 91 (100), 105
24), 117 (19), 141 (5), 156 (14), 218 (22).
Anal. calcd for C H O (218.25): C, 71.54; H, 6.47. Found: C,
1
3
C NMR (75 MHz, CDCl ): d = 17.8, 18.6, 27.8, 80.1, 84.9, 121.9,
3
29.1, 154.4.
(
1
1
3
14
3
GC-MS (70 eV): m/z (%) = 56 (100), 69 (46), 73 (44), 79 (7), 84 (7),
7 (3), 101 (2).
7
1.13; H, 6.44.
9
Synthesis 2005, No. 15, 2609–2614 © Thieme Stuttgart · New York

SPECIAL TOPIC
,5-trans-4-nonyl-5-ethenyl-1,3-dioxolan-2-one (4,5-trans-12e)
a-Hydroxy Allylation Reaction of Aldehydes in Water
2613
4
1
GC-MS (70 eV): m/z (%) = 51 (11), 63 (11), 77 (11), 127 (32), 128
(42), 140 (100), 155 (31), 167 (26), 195 (14), 240 (36).
H NMR (300 MHz, CDCl ): d = 0.89 (t, J = 7.3 Hz, 3 H), 1.20–
3
1
4
5
.42 (m, 14 H), 1.63–1.86 (m, 2 H), 4.31 (dt, J = 5.0, 7.6 Hz, 1 H),
.64 (br dt, J = ca. 1.0, 7.4 Hz, 1 H), 5.43 (dt, J = 1.0, 10.3 Hz, 1 H),
.50 (dt, J = 1.0, 17.4 Hz, 1 H), 5.88 (ddd, J = 7.2, 10.3, 17.4 Hz, 1
Anal. calcd for C H O (240.25): C, 74.99; H, 5.03. Found: C,
3
1
5
12
7
4.43; H, 5.06.
H).
4
12g)
,5-cis-4-(1-Naphthyl)-5-ethenyl-1,3-dioxolan-2-one (4,5-cis-
1
3
C NMR (50 MHz, CDCl ): d = 14.0, 22.6, 24.6, 29.1, 29.2, 29.26,
3
1
2
9.3, 31.8, 32.9, 81.9, 82.6, 121.1, 132.2, 154.3.
H NMR (300 MHz, CDCl ): d = 4.97 (dt, J = 1.0, 10.3 Hz, 1 H),
3
5
H), 5.63 (ddt, J = 1.0, 6.7, 8.1 Hz, 1 H), 6.57 (d, J = 8.1 Hz, 1 H),
.16 (ddd, J = 6.7, 10.3, 17.0 Hz, 1 H), 5.32 (dt, J = 1.0, 17.0 Hz, 1
GC-MS (70 eV): m/z (%) = 55 (100), 69 (86), 80 (87), 83 (84), 93
(
(
33), 95 (33), 97 (41), 107 (18), 121 (25), 135 (24), 149 (14), 163
3), 178 (1), 196 (1).
7
.51–7.68 (m, 5 H), 7.86–7.98 (m, 2 H).
1
3
C NMR (75 MHz, CDCl ): d = 78.3, 80.6, 120.9, 121.8, 123.2,
3
Anal. calcd for C H O (240.34): C, 69.96; H, 10.07. Found: C,
24
14
3
1
1
25.4, 126.2, 126.9, 128.8, 129.30, 129.34, 129.41, 129.43, 133.4,
54.2.
6
9.71; H, 9.99.
4
,5-cis-4-Nonyl-5-ethenyl-1,3-dioxolan-2-one (4,5-cis-12e)
H NMR (300 MHz, CDCl ): d = 0.89 (t, J = 7.3 Hz, 3 H), 1.22–
GC-MS (70 eV): m/z (%) = 51 (5), 63 (8), 77 (7), 127 (32), 128 (46),
140 (100), 155 (29), 167 (25), 195 (13), 240 (42).
1
3
1
1
1
.40 (m, 14 H), 1.48–1.75 (m, 2 H), 4.70 (ddd, J = 3.9, 7.6, 9.8 Hz,
H), 5.08 (br dt, J = ca. 1.0, 7.6 Hz, 1 H), 5.47 (dt, J = 1.0, 10.5 Hz,
H), 5.51 (dt, J = 1.0, 17.6 Hz, 1 H), 5.85 (ddd, J = 7.3, 10.5, 17.6
Anal. calcd for C H O (240.25): C, 74.99; H, 5.03. Found: C,
1
5
12
3
7
4.45; H, 4.99.
Hz, 1 H).
4,5-trans-4-(4-Methoxyphenyl)-5-ethenyl-1,3-dioxolan-2-one
(4,5-trans-12h)
Mp 98–99 °C.
1
3
C NMR (75 MHz, CDCl ): d = 13.9, 22.5, 25.3, 29.0, 29.1, 29.2,
3
2
9.3, 29.8, 31.7, 79.9 (2C), 121.2, 129.4, 154.3.
1
GC-MS (70 eV): m/z (%) = 55 (100), 69 (92), 80 (75), 83 (98), 93
H NMR (300 MHz, CDCl ): d = 3.83 (s, 3 H), 4.89 (ddt, J = 1.0,
3
(
(
29), 95 (31), 97 (49), 107 (17), 121 (23), 135 (21), 149 (14), 163
3), 178 (1), 196 (1).
7.1, 8.3 Hz, 1 H), 5.22 (d, J = 8.3 Hz, 1 H), 5.44 (dt, J = 1.0, 17.7
Hz, 1 H), 5.45 (dt, J = 1.0, 10.6 Hz, 1 H), 5.96 (ddd, J = 7.1, 10.6,
1
7.7 Hz, 1 H), 6.96 (d, J = 9.1 Hz, 2 H), 7.40 (d, J = 9.1 Hz, 2 H).
Anal. calcd for C H O (240.34): C; 69.96, H, 10.07. Found: C,
24
14
3
1
3
6
9.33; H, 10.12.
C NMR (50 MHz, CDCl ): d = 55.4, 83.1, 84.6, 114.6, 121.7,
3
1
26.4, 127.7, 131.3, 160.7.
4
,5-trans-4-Phenyl-5-ethenyl-1,3-dioxolan-2-one (4,5-trans-12f)
H NMR (200 MHz, CDCl ): d = 4.89 (ddt, J = 1.0, 7.0, 8.1 Hz, 1
GC-MS (70 eV): m/z (%) = 51 (23), 63 (15), 65 (11), 77 (38), 91
1
3
(
(
40), 105 (11), 115 (12), 120 (76), 135 (100), 147 (37), 159 (5), 176
4), 220 (45).
H), 5.29 (d, J = 8.9 Hz, 1 H), 5.47 (dt, J = 1.0, 16.5 Hz, 1 H), 5.49
(
dt, J = 1.0, 10.6 Hz, 1 H), 6.00 (ddd, J = 7.0, 10.6, 16.5 Hz, 1 H),
.32–7.54 (m, 5 H).
Anal. calcd for C H O (220.07): C, 65.45; H, 5.49. Found: C,
12 12
7
4
6
4.87; H,5.45.
1
3
C NMR (75 MHz, CDCl ): d = 82.8, 84.5, 121.8, 125.8, 129.0,
3
1
29.5, 131.1, 134.6, 153.8.
4,5-cis-4-(4-methoxyphenyl)-5-ethenyl-1,3-dioxolan-2-one (4,5-
cis-12h)
GC-MS (70 eV): m/z (%) = 51 (48), 55 (18), 63 (24), 77 (73), 91
41), 105 (77), 117 (100), 131 (14), 145 (35), 190 (17).
1
(
H NMR (200 MHz, CDCl ): d = 3.83 (s, 3 H), 5.18–5.52 (m, 4 H),
3
5.74 (d, J = 7.2 Hz, 1 H), 6.93 (d, J = 9.1 Hz, 2 H), 7.17 (d, J = 9.1
Hz, 2 H).
Anal. calcd for C H O (190.20); C, 69.46, H, 5.30. Found: C,
3
1
1
10
7
0.09; H, 5.25.
1
3
C NMR (50 MHz, CDCl ): d = 55.3, 80.7, 81.2, 114.2, 121.1,
3
4
,5-cis-4-Phenyl-5-ethenyl-1,3-dioxolan-2-one (4,5-cis-12f)
H NMR (200 MHz, CDCl ): d = 5.18–5.53 (m, 4 H), 5.78 (d,
125.0, 127.7, 130.4, 160.3.
1
3
GC-MS (70 eV): m/z (%) = 51 (22), 63 (15), 65 (11), 77 (39), 91
(37), 105 (12), 115 (11), 120 (71), 135 (100), 147 (30), 159 (6), 176
(4), 220 (38).
J = 7.5 Hz, 1 H), 7.20–7.30 (m, 2 H), 7.36–7.46 (m, 3 H).
1
3
C NMR (75 MHz, CDCl ): d = 80.6, 81.1, 121.2, 126.1, 128.7,
3
1
29.2, 130.1, 133.0, 154.4.
Anal. calcd for C H O (220.07): C, 65.45; H, 5.49. Found: C,
1
2
12
4
GC-MS (70 eV): m/z (%) = 51 (49), 55 (15), 63 (26), 77 (71), 91
34), 105 (74), 117 (100), 131 (13), 145 (36), 190 (18).
65.14; H, 5.52.
(
4,5-trans-4-(4-Fluorophenyl)-5-ethenyl-1,3-dioxolan-2-one (4,5-
trans-12i)
Anal. calcd for C H O (190.20): C, 69.46; H, 5.30. Found: C,
10
11
3
6
9.77; H, 5.28.
1
H NMR (300 MHz, CDCl ): d = 4.85 (ddt, J = 0.7, 7.1, 8.0 Hz, 1
3
H), 5.26 (d, J = 8.0 Hz, 1 H), 5.46 (dt, J = 0.7, 17.4 Hz, 1 H), 5.50
(
7
4,5-trans-4-(1-Naphthyl)-5-ethenyl-1,3-dioxolan-2-one (4,5-
trans-12g)
Mp 95–98 °C.
dt, J = 0.7, 10.5 Hz, 1 H), 5.98 (ddd, J = 7.1, 10.5, 17.4 Hz, 1 H),
.10–7.19 (m, 2 H), 7.32–7.40 (m, 2 H).
1
3
1
C NMR (75 MHz, CDCl ): d = 82.3, 84.7, 116.2 (d, JC-F = 22 Hz),
3
H NMR (300 MHz, CDCl ): d = 5.04 (ddt, J = 1.0, 6.2, 7.2 Hz, 1
3
1
1
22.3, 127.9 (d, JC-F = 8.5 Hz), 130.4 (d, JC-F = 3.1 Hz), 130.9,
53.7, 163.3 (d, JC-F = 250 Hz).
H), 5.53 (dt, J = 1.0, 17.9 Hz, 1 H), 5.56 (dt, J = 1.0, 10.5 Hz, 1 H),
6
7
.07 (d, J = 6.2 Hz, 1 H), 6.18 (ddd, J = 7.2, 10.5, 17.9 Hz, 1 H),
.52–7.61 (m, 3 H), 7.66 (dt, J = 1.0, 7.1 Hz, 1 H), 7.73–7.80 (m, 1
GC-MS (70 eV): m/z (%) = 55 (17), 57 (18), 75 (24), 95 (42), 97
(38), 108 (100), 123 (80), 125 (80), 135 (86), 147 (9), 163 (21), 164
(16), 208 (17).
H), 7.91–7.99 (m, 2 H).
1
3
C NMR (75 MHz, CDCl ): d = 80.3, 83.8, 122.0, 122.2, 123.2,
3
1
25.3, 126.2, 126.9, 129.3, 129.5, 129.9, 130.8, 131.9, 133.8, 154.2.
Anal. calcd for C H FO (208.19): C, 63.46; H, 4.36. Found: C,
1
1
9
3
6
3.75; H, 4.40.
Synthesis 2005, No. 15, 2609–2614 © Thieme Stuttgart · New York

2
614
M. Lombardo et al.
SPECIAL TOPIC
4,5-cis-4-(4-Fluorophenyl)-5-ethenyl-1,3-dioxolan-2-one (4,5-
cis-12i)
GC-MS (70 eV): m/z (%) = 51 (8), 55 (6), 68 (12), 77 (14), 91 (9),
104 (16), 115 (100), 131 (22), 143 (6), 154 (3), 172 (1), 216 (1).
1
H NMR (300 MHz, CDCl ): d = 5.22–5.49 (m, 4 H), 5.77 (d,
3
Anal. calcd for C H O (216.23): C,72.21; H, 5.59. Found: C,
1
3
12
2
J = 7.9 Hz, 1 H), 7.06–7.16 (m, 2 H), 7.19–7.26 (m, 2 H).
7
2.00; H, 5.56.
1
3
C NMR (75 MHz, CDCl ): d = 80.0, 81.0, 115.9 (d, J = 22 Hz),
C-F
3
1
1
21.4, 128.1 (d, JC-F = 8.6 Hz), 128.9 (d, JC-F = 3.7 Hz), 130.0,
54.2, 163.0 (d, JC-F = 248 Hz).
Acknowledgment
GC-MS (70 eV): m/z (%) = 55 (15), 57 (20), 75 (28), 95 (50), 97
45), 108 (100), 123 (88), 125 (77), 135 (81), 147 (12), 163 (21),
64 (14), 208 (20).
This work was supported by M.I.U.R. (Rome) grants (PRIN project
‘Stereoselezione nella sintesi organica’ and FIRB project ‘Progetta-
zione, preparazione e valutazione biologica e farmacologica di
nuove molecole organiche quali potenziali farmaci innovativi’) and
by the University of Bologna (Funds for selected research topics).
(
1
Anal. calcd for C H FO (208.19): C, 63.46; H, 4.36. Found: C,
3
11
9
6
4.01; H, 4.33.
4
(
,5-trans-4-[(E)-2-Phenylethenyl]-5-ethenyl-1,3-dioxolan-2-one
4,5-trans-12i)
References
1
H NMR (300 MHz, CDCl ): d = 4.82 (ddt, J = 0.7, 6.8, 8.1 Hz, 1
3
(1) Pétrier, C.; Luche, J.-L. J. Org. Chem. 1985, 50, 912.
(2) Li, C.-J. Green Chem. 2002, 4, 1.
(3) (a) Lindström, U. L. Chem. Rev. 2002, 102, 2751. (b) Li, C.
H.; Chan, T. H. Tetrahedron 1999, 55, 11149.
H), 4.90 (br dt, J = ca. 1.0, 8.0 Hz, 1 H), 5.48 (dt, J = 0.7, 10.5 Hz,
H), 5.53 (dt, J = 0.7, 17.4 Hz, 1 H), 5.97 (ddd, J = 6.8, 10.5, 17.4
Hz, 1 H), 6.18 (dd, J = 7.5, 15.9 Hz, 1 H), 6.78 (dd, J = 1.0, 15.9 Hz,
1
1
H), 7.30–7.48 (m, 5 H).
(c) Lubineau, A.; Augé, J.; Queneau, Y. Synthesis 1994, 741.
(4) (a) Shaughnessy, K. H.; DeVasher, R. B. Curr. Org. Chem.
1
3
C NMR (75 MHz, CDCl ): d = 82.5, 82.8, 121.2, 121.6, 126.9,
3
2
2
005, 9, 585. (b) Bai, L.; Wang, J.-X. Curr. Org. Chem.
005, 9, 535.
1
28.7, 129.0, 131.0, 134.7, 136.9, 153.9.
GC-MS (70 eV): m/z (%) = 51 (10), 55 (7), 68 (14), 77 (15), 91 (8),
04 (17), 115 (100), 131 (22), 143 (5), 154 (3), 172 (1), 216 (1).
(
5) (a) Kobayashi, S.; Manabe, K. Acc. Chem. Res. 2002, 35,
09. (b) Manabe, K.; Kobayashi, S. Chem.–Eur. J. 2002, 8,
4094.
1
2
Anal. calcd for C H O (216.23): C, 72.21; H, 5.59. Found: C,
12
13
2
7
1.50; H,5.60.
(6) Li, C.-J. In Organic Reactions in Aqueous Media; Chan, T.-
H., Ed.; Wiley: New York, 1997, 199.
4
(
,5-cis-4-[(E)-2-Phenylethenyl]-5-ethenyl-1,3-dioxolan-2-one
4,5-cis-12i)
(7) Breslow, R. Acc. Chem. Res. 2004, 37, 471.
(8) (a) Girotti, R.; Lombardo, M.; Morganti, S.; Trombini, C.
Chem. Commun. 2001, 2310. (b) Lombardo, M.; Morganti,
S.; Trombini, C. J. Org. Chem. 2003, 68, 997.
(9) Lombardo, M.; Licciulli, S.; Trombini, C. Pure Appl. Chem.
2004, 76, 657.
(10) Dauben, H. J. Jr.; McCoy, L. L. J. Am. Chem. Soc. 1959, 81,
1
H NMR (300 MHz, CDCl ): d = 5.23 (ddt, J = 1.0, 6.8, 7.8 Hz, 1
3
H), 5.34 (dt, J = 1.0, 7.8 Hz, 1 H), 5.47 (dt, J = 1.0, 10.5 Hz, 1 H),
.54 (dt, J = 0.7, 17.4 Hz, 1 H), 5.85 (ddd, J = 6.8, 10.5, 17.4 Hz, 1
H), 6.09 (dd, J = 7.8, 15.9 Hz, 1 H), 6.76 (dd, J = 1.0, 15.9 Hz, 1 H),
5
7
.30–7.48 (m, 5 H).
4
863.
1
3
C NMR (75 MHz, CDCl ): d = 80.2, 80.4, 120.2, 121.2, 126.9,
3
(
(
11) Minami, I.; Tsuji, J. Tetrahedron 1987, 43, 3903.
12) Jiang, S.; Agoston, G. E.; Chen, T.; Cabal, M. P.; Turos, E.
Organometallics 1995, 14, 4697.
1
28.7, 128.9, 129.8, 135.0, 136.5, 154.1.
Synthesis 2005, No. 15, 2609–2614 © Thieme Stuttgart · New York