High yield regioselective ring opening of epoxides using samarium chloride hexahydrate

Article abstract of DOI:10.1081/SCC-120018790

Epoxides were converted to the corresponding β-azidohydrins and β-iodohydrins using SmCl₃·6H₂O/NaN₃ in DMF and SmCl₃·6H₂/NaI in acetonitrile respectively. The reactions were highly regio-selective, ef

Full text of DOI:10.1081/SCC-120018790

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High Yield Regioselective Ring Opening of Epoxides
Using Samarium Chloride Hexahydrate
Kankan Bhaumik a , Umesh W. Mali a & K. G. Akamanchi a
a Department of Pharmaceutical Sciences and Technology , Mumbai University Institute of
Chemical Technology , Matunga, Mumbai, India
Published online: 16 Aug 2006.
To cite this article: Kankan Bhaumik , Umesh W. Mali & K. G. Akamanchi (2003) High Yield Regioselective Ring Opening
of Epoxides Using Samarium Chloride Hexahydrate, Synthetic Communications: An International Journal for Rapid
Communication of Synthetic Organic Chemistry, 33:9, 1603-1610, DOI: 10.1081/SCC-120018790
To link to this article: http://dx.doi.org/10.1081/SCC-120018790
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SYNTHETIC COMMUNICATIONSÕ
Vol. 33, No. 9, pp. 1603–1610, 2003
High Yield Regioselective Ring Opening of
Epoxides Using Samarium Chloride Hexahydrate
*
Kankan Bhaumik,Umesh W. Mali,and K. G. Akamanchi
Department of Pharmaceutical Sciences and
Technology, Mumbai University Institute of Chemical
Technology, Matunga, Mumbai, India
ABSTRACT
Epoxides were converted to the corresponding b-azidohydrins and
b-iodohydrins using SmCl3ꢀ6H2O/NaN3 in DMF and SmCl3ꢀ6H2O/
NaI in acetonitrile respectively. The reactions were highly regio-
selective, efficient, and gave excellent yields under mild and neutral
conditions.
Key Words: Samarium chloride; Azidohydrins; Iodohydrins;
Epoxides.
*Correspondence: K. G. Akamanchi, Department of Pharmaceutical Sciences
and Technology, Mumbai University Institute of Chemical Technology,
Nathalal Parikh Marg, Matunga, Mumbai 400 019, India; Fax: 91-(222)
4145614; E-mail: kgap@rediffmail.com.
1603
DOI: 10.1081/SCC-120018790
Copyright & 2003 by Marcel Dekker, Inc.
0039-7911 (Print); 1532-2432 (Online)
www.dekker.com

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1604
Bhaumik,Mali,and Akamanchi
INTRODUCTION
The ring opening reactions of epoxides are intriguing research area
that can still be considered interesting. vic-Azidohydrins and halohydrins
are of considerable importance in the synthesis of natural products and in
many organic transformations. 1,2-Azidoalcohols are interesting inter-
mediates for the synthesis of chiral aziridines[1] as well as precursors of
vicinal amino alcohols that occur widely in nature and often constitute
the moiety in structures of biologically active compounds,[2,3] natural
products,[4,5] cardiovascular agents,[6,7] antibiotics,[8] immunostimulants,[9]
and chiral ligands for asymmetric catalysis.[10] They are also important
in the chemistry of carbohydrates and nucleosides.
There are several reports on synthesis of azidohydrins
and halohydrins. 1,2-Azidoalcohols can be synthesized by ring
opening of epoxides using Ti(OiPr)4/TMSN3,[11] V(OiPr)3/TMSN3,[12]
Yb(OiPr)3/TMSN3,[13] Cr(salen)2/TMSN3,[14] Lewis acid/TMSN3,[15]
PTC/TMSN3,[16] NaN3/M(NO3)2, [M¼Cu, Co, Ni, Zn, Zr],[17] NaN3/
Mg(ClO4)2,[20f ] NaN3/SnCl2ꢀ2H2O–MgI2 in THF,[18] NaN3/LiOTf,[20f ]
NaN3/Clay/Zeolite,[19] NaN3/NH4Cl,[20] HN3 with DIPEA,[21]
Al(N3)3,[22a] Bu2Sn(N3)2 in DMF at 60 C, Ti(N3)4
in organic sol-
[23]
ꢁ
[22b]
vent, polymer supported azide[24] systems. Many of these reactions are
complicated by isomerization, epimerization, and the rearrangement
products. Conventionally, epoxides are transformed to halohydrins by
electrophilic cleavage with hydrogen halide[25] but it requires harsh
reaction conditions with often low regioselectivity. Competing reagents
and side reactions with other acid-sensitive functionalities limit the use
of strong Lewis acids, such as BF3.[26] The hydrophobic nature of LiI[27]
limits its use to iodohydrin formation. Iodohydrins can also be pre-
pared by iodomethylation of carbonyl compounds with CH2I2 in presence
[28]
of SmI2
and elemental iodine,[29] however all such methods
require excess reagents. Other methods include MgI2 in ether,[30]
TMSCl/NaI[30b] in acetonitrile, NaI(aq) (pH 2),[31] InCl3/NaI,[31]
[34]
CeCl3ꢀ7H2O/NaI,[32] Ti(OiPr)4/NaI,[33] triphenylphosphoniumiodide,
and others.[35] Most of these reactions give poor yield and less regioselec-
tivity and longer reaction time. Therefore, there is a scope for new reaction
systems.
The use of lanthanides based reaction systems are our current
interest. In the present work we describe the use of samarium(III)
chloride hexahydrate as a catalyst for the regioselective ring opening of
epoxides to get azidohydrins and iodohydrins. Azidohydrin formation in
acetonitrile was very slow and even after 24 h of reaction time no signi-
ficant transformation was observed and all the starting epoxide was

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High Yield Regioselective Ring Opening of Epoxides
1605
recovered unreacted. The reaction was complete within 5–6 h at room
temperature in DMF, however iodohydrin formation was complete
within 10–20 min in acetonitrile. All the reactions were carried out in
laboratory grade solvent without further drying.
Except the reaction of epoxides, styrene oxide (Table 1, Entry 6) and
heptene oxide (Table 1, Entry 8) which produce a small percentage of
Table 1. Regioselective ring opening of epoxidesa using SmCl3Á6H2O.
Isolated
yieldc (%)
Entry
1
Epoxide
Major productb
X
N3
I
90
95
2
3
N3
I
91
94
N3
I
92
96
4
5
6
N3
I
90
95
N3
I
92
96
N3
I
91 (10:1)
95 (11:1)
7
8
N3
I
94
97
N3
I
89 (9:1)
92 (10:1)
93
9
N3
I
98
92
10
N3
I
97
aAll the reactions were carried out at roomtemperature.
bStructure and regiochemical ratios determined for the products by
proton-NMR.[36]
cYields refer to the isolated product and figures in the bracket indicate ratio of
regioisomers wherein observed.

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1606
Bhaumik,Mali,and Akamanchi
other regioisomer, the reaction of other epoxides were found to be highly
regioselective and only one isomer was obtained. The high regioselectivity
of glycidyl ethers (Table 1, Entries 1–5) could be attributed to metal
chelation and the attack of the nucleophile at C-3, a less hindered
position. As expected in case of styrene oxide 2-azido- and 2-iodo-2-
phenylethanols (Table 1, Entry 6) were obtained as the major products
due to formation of stabilized benzylic cation during the reaction. It is
noteworthy that there was no formation of any Michael addition product
in the case of glycidyl methacrylate (Table 1, Entry 10).
In conclusion, we have demonstrated a highly efficient, regioselective
conversion of epoxides to azidohydrins and iodohydrins under mild and
neutral conditions. It has several advantages such as very less reaction
time, easy handling, room temperature reaction, and no need of dry
solvent.
EXPERIMENTAL
1H-NMR spectra were recorded in CDCl3 on FT–NMR JEOL
(60 MHz) instrument using TMS as internal standard. IR spectra were
recorded in CHCl3 using BUCK SCIENTIFIC 500 instrument. All
solvents were obtained commercially and were used without further
purification. All substrates were purified before use.
Typical Procedure for Azidohydrin Formation of
Glycidyl Methacrylate
To a slurry of SmCl3ꢀ6H2O (1.28 g, 3.51 mmol) and DMF (35 mL),
glycidyl methacrylate (0.5 g, 3.51 mmol) in DMF (6 mL) was added and
stirred at room temperature for 1 min. Then, NaN3 (0.25 g, 3.85 mmol)
was added to it and stirred. The reaction was monitored by TLC
(reaction was complete within 5 h). On completion, solution was filtered
and solvent was removed under reduced pressure and the crude product
was purified by silica gel (60–120 mesh) column chromatography using
ethyl acetate and hexane (9:1 by volume) to yield a viscous oil. The
product, 3-azido-2-hydroxypropyl methacrylate (0.60 g, 92%) obtained
1
1
was characterized by H-NMR, IR spectral data. H-NMR (CDCl3):
ꢀ 1.89 (s, 3H), 3.09–4.23 (m, 6H), 5.53 (s, 1H), 6.06 (s, 1H). IR
(CHCl3): 3366, 2924, 2860, 2099, 1714, 1660, 1439, 1168 cmꢂ1
.

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High Yield Regioselective Ring Opening of Epoxides
1607
Typical Procedure for Iodohydrin Formation of
Glycidyl Methacrylate
To a slurry of SmCl3ꢀ6H2O (1.28 g, 3.51 mmol) and acetonitrile
(35 mL), glycidyl methacrylate (0.5 g, 3.51 mmol) in acetonitrile (6 mL)
was added and stirred at room temperature for 1 min. Then, NaI (0.58 g,
3.87 mmol) was added to it, and the reaction mixture stirred. The reaction
was monitored by TLC (reaction was complete within 15 min). On com-
pletion, solution was filtered and solvent was removed under reduced
pressure and the crude product was purified by silica gel (60–120 mesh)
column chromatography using ethyl acetate and hexane (9:1 by volume).
The product, 3-iodo-2-hydroxypropyl methacrylate (0.92 g, 92%)
1
obtained was an oil and characterized by H-NMR, IR spectral data.
1H-NMR (CDCl3): ꢀ 1.87 (s, 3H), 3.25 (m, 2H), 3.85–4.12 (m, 4H), 5.54
(s, 1H), 6.06 (s, 1H). IR (CHCl3): 3416, 2964, 1716, 1700, 1634,
1162 cmꢂ1
.
ACKNOWLEDGMENT
KB and UWM thank UGC for SRF fellowships.
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36. IR values are expressed in cmÀ1 and 1H-NMR values are expressed
in d scale in ppm. Entry 1. 1-Azido-3-(2-naphthyloxy-2-propanol.
1H-NMR (CDCl3). ꢀ 2.58 (m, 1H), 3.69–3.72 (m, 2H), 4.12 (m, 3H),
6.98–7.73 (m, 7H). IR (CHCl3): 3360, 2921, 2867, 2099, 1597, 1388,
1257. 1-Iodo-3-(2-naphthyloxy)-2-propanol. 1H-NMR (CDCl3): ꢀ
2.33 (m, 1H), 3.28–3.37 (m, 2H), 3.90–4.02 (m, 3H), 7.02–7.68 (m,
7H). IR (CHCl3): 3405, 3044, 2917, 1460, 1392, 1257, 1216. Entry 2.
1-Azido-3-(3-chlorophenoxy)-2-propanol. 1H-NMR (CDCl3): ꢀ 2.81
(m, 1H), 3.37–3.68 (m, 2H), 3.93–3.99 (m, 3H), 6.64–7.27 (m, 4H).
IR (CHCl3): 3374, 3050, 2921, 2871, 2099, 1591, 1475, 1241. 1-Iodo-
3-(3-chlorophenoxy)-2-propanol. 1H-NMR (CDCl3): ꢀ 2.80 (m,
1H), 3.26–3.64 (m, 2H), 3.91 (m, 3H), 6.41–7.25 (m, 4H). IR
(CHCl3): 3380, 3035, 2918, 2866, 1582, 1478, 1244. Entry 3. 1-
Azido-3-(2-nitrophenoxy)-2-propanol. 1H-NMR (CDCl3): ꢀ 3.08
(m, 1H), 3.68–3.84 (m, 2H), 4.20 (m, 3H), 6.90–7.88 (m, 4H). IR
(CHCl3): 3350, 3041, 2921, 2877, 2101, 1603, 1520, 1352, 1281, 1254.
1-Iodo-3-(2-nitrophenoxy)-2-propanol. 1H-NMR (CDCl3): ꢀ 3.17
(m, 1H), 3.23–3.42 (m, 2H), 3.99–4.22 (m, 3H), 6.88–7.87 (m, 4H).
IR (CHCl3): 3504, 3050, 2938, 2872, 1602, 1518, 1349, 1281, 1253.
Entry 4. 1-Azido-3-(4-chlorothiophenoxy)-2-propanol. 1H-NMR
(CDCl3): ꢀ 2.74 (m, 1H), 4.01–4.09 (m, 2H), 4.39–4.49 (m, 3H),
7.09–7.24 (d, 2H), 7.52–7.66 (d, 2H). IR (CHCl3): 3356, 2923,

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1610
Bhaumik,Mali,and Akamanchi
2870, 2100, 1591, 1489, 1234. 1-Iodo-3-(4-chlorothiophenoxy)-2-
1
propanol. H-NMR (CDCl3): ꢀ 2.30–2.32 (m, 1H), 3.33–3.41 (m,
2H), 3.97 (m, 3H), 6.70–6.87 (d, 2H), 7.14–7.29 (d, 2H). IR
(CHCl3): 3378, 2917, 2877, 1589, 1489, 1233. Entry 5. 1-Azido-3-
1
(4-chlorophenoxy)-2-propanol. H-NMR (CDCl3): ꢀ 2.84 (m, 1H),
4.01–4.09 (m, 2H), 4.39–4.49 (m, 3H), 7.09–7.24 (d, 2H), 7.52–7.66
(d, 2H). IR (CHCl3): 3356, 2923, 2870, 2100, 1591, 1489, 1242. 1-
Iodo-3-(4-chlorophenoxy)-2-propanol. 1H-NMR (CDCl3):
ꢀ
2.34–2.37 (d, 1H), 3.33–3.41 (m, 2H), 3.97 (m, 3H), 6.70–6.87 (d,
2H), 7.14–7.29 (d, 2H). IR (CHCl3): 3378, 2917, 2877, 1589, 1489,
1
1241. Entry 6. 2-Azido-2-phenylethanol. H-NMR (CDCl3): ꢀ 2.23
(s, 1H), 3.84–4.10 (m, 2H), 5.10 (m, 0.09H, minor), 5.20–5.27 (m,
0.91H, major), 7.40 (m, 5H). IR (CHCl3): 3368, 3020, 2980, 2870,
1
1249, 1063. 2-Iodo-2-phenylethanol. H-NMR (CDCl3): ꢀ 2.22 (s,
1H), 3.85–4.04 (m, 2H), 5.05–5.10 (m, 0.08H, minor), 5.11–5.29 (m,
0.92H, major), 7.36 (m, 5H). IR (CHCl3): 3368, 3020, 2980, 2870,
2101, 1249, 1063. Entry 7. 1-Azido-2-cyclohexanol. 1H-NMR
(CDCl3): ꢀ 0.96–1.82 (m, 8H), 2.65 (s, 1H), 3.26–3.27 (m, 2H). IR
(CHCl3): 3380, 2921, 2868, 2100, 1460, 1257, 1094. 1-Iodo-2-cyclo-
hexanol. 1H-NMR (CDCl3): ꢀ 0.95–1.79 (m, 8H), 2.62 (s, 1H),
3.23–3.25 (m, 2H). IR (CHCl3): 3376, 2962, 2851, 1458, 1016.
1
Entry 8. 1-Azido-2-heptanol. H-NMR (CDCl3): ꢀ 0.90 (m, 3H),
0.92–1.38 (m, 8H), 2.71 (s, 1H), 3.19–3.35 (m, 2.7H, major),
3.36–3.63 (m, 0.3H, minor). IR (CHCl3): 3384, 2970, 2872, 2098,
1
1460, 1257, 1094. 1-Iodo-2-heptanol. H-NMR (CDCl3): ꢀ 0.89 (s,
3H), 0.91–1.36 (m, 8H), 2.60 (s, 1H), 3.11–3.33 (m, 2.73H, major),
3.35–3.67 (m, 0.27H, minor). IR (CHCl3): 3363, 2956, 2920, 2851,
1458, 1017. Entry 9. 1-Azido-3-chloro-2-propanol. 1H-NMR
(CDCl3): ꢀ 2.58 (s, 1H), 3.72–3.74 (m, 4H), 4.10–4.08 (m, 1H). IR
(CHCl3): 3379, 2970, 2868, 2098, 1460, 1258, 1092. 3-Chloro-1-iodo-
1
2-propanol. H-NMR (CDCl3): ꢀ 2.54 (s, 1H), 3.71–3.73 (m, 4H),
4.06–4.08 (m, 1H). IR (CHCl3): 3360, 2922, 2860, 1458, 1258, 1017.