I2-mediated photochemical preparation of 2-substituted 1,3-dioxolanes and tetrahydrofurans from alcohols with polymer-supported hypervalent iodine reagent, PSDIB

Article abstract of DOI:10.1055/s-2005-864802

Various 2-substituted 1,3-dioxolanes, 1,3-dioxanes, and tetrahydrofurans were obtained selectively in good to moderate yields from the corresponding alcohols with PSDIB in the presence of iodine under irradiation conditions. Moreover, PSDIB was repeatedly used for the same reactions keeping good yield of the cyclic product.

Full text of DOI:10.1055/s-2005-864802

LETTER
923
I2-Mediated Photochemical Preparation of 2-Substituted 1,3-Dioxolanes and
Tetrahydrofurans from Alcohols with Polymer-Supported Hypervalent Iodine
Reagent, PSDIB
I
-Mediated
P
ho
o
tochemical
P
reparation of 2-Sub
o
stituted 1,3-
m
Dioxolane
s
asa Teduka,a Hideo Togo*a,b
2
a
Graduate School of Science and Technology, Chiba University, Yayoi-cho 1-33, Inage-ku, Chiba 263-8522, Japan
b
Department of Chemistry, Faculty of Science, Chiba University, Yayoi-cho 1-33, Inage-ku, Chiba 263-8522, Japan
E-mail: togo@faculty.chiba-u.jp
Received 24 January 2005
At first, the formation of 2-aryl-1,3-dioxolane from 2-
(arylmethoxy)ethanol with PSDIB in the presence of io-
dine under irradiation with a tungsten lamp was exam-
ined. Thus, when 2-(benzyloxy)ethanol (1a) was treated
Abstract: Various 2-substituted 1,3-dioxolanes, 1,3-dioxanes, and
tetrahydrofurans were obtained selectively in good to moderate
yields from the corresponding alcohols with PSDIB in the presence
of iodine under irradiation conditions. Moreover, PSDIB was re-
peatedly used for the same reactions keeping good yield of the with PSDIB (1.6 equiv) and iodine (0.6 equiv) in acetoni-
cyclic product.
trile at 30 °C under irradiation, 2-phenyl-1,3-dioxolane
(2a) was obtained in 72% yield as shown in Table 1 (entry
1). In spite of the heterogeneous solution, photolytic radi-
cal reaction proceeded effectively. Other alcohols (1)
bearing p- and m-substituted aryl group also provided 2-
aryl-1,3-dioxolanes 2 in good to moderate yields under
Key words: poly[4-(diacetoxyiodo)styrene] (PSDIB), 1,3-diox-
olane, 1,3-dioxane, tetrahydrofuran, alkoxyl radical, cyclization,
iodine, 1,5-H shift
Recently, extensive study on hypervalent iodine com- the same reaction conditions (entries 2–7). The same
pounds has been carried out and the compounds have been treatment of 4-phenylbutanol and 5-phenylpentanol also
widely used for organic synthesis.1 Since Suárez and co- provided 2-phenyltetrahydrofuran and 2-benzyltetrahy-
workers first reported that alkoxyl radicals could be gen- drofuran in good yields, respectively (entries 8, 9). In en-
erated from alcohols by the reaction of (diacetoxy- try 9, 2-phenyltetrahydropyran, cyclized through 1,6-H
iodo)benzene (DIB) or iodosylbenzene with iodine under shift, was also obtained in 2% yield, as a by-product.
irradiation conditions, providing a tetrahydrofuran skele- Then, alcohols (1j–m) bearing a tertiary carbon at the
ton,2a synthetic use of hypervalent iodine compounds d-position were employed as substrates under the same
through radical pathways has been extensively studied.2 reaction conditions, and the corresponding spiro cyclic
This method is very useful because a new carbon–oxygen compounds (2j–m) bearing a 1,3-dioxolane skeleton were
bond can be formed at non-activated positions, and the obtained again in good to moderate yields as shown in
reaction can be carried out under mild and neutral condi- Table 2. In these reactions, 6-membered cyclic com-
tions. Therefore, direct conversion of 2-alkoxyalcohols to pounds through 1,6-H shift were not obtained. Thus, se-
1,3-dioxolanes, cyclic acetals, is also possible.2e On the lective preparation of 2-substituted 1,3-dioxanes was
other hand, polymer-supported reagents have recently be- carried out by the same treatment. When 3-(aryl-
come important and popular,3 since reactions can be mon- methoxy)propanols were used under the same conditions,
itored by standard methods (TLC, GC, HPLC, etc.), 2-aryl-1,3-dioxanes, cyclized through 1,6-H shift, were
reaction products can be obtained by simple filtration to predominantly formed in good yields as shown in
remove the polymer-supported reagent, and regeneration Equation 1.
and reuse of the recovered polymer-supported reagents
A plausible reaction mechanism for the formation of 1,3-
are possible, thus providing an environmentally benign
dioxolanes is shown in Scheme 1. Thus, after stirring a
system. Here, as a part of our study toward environmen-
mixture of alcohol and PSDIB in the presence of iodine in
tally benign organic synthesis using polymer-supported
acetonitrile, alkyl hypoiodite is formed at first. Under
hypervalent iodine reagents,4 we would like to report an
irradiation with a tungsten lamp, bond cleavage of the O-
efficient, simple, and environmentally benign preparation
I bond in the alkyl hypoiodite formed occurs to generate
of 2-substituted 1,3-dioxolanes and tetrahydrofurans, that
the corresponding alkoxyl radical. This alkoxyl radical in-
are important skeletons for natural products and pharma-
duces 1,5-H shift to generate 1,4-iodohydrine, and finally,
ceuticals,5 from alcohols with poly[4-(diacetoxyiodo)sty-
cyclization of 1,4-iodohydrine occurs to provide 1,3-diox-
rene] (PSDIB) under irradiation with a tungsten lamp.
olane. After these reactions, polymer species were recov-
ered, regenerated, and reused. Thus, preparation of 2-
phenyl-1,3-dioxolane (2a) from 2-benzyloxyethanol (1a)
SYNLETT 2005, No. 6, pp 0923–0926
0
6.
0
4.
2
0
0
5
Advanced online publication: 23.03.2005
DOI: 10.1055/s-2005-864802; Art ID: U02605ST
© Georg Thieme Verlag Stuttgart · New York

924
T. Teduka, H. Togo
LETTER
Table 1 Photochemical Preparation of 2-Aryl-1,3-dioxolanes and 2-Aryl-1,3-tetrahydrofurans from Alcohols with PSDIB in the
Presence of I2
I(OAc)2 (PSDIB) (1.6 equiv)
O
I2 (0.6 equiv), hν
OH
R
X
MeCN, 30 °C
X
R
1
2
Entry
1
R
Product
Time (h)
2
Yield (%)
X = O
X = O
2a
72
(71)a
(76)b
2
2b
1
54
H3C
3
4
5
6
7
X = O
X = O
X = O
X = O
X = O
2c
2d
2e
2f
1
57
57
63
47
76
Br
Cl
F
1
1
1.5
2
O2N
O2N
2g
8
9
X = CH2
X = CH2
2h
2i
2
3
58
55c
a Yield with the first-regenerated PSDIB.
b Yield with the second-regenerated PSDIB.
c 2-Phenyltetrahydropyran was obtained in 2% yield.
OH
I(OAc)2
+
R
O
I(OAc)2
(1.6 equiv)
R
O
I2 (0.6 equiv), hν
O
R
O
OH
O
R
MeCN, 30 °C
O
+
HOAc
I
OAc
70% (2n)
62% (2o)
1.5 h
1.5 h
R =
I2
O2N
hν
OI
O
R
O
R
O
1,5-H shift
Equation 1
I
O
I2
OH
R
O
OH
–HI
O
R
O
I–
R
with the first-regenerated PSDIB and the second-regener-
ated PSDIB in the presence of iodine was carried out un-
der the same conditions, and yields of 2-phenyl-1,3-
dioxolane (2a) using the first-regenerated PSDIB and the
second-regenerated PSDIB were almost the same as that
using the original PSDIB as shown in entry 1 (Table 1).
–e–
OH
R
O
Scheme 1 Plausible reaction mechanism
Synlett 2005, No. 6, 923–926 © Thieme Stuttgart · New York

LETTER
I2-Mediated Photochemical Preparation of 2-Substituted 1,3-Dioxolanes
925
Table 2 Photochemical Preparation of Spiro Cyclic Compounds Bearing 1,3-Dioxolane Skeleton from Alcohols
I(OAc)2 (1.6 equiv)
I2 (0.6 equiv), hν
Substrate
Product
2
MeCN, 30 °C
1
Entry
1
Substrate
Product
Time (h)
1.5
Yield (%)
88
O
O
O
OH
1j
2j
2
3
2
95
71
O
OH
O
O
1k
2k
1.5
OH
O
O
O
t-Bu
t-Bu
1la
2l
4
3b
41
C8H17
C8H17
OH
O
O
O
1m
2m
a Isomeric ratio = 1:1.2.
b Solvent was 1,2-dichloroethane.
a tungsten lamp (300 W) for 1.5 h at 30 °C. The resulting mixture
was quenched with aq Na2SO3, and Et2O was added into the solu-
tion to precipitate the polymer species. The solution was filtered to
remove the polymer species, and the filtrate was poured into H2O
and extracted with Et2O (3 ꢀ 20 mL). The extract was dried over
Na2SO4 and evaporated. The residue was purified by flash column
chromatography (eluent: hexane–EtOAc, 1:1) to give 2-(4¢-nitro-
phenyl)-1,3-dioxolane in 47% yield.
In conclusion, various 2-substituted 1,3-dioxolanes, 1,3-
dioxanes, and tetrahydrofurans were obtained selectively
in good to moderate yields from the corresponding alco-
hols with PSDIB in the presence of iodine under irradia-
tion conditions with a tungsten lamp. Moreover, PSDIB
was repeatedly used for the same reactions, keeping good
yield of the cyclized product. Thus, the present method is
useful and environmentally benign for the preparation of
2-substituted 1,3-dioxolanes, 1,3-dioxanes, and tetrahy-
drofurans.
2-(4¢-Nitrophenyl)-1,3-dioxolane (2f): mp 87–88 °C (lit.8 mp
1
90 °C). IR (KBr): 2980, 2900, 1520, 1350, 1080, 850 cm–1. H
NMR (400 MHz, CDCl3): d = 4.06–4.15 (4 H, m), 5.90 (1 H, s),
7.66 (2 H, d, J = 8.6 Hz), 8.24 (2 H, d, J = 8.6 Hz).
Typical Experimental Procedure:7 Preparation of 2-(4¢-Nitro-
phenyl)-1,3-dioxolane from 2-(4¢-Nitrobenzyloxy)ethanol
After stirring a mixture of PSDIB6 (0.52 g, 0.8 mmol) and 2-(4¢-ni-
trobenzyloxy)ethanol (0.5 mmol) for 0.5 h under dark conditions,
iodine (0.6 mmol) was added. Then, the solution was irradiated with
Acknowledgment
Financial support from a Grant-in-Aid for Scientific Research
(16655012) by the Ministry of Education, Science, Sports and
Culture is gratefully acknowledged.
Synlett 2005, No. 6, 923–926 © Thieme Stuttgart · New York

926
T. Teduka, H. Togo
LETTER
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1 1997, 787. (m) Hernández, R.; León, E. I.; Moreno, P.;
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(v) Hernandez, R.; Leon, E. I.; Moreno, P.; Riesco-Fagundo,
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Synlett 2005, No. 6, 923–926 © Thieme Stuttgart · New York