BiI3 mediated difunctionalization of α-methylstyrenes, including azidohydroxylation and azidoiodination

Article abstract of DOI:10.1016/j.tet.2018.01.023

BiI₃ mediated vicinal azidohydroxylation of α-methylstyrenes 1 with NaN₃ in wet DMF affords β-azidoalcohols 4 in good yields. In dry DMF, β-azidoiodides 6 are also obtained by BiI₃ mediated vicinal azidoiodination of α-met

Full text of DOI:10.1016/j.tet.2018.01.023

Tetrahedron 74 (2018) 1002e1008
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BiI3 mediated difunctionalization of a-methylstyrenes, including
azidohydroxylation and azidoiodination
, b, *
Nai-Chen Hsueh a, Chieh-Kai Chan a, Meng-Yang Chang a
a Department of Medicinal and Applied Chemistry, Kaohsiung Medical University, Kaohsiung 807, Taiwan
b Department of Medical Research, Kaohsiung Medical University Hospital, Kaohsiung 807, Taiwan
a r t i c l e i n f o
a b s t r a c t
Article history:
BiI3 mediated vicinal azidohydroxylation of
a
-methylstyrenes 1 with NaN3 in wet DMF affords
-azidoiodides 6 are also obtained by BiI3 mediated vicinal
-methylstyrenes 1 with NaN3. This present protocol provides the bond formations of
b-azi-
Received 17 November 2017
Received in revised form
9 January 2018
Accepted 12 January 2018
Available online 24 January 2018
doalcohols 4 in good yields. In dry DMF,
azidoiodination of
b
a
carbon-azido/carbon-hydroxy (N3eCCeOH) bond and carbon-azido/carbon-iodo (N3eCCeI) under
water-controlled conditions.
© 2018 Elsevier Ltd. All rights reserved.
Keywords:
Bismuth iodide
Azidohydroxylation
a
b
-methylstyrenes
-Azidoalcohols
1. Introduction
hydroxytrifluoromethylation (F3CeCCeOH),1k Fe3þ catalyzed acy-
loxyalkylation (ReCCeOCOR),1l Cuþ/Mn2þ cyanophosphinoylation
Vicinal difunctionalization of olefin has attracted much atten-
tion, resulting in various synthetic strategies for its construction.
Among these diversified routes, halogenation, halohydroxylation
and dihydroxylation reactions are commonly found di-
heterofunctionalization reactions in fundamental textbooks.
These organic molecules containing vicinal di-heteroatoms form
one of the most important motifs present in natural sources,
functionalized materials and bioactive molecules. Recently, a
number of transition metal complexes, bases or oxidants mediated
one-pot methods for preparing various 1,2-difunctionalized al-
kenes have been developed,1 including Ni2þ catalyzed alkyl-
(NCeCCePOR2)1m and Cu2þ/I3þ catalyzed azidocyananation
(N3eCCeCN).1n However, straightforward vicinal azidohydrox-
ylation (N3eCCeOH) across unsymmetrical olefins in a requisite
regioselective fashion is rare.2
For this 1,2-azidohydroxylation reaction, different organo-
reagents promoting the intermolecular one-step are the major
pathways, as shown in Scheme 1. Sudalai and coworkers developed
a I2/TBHP-controlled regiodivergent azidohydroxylation of alkenes
with NaN3.2a Studer and Zhang demonstrated
a TEMPONa-
mediated stereoselective radical azidooxygenation of alkenes
with a N3-iodine(III) reagent.2b Liang et al. reported a PhI(OAc)2-
mediated metal-free three-component oxyazidation of alkenes,
TMSN3 and N-hydroxyphthalimide (NHPI).2c Chavan and Subbarao
described a (NH4)2Ce(NO3)6 mediated azidoalkoxylation of olefins
with NaN3 and alcohols.2d Jiao group investigated a MnBr2-medi-
ated hydroxyazidation of olefins with TMSN3 under open-vessel
condition.2e Yang and Lu explored a visible-light (LEDs)-promoted
aerobic hydroxyazidation of olefins with TMSN3.2f For the present
1,2-azidohydroxylation, diverse oxidants or catalysts and azido
sources have been highlighted via a one-pot, direct route under
different reaction conditions.
arylation
(ReCCeAr),1a
H2O2/SeO2
Pd2þ/Cu2þ
promoted
catalyzed
diarylation
(AreCCeAr),1b
alkoxyhydroxylation
(HOeCCeOR),1c-1d I3þ mediated diacetalation (ROCOeCCeOCOR),1e
organocatalyst mediated bromohydroxylation (BreCCeOH),1f Bi3þ
promoted hydroarylation (HeCCeAr),1g Select fluoro mediated
aminofluorination (FeCCeNHR),1h Er3þ promoted amino-
hydroxylation (HOeCCeNHR),1i Iꢀ/S2O82ꢀ mediated acet-
amidosulfenylation
(RSeCCeNHCOR),1j
Cuþ
mediated
The literature reveals that intermolecular direct installation of
hydroxyl and azido synthons into alkenes could provide the most
convenient access to vicinal azidohydroxylation of substituted a-
* Corresponding author. Department of Medicinal and Applied Chemistry,
Kaohsiung Medical University, Kaohsiung 807, Taiwan.
E-mail address: mychang@kmu.edu.tw (M.-Y. Chang).
https://doi.org/10.1016/j.tet.2018.01.023
0040-4020/© 2018 Elsevier Ltd. All rights reserved.

N.-C. Hsueh et al. / Tetrahedron 74 (2018) 1002e1008
1003
Table 1
Me
Me
Me
Me
Reaction Conditions.a
Ph
Ph
I
I , TBHP
2
TEMPO-Na
CH Cl
N
Me OH
Ph
Me
Ph
O
+
+
O
N
3
Me
Me
N
3
Et N, DMSO
3
(Sudalai work)
2
2
NaN
3
(Studer work)
N
3
O
Me
Me
Me
Ph
N
Me OMe
Ph
3
PhI(OAc)
2
(NH ) Ce(NO )
Ph
Ph
4
2
3
6
entry
2, azides
solvent
temp (ꢁC)
time (h)
4a (%)b
O
+
+
O
O
N
3
NHPI, (CH Cl)
MeOH
(Chavan work)
c
c
2
2
TMSN
NaN
3
N
1
2
3
4
5
6
7
8
2a, NaN3
2a, NaN3
2a, NaN3
2a, NaN3
2a, NaN3
2a, NaN3
2a, NaN3
2a, NaN3
2a, NaN3
2b, LiN3
DMF
DMF
DMF
DMF
DMF
DMF
MeCN
MeNO2
DMSO
DMF
DMF
DMF
25
25
100
2
20
2
2
3
1
2
2
2
2
2
2
－
－
3
(Liang work)
30
82
78
69
66
15
Me
Me
reflux
reflux
reflux
reflux
reflux
reflux
reflux
reflux
reflux
Me OMe
Ph
Me OH
Ph
MnBr
2
blue LEDs
air, toluene
Ph
Ph
+
+
air, MeCN
then PPh
(Jiao work)
N
N
3
3
TMSN
TMSN
3
3
then PPh
3
3
(Lu work)
d
9
－
10
11
12
58
Scheme 1. Synthetic routes for azidohydroxylation.
c
2c, TMSN3
2a, NaN3
－
－
cee
a
Reactions were run on a 0.5 mmol scale with 1a, azides (2, 1.2 equiv) in H2O
(0.5 mL), BiI3 (3a, 1.2 equiv), solvent (5 mL), 2 h.
methylstyrenes. Based on the above-mentioned routes, herein, we
developed an economical synthesis of -azidoalcohol 4 via a bis-
muth iodide (BiI3, 3a) mediated regioselective 1,2-
azidohydroxylation of substituted -methylstyrene 1 (an unsym-
b
b
Isolated yields.
No reaction.
Complex mixture.
c
d
a
e
No addition of BiI3 (3a).
metrical olefin) with sodium azide (NaN3, 2a) in wet DMF (a
cosolvent of DMF and H2O, v/v ¼ 10:1) at rt in good yields (Scheme
2). BiI3 is a stable, commercially available solid that has been
underutilized in organic synthesis.3,4 BiI3 mediated functional
group transformations included: (1) guanylation of thioureas,4a (2)
deprotection of ketals or acetals,4b (3) allylation of aldehydes,4c-e
and (4) sulfenylation of carbonyl synthons.4f
TMSN3 (entries 10e11). Other metal iodides (3b, AgI; 3c, CuI; 3d,
MgI2; 3e, InI3) were also investigated, but no reactions were initi-
ated under the above conditions (boiling DMF, NaN3, 2 h). By the
removal of BiI3, no reaction was observed, and 4a was not isolated
(entry 12). In terms of optimal yield and reactivity, we believe that
the BiI3/NaN3 combination system should be an optimal combi-
nation for the formation of 4a.
2. Results and discussion
According to above optimal reaction conditions, we explored
the substrate scope, and the results are shown in Scheme 3. To
adjust the Ar group of 1a-1j (Ar ¼ a, Ph; b, 4-FC6H4; c, 4-NO2C6H4;
d, 4-CF3C6H4; e, 4-PhC6H4; f, 3,4-Cl2C6H3; g, 3-FC6H4; h, 4-
pyridinyl; i, 4-naphthyl; j, tetralinyl), 4a-4j were provided in a
range of 43%e82% yields. For the Ar substituent, the electron-
neutral aryl groups and electron-withdrawing aryl groups were
well tolerated. The heterocyclic (for 1h) and bicyclic (for 1i, 1j) ring
systems also performed well, especially, for the BiI3 mediated re-
action of 1k-1l with the electron-donating aryl group (k, 3,4-
CH2O2C6H3; l, 3,4,5-(MeO)3C6H2) and NaN3, where no desired 1,2-
azidoalcohol product was obtained, and only 5a-5b having the
indane skeleton were isolated in 67% and 63% yield, respectively.5
According to reports on the direct azidohydroxylation of
a-
methylstyrene 1 having an unsymmetrical olefin motif, Sudalai,2a
Studer,2b Liang2c and Chavan2d showed that oxidants promoted
carbon-azido and carbon-hydroxy bond formations with different
azido sources (NaN3, TMSN3 and N3-iodine(III) reagent). In the
study, three azides (2a, NaN3; 2b, LiN3; 2c TMSN3) were examined
first for different reaction solvents (DMF, MeNO2, MeCN and
DMSO), temperature (rt and reflux) and time (1, 2, 3 and 20 h)
during BiI3 (3a) mediated azidohydroxylation of the model sub-
strate 1a process, as shown in Table 1. When the reaction of 1a and
3a was treated with NaN3 in DMF at rt for 2 and 20 h (entries 1e2),
no reactions were observed. After elevating the temperature
(25 /100 / reflux), the isolated yields of the desired 4a were
increased to 30% and 82% for 2 h, respectively (entries 3e4). The
optimal yield was obtained in 2 h, and prolonging or shortening
reaction time to 3 or 1 h afforded lower yields of the desired 4a
(entries 5e6). Furthermore, the factor of reaction solvent was
studied. After changing the solvents from boiling DMF to MeNO2,
MeCN or DMSO, the results showed that only MeCN (entry 7)
provided a moderate yield producing 4a (66%) in contrast to MeNO2
Me
Me
Me
BiI (3a)
3
Me OH
Ar
NaN (2a)
+
Ar
3
Ar
1a-1l
wet DMF
N
3
Me
Ar
4a-4j
(for 1a-1j)
5a-5b
(for 1k-1l)
Me OH
Me OH
Me OH
Me OH
Me OH
and DMSO (entries 8e9). For the azidohydroxylation of
a
-methyl-
Cl
Cl
F
styrene 1a, we believe that DMF should be an optimal solvent
among these polar solvents. With the results in hand, other azide
sources (2b and 2c) were explored next. Under similar conditions,
LiN3 gave only a 58% yield of 4a; however, there was no reaction for
N
N
N
N
N
N
3
3
3
3
3
Y
4f (70%)
4g (81%)
4h (70%)
4i (72%)
4a, Y = H (82%)
4b, Y = F (80%)
4c, Y = NO (76%)
2
4d, Y = CF (75%)
4e, Y = Ph (73%)
3
Me
Me
Me
Me
MeO
MeO
O
O
Me OH
N
3
OH
Me
1
BiI (3a)
3
Me
Ar
OMe
OMe
Me
5a (67%)
Scheme 3. Synthesis of 4e5.
O
Me
N
3
NaN (2a)
+
3
MeO
Ar
wet DMF
O
4j (43%)
5b (63%)
4
MeO
Scheme 2. Our route for azidohydroxylation.

1004
N.-C. Hsueh et al. / Tetrahedron 74 (2018) 1002e1008
1 + H O
From the results, we found that dimerization of vinylarenes having
an oxygenated aryl group was easier to initiate than the azidohy-
droxylation route because the electron-donating group could sta-
bilize the intermediate with tertiary carbocation. Overall, for the
2
I
or
H O
OH
Bi
2
I
Me
Me
BiI
Me
1
Me
A
1
3
I
Me
Ar
I
Bi
OH
Ar
C-2
Bi
for 1k-1l
Ar
Ar
DMF
I
I
Ar
dry DMF
I
for 1a-1b, 1d, 1f, 1h
wet DMF
H O
electronic effect of a Y substituent on the skeleton of
a-methyl-
B
2
styrenes 1, the electron-donating oxygenated group was inappro-
priate for the formation of 4.
for 1a-1j
OH
Bi
OH
Me
HI
I
I
HO
OH
Bi
N
3
With the results at hand, an anhydrous reaction condition was
examined next. Interestingly, when water was removed from the
BiI3 mediated reaction of 1 with NaN3 under a dry DMF condition, 6,
having the skeleton of 1,2-azidoiodide was generated. As shown in
Scheme 4, treatment of 1a-b, 1d, 1f and 1h (Ar ¼ a, Ph; b, 4-FC6H4;
d, 4-CF3C6H4; f, 3,4-Cl2C6H3; h, 4-pyridinyl) with BiI3 and NaN3 in
the absence of H2O, provided 6a-6e in a range of 51%e76% yields.
Based on the results, three possible reaction mechanisms were
combined and shown in Scheme 5. Initially, the intermediate A was
generated from the complex of 1a with BiI3. Next, A was converted
to intermediate B of a Bi3þ complex along with the removal of an
iodide ion. For the reactions of 1a-1j, C-1 was produced by inter-
molecular substitution of B with the water (a wet DMF con-
dition).3i,6 Among the process, in-situ formed HI and azide could
generate iodide and HN3. Then, iodide ion inserted into C-1 to
afford the resulting D. Subsequently, the coordination of D with
HN3 led to 4 via the five-membered ring transition state. The
releasing dioxybismuth iodide ion trapped excess H2O to produce
Bi(OH)3 and iodide ion.3i,4b
For the reactions of 1k-1l, C-2 was produced by intermolecular
substitution of the other 1 via the ene-reaction route. By intra-
molecular Friedel-Crafts alkylative ring-closure of C-2 and
sequential dehydrogenative aromatization of E, F was formed by
the cascade dimerization process. Furthermore, the resulting HN3
continued the debismuthation from F to 5.7 The resulting azido-
bismuth dihydroxide ion trapped excess H2O to produce Bi(OH)3
and HN3. This results was similar to Hua work (by BiCl3-mediated
dimerization reaction of 1).5a
Ar
Me
Ar
Me
Bi
I
OH
Ar
E
Ar
H
N
H
I +
3
Me
C-3
C-1
N
I
3
HI
I
I
N
3
H O
2
Me
Ar
Bi
N
3
H
H
N
OH
3
I +
HO
HO
I
N
3
Me
Me
Me
Bi(OH) + I
3
Bi
Bi
OH
G
Ar
OH
H
Ar
H O
work-up
I
OH
Bi
2
D
N
3
Ar
Bi
O
O
I
I
Me
Me
F
Me
Ar
Me OH
Ar
Me
Ar
I
OH
Bi
OH
Bi(OH)
+
3
H O
2
Ar
5
N
N H
3
3
N
3
N
3
6
4
Scheme 5. Possible mechanisms.
Me
Me OH
Me
Ar
BiI (3a)
3
SPh
or
+
NaSPh (2d)
wet DMF
SPh
SPh
O N
2
Cl
Cl
Cl
1c, 1m
7a (26%)
for 1c
7b (61%)
for 1m
7b-1 (10%)
for 1m
Me OH
Me OH
Me
Ar
BiI (3a)
3
or
SO Ph
NaSO Ph (2e)
2
SO Ph
2
2
O N
wet DMF
2
1c, 1m
8a (49%)
for 1c
8b (77%)
for 1m
OH
BiI (3a)
3
Ph
Ph
1n
NaN (2a)
3
wet DMF
N
3
For the reactions of 1a-1b, 1d, 1f and 1h, C-3 was produced via
intermolecular substitution with the releasing iodide ion (a dry
DMF condition). After the nucleophilic substitution of C-3 with
azide occurred, G was formed. Following a work-up process, 6 was
yielded along with the generation of oxybismuth diiodide ion. By
the involvement of water¸ the suspended solids of Bi(OH)3 were
produced.
4n (56%)
Scheme 6. Synthesis of 7e8.
electronic inductive effect. For the generation of 7a with a more
stable trisubstituted endo-olefin (via Zaitsev rule), a stronger
deactivating nitro group could stabilize the in-situ formed tertiary
carbocation under the thermodynamic condition. In the other way,
a weaker deactivating chloro group could not stabilize easily the
formed tertiary carbocation such that 7b-1 having a terminal exo-
olefin was obtained in low yield (by Hoffman rule). By BiI3 mediated
hydroxysulfenylation of 1 with 2d, obvious variants were detected
in the distribution of different products. Furthermore, attempts to
produce BiI3 mediated hydroxysulfonylation of 1c and 1m with 2e
also provided 8a and 8b in 49% and 77% yields, respectively. The
structural frameworks of 8a and 8b were determined by single-
A
variety of hydroxysulfenylated and hydroxysulfonylated
products were obtained when the sodium salt was changed from
NaN3 (2a) to NaSPh (2d) or NaSO2Ph (2e), respectively, as shown in
Scheme 6. Under the similar conditions, BiI3 mediated reaction of
1c (Ar ¼ 4-NO2C6H4) with 2d was studied first. However, no
hydroxysulfenylated product was detected and only 7a was isolated
in a low (26%) yield because the nitro substituent is a strong
electron-withdrawing group. After changing 1c to 1m (Ar ¼ 4-
ClC6H4), the desired 1,2-hydroxysulfide 7b was produced in a 61%
yield along with 10% dehydrated 7b-1. For the isolation of different
olefinic isomers 7a and 7b-1, the results should be controlled by
crystal X-ray crystallography (Figs. 1e2).8 Besides the
a-methyl-
stryrene (1a), a simple styrene (1n) was treated with the optimal
condition, however, the desired 4n was isolated in only a 56% yield.
Based on the experimental results, the present optimal BiI3/NaN3
mediated conditions were appropriate for the hydroxysulfenylation
Me
BiI (3a)
3
Me
Ar
I
NaN (2a)
+
3
Ar
1a-1b, 1d, 1f, 1h
and hydroxysulfonylation of
droxylation of styrene.
a
-methylstyrenes and the azidohy-
dry DMF
N
3
6a-6e
Me
As an extension for vicinal difunctionalization of
a
-methylstyr-
Me
I
Me
I
Me
I
I
Me
I
ene, changing the promoter from BiI3 to I2 was explored next, as
shown in Scheme 7. By the removal of NaN3, treatment of 1g with I2
provided 9a in a 64% yield. This implies that I2 activates 1g to afford
the iodonium ion intermediate. After intermolecular cross-
coupling of the resulting tertiary carbocation of 1g and another
Cl
N
N
N
N
N
N
3
3
3
3
3
F
F C
3
Cl
6a (76%)
6b (68%)
6c (73%)
6d (70%)
6e (51%)
Scheme 4. Synthetic route to azidoiodination.

N.-C. Hsueh et al. / Tetrahedron 74 (2018) 1002e1008
1005
with NaN3 in wet and dry DMF afford
b-azidoalcohols and
b
-azi-
doiodides in moderate to good yields. The plausible mechanisms
have been discussed and proposed. On the other hand, we also
described BiI3 mediated hydroxysulfenylation and hydrox-
ysulfonylation of
wet DMF. Further investigation regarding synthetic applications of
-methylstyrenes will be conducted and published in due course.
a-methylstyrenes with NaSPh and NaSO2Ph in
a
4. Experimental section
4.1. General
All reagents and solvents were obtained from commercial
sources and used without further purification. Reactions were
routinely carried out under an atmosphere of dry air with magnetic
stirring. Products in organic solvents were dried with anhydrous
magnesium sulfate before concentration in vacuo. Melting points
were determined with a SMP3 melting apparatus. 1H and 13C NMR
spectra were recorded on a Varian INOVA-400 spectrometer oper-
Fig. 1. X-ray structure of 8a.
ating at 400 and 100 MHz, respectively. Chemical shifts (d) are re-
ported in parts per million (ppm) and the coupling constants (J) are
given in Hertz. High resolution mass spectra (HRMS) were
measured with a mass spectrometer Finnigan/Thermo Quest MAT
95XL. X-ray crystal structures were obtained with an Enraf-Nonius
FR-590 diffractometer (CAD4, Kappa CCD).
4.2. A representative synthetic procedure of compounds 4a-4j, 4n
and 5a-5b is as follows
BiI3 (3a, 354 mg, 0.6 mmol) was added to a stirred solution of
1a-1l, 1n (0.5 mmol) in DMF (5 mL) at 25 ꢁC. The reaction mixture
was stirred at 25 ꢁC for 15 min NaN3 (2a, 39 mg, 0.6 mmol) in H2O
(0.5 mL) was added to the reaction mixture at 25 ꢁC. Then, the re-
action mixture was stirred at reflux for 2 h. The reaction mixture
was cooled to 25 ꢁC and the solvent was concentrated. The residue
was diluted with water (10 mL) and the mixture was extracted with
CH2Cl2 (3 ꢂ 20 mL). The combined organic layers were washed with
brine, dried, filtered and evaporated to afford crude product under
reduced pressure. Purification on silica gel (hexanes/EtOAc ¼ 8/
1e4/1) afforded 4a-4j, 4n and 5a-5b.
4.2.1. 1-Azido-2-phenylpropan-2-ol (4a)
Fig. 2. X-ray structure of 8b.
Yield ¼ 82% (73 mg); Colorless oil; HRMS (ESI-TOF) m/z: [M þ
H]þ calcd for C9H12N3O 178.0980, found 178.0985; 1H NMR
(400 MHz, CDCl3):
d 7.48e7.45 (m, 2H), 7.41e7.36 (m, 2H),
I
7.33e7.28 (m, 1H), 3.61 (d, J ¼ 12.4 Hz, 1H), 3.45 (d, J ¼ 12.0 Hz, 1H),
Me
F
Me
2.21 (br s, 1H), 1.60 (s, 3H); 13C NMR (100 MHz, CDCl3):
d 144.62,
I
2
F
128.45 (2ꢂ), 127.48, 124.80 (2ꢂ), 74.54, 62.09, 27.08.
wet DMF
HO
9a (64%)
Me
F
1g
4.2.2. 1-Azido-2-(4-fluorophenyl)propan-2-ol (4b)
Yield ¼ 80% (78 mg); Colorless oil; HRMS (ESI-TOF) m/z: [M þ
I
I
I
+
I
H]þ calcd for C9H11FN3O 196.0886, found 196.0892; 1H NMR
Me
Me
Me
F
F
F
(400 MHz, CDCl3):
J ¼ 12.0 Hz, 1H), 3.43 (d, J ¼ 12.0 Hz, 1H), 2.38 (br s, 1H), 1.58 (s, 3H);
13C NMR (100 MHz, CDCl3):
d 7.45e7.40 (m, 2H), 7.08e7.02 (m, 2H), 3.57 (d,
Me
Me
H O
2
d
162.09 (d, J ¼ 244.8 Hz), 140.41 (d,
F
F
J ¼ 3.0 Hz), 126.69 (d, J ¼ 7.6 Hz, 2ꢂ), 115.22 (d, J ¼ 21.3 Hz, 2ꢂ),
74.24, 62.12, 27.19.
Scheme 7. Synthesis of 9a.
1g, a resulting dimer with a new tertiary carbocation was gener-
ated. Subsequently, 9a was generated in the presence of water.
4.2.3. 1-Azido-2-(4-nitrophenyl)propan-2-ol (4c)
Yield ¼ 76% (84 mg); Colorless oil; HRMS (ESI-TOF) m/z: [M þ
H]þ calcd for C9H11N4O3 223.0831, found 223.0839; 1H NMR
3. Conclusion
(400 MHz, CDCl3):
d
8.19 (d, J ¼ 8.8 Hz, 2H), 7.63 (d, J ¼ 9.2 Hz, 2H),
3.61 (d, J ¼ 12.4 Hz, 1H), 3.52 (d, J ¼ 12.4 Hz, 1H), 2.60 (br s, 1H), 1.61
In summary, we have shown that BiI3 mediated vicinal azido-
hydroxylation and azidoiodination of substituted
(s, 3H); 13C NMR (100 MHz, CDCl3):
d
151.97, 147.10, 126.06 (2ꢂ),
a
-methylstyrenes
123.54 (2ꢂ), 74.47, 61.53, 27.06.

1006
N.-C. Hsueh et al. / Tetrahedron 74 (2018) 1002e1008
4.2.4. 1-Azido-2-(4-trifluoromethylphenyl)propan-2-ol (4d)
Yield ¼ 75% (92 mg); Colorless oil; HRMS (ESI-TOF) m/z: [M þ
H]þ calcd for C10H11F3N3O 246.0854, found 246.0859; 1H NMR
4.2.11. 5-Benzo[1,3]dioxol-5-yl-5,7,7-trimethyl-6,7-dihydro-5H-
indeno[5,6-d][1,3]dioxole (5a)
Yield ¼ 67% (54 mg); Colorless oil; HRMS (ESI-TOF) m/z: [M þ
(400 MHz, CDCl3):
3.61 (d, J ¼ 12.4 Hz, 1H), 3.49 (d, J ¼ 12.4 Hz, 1H), 2.43 (br s, 1H), 1.60
(s, 3H); 13C NMR (100 MHz, CDCl3):
d
7.64 (d, J ¼ 8.4 Hz, 2H), 7.58 (d, J ¼ 8.4 Hz, 2H),
H]þ calcd for C20H21O4 325.1440, found 325.1438; 1H NMR
(400 MHz, CDCl3):
d 6.71e6.62 (m, 4H), 6.53 (s, 1H), 5.96 (d,
d
148.62, 129.71 (q, J ¼ 32.6 Hz),
J ¼ 1.6 Hz, 1H), 5.95 (d, J ¼ 1.2 Hz, 1H), 5.91 (d, J ¼ 2.0 Hz, 1H), 5.91
(d, J ¼ 1.6 Hz, 1H), 2.34 (d, J ¼ 13.2 Hz, 1H), 2.16 (d, J ¼ 12.8 Hz, 1H),
1.61 (s, 3H), 1.29 (s, 3H), 1.05 (s, 3H); 13C NMR (100 MHz, CDCl3):
125.36 (4ꢂ), 121.34 (d, J ¼ 270.6 Hz), 74.42, 61.77, 27.08.
d
147.35, 147.19, 146.73, 145.33, 145.19 (2ꢂ), 141.49, 119.42, 107.63,
4.2.5. 1-Azido-2-biphenyl-4-ylpropan-2-ol (4e)
107.41, 104.90, 102.79, 101.01, 100.77, 59.68, 50.33, 42.56, 30.93,
30.87, 30.37.
Yield ¼ 73% (92 mg); Colorless oil; HRMS (ESI-TOF) m/z: [M þ
H]þ calcd for C15H16N3O 254.1293, found 254.1299; 1H NMR
(400 MHz, CDCl3):
d
7.63e7.58 (m, 4H), 7.53 (d, J ¼ 8.4 Hz, 2H),
7.47e7.43 (m, 2H), 7.38e7.34 (m, 1H), 3.66 (d, J ¼ 12.4 Hz, 1H), 3.50
4.2.12. 4,5,6-Trimethoxy-1,1,3-trimethyl-3-(3,4,5-
trimethoxyphenyl)indan (5b)
(d, J ¼ 12.4 Hz, 1H), 2.20 (br s, 1H), 1.64 (s, 3H); 13C NMR (100 MHz,
CDCl3):
d
143.66, 140.56, 140.43, 128.78 (2ꢂ), 127.38, 127.19 (2ꢂ),
Yield ¼ 63% (66 mg); Colorless oil; HRMS (ESI-TOF) m/z: [M þ
H]þ calcd for C24H33O6 417.2277, found 417.2273; 1H NMR
127.08 (2ꢂ), 125.33 (2ꢂ), 74.51, 62.10, 27.18.
(400 MHz, CDCl3):
d 6.43 (s, 1H), 6.37 (s, 2H), 3.85 (s, 3H), 3.78 (s,
3H), 3.76 (s, 3H), 3.72 (s, 6H), 3.57 (s, 3H), 2.29 (d, J ¼ 12.8 Hz, 1H),
4.2.6. 1-Azido-2-(3,4-dichlorophenyl)propan-2-ol (4f)
2.09 (d, J ¼ 13.2 Hz, 1H), 1.73 (s, 3H), 1.27 (s, 3H), 1.05 (s, 3H); 13C
Yield ¼ 70% (86 mg); Colorless oil; HRMS (ESI-TOF) m/z: [M þ
NMR (100 MHz, CDCl3):
d
153.68, 152.21 (2ꢂ), 149.99, 147.48,
H]þ calcd for C9H10Cl3N3O 246.0201, found 246.0208; 1H NMR
146.73, 140.81, 135.52, 132.56, 130.75 (2ꢂ), 100.66, 60.52, 60.25,
(400 MHz, CDCl3):
d
7.56 (d, J ¼ 2.4 Hz, 1H), 7.43 (d, J ¼ 8.4 Hz, 1H),
59.97, 59.82, 55.84, 55.76, 55.74, 50.79, 43.19, 30.81, 30.34, 28.91.
7.25 (dd, J ¼ 2.4, 8.4 Hz, 1H), 3.55 (d, J ¼ 12.4 Hz, 1H), 3.44 (d,
J ¼ 12.4 Hz, 1H), 2.41 (br s, 1H), 1.56 (s, 3H); 13C NMR (100 MHz,
CDCl3):
27.00.
d 144.94, 132.60, 131.52, 130.33, 127.31, 124.40, 73.97, 61.65,
4.2.13. 1-Azido-2-phenylethan-2-ol (4n)
Yield ¼ 56% (46 mg); Colorless oil; HRMS (ESI-TOF) m/z: [M þ
H]þ calcd for C8H10N3O 164.0824, found 164.0823; 1H NMR
(400 MHz, CDCl3):
d
7.40e7.32 (m, 5H), 4.88 (dd, J ¼ 3.6, 8.0 Hz, 1H),
4.2.7. 1-Azido-2-(3-fluorophenyl)propan-2-ol (4g)
3.48 (dd, J ¼ 8.0, 12.4 Hz, 1H), 3.42 (dd, J ¼ 3.6, 12.4 Hz, 1H), 2.60 (br
Yield ¼ 81% (79 mg); Colorless oil; HRMS (ESI-TOF) m/z: [M þ
s, 1H); 13C NMR (100 MHz, CDCl3):
d
140.66, 128.75 (2ꢂ), 128.34,
H]þ calcd for C9H11FN3O 196.0886, found 196.0892; 1H NMR
125.92 (2ꢂ), 73.25, 58.11.
(400 MHz, CDCl3):
(m, 1H), 3.55 (d, J ¼ 12.4 Hz, 1H), 3.41 (d, J ¼ 12.4 Hz, 1H), 2.41 (br s,
1H), 1.54 (s, 3H); 13C NMR (100 MHz, CDCl3):
162.91 (d,
d 7.33e7.27 (m,1H), 7.18e7.14 (m, 2H), 6.98e6.93
d
4.3. A representative synthetic procedure of compounds 6a-6e is as
follows
J ¼ 244.0 Hz), 147.42 (d, J ¼ 6.8 Hz), 129.98 (d, J ¼ 8.3 Hz), 120.44 (d,
J ¼ 3.0 Hz), 114.33 (d, J ¼ 21.2 Hz), 112.32 (d, J ¼ 22.8 Hz), 74.28 (d,
J ¼ 1.5 Hz), 61.85, 27.05.
BiI3 (3a, 354 mg, 0.6 mmol) was added to a stirred solution of
1a-1b, 1d, 1f and 1h (0.5 mmol) in dry DMF (5 mL) at 25 ꢁC. The
reaction mixture was stirred at 25 ꢁC for 15 min NaN3 (2a, 39 mg,
0.6 mmol) was added to the reaction mixture at 25 ꢁC. Then, the
reaction mixture was stirred at reflux for 2 h. The reaction mixture
was cooled to 25 ꢁC and the solvent was concentrated. The residue
was diluted with water (10 mL) and the mixture was extracted with
CH2Cl2 (3 ꢂ 20 mL). The combined organic layers were washed with
brine, dried, filtered and evaporated to afford crude product under
reduced pressure. Purification on silica gel (hexanes/EtOAc ¼ 8/
1e4/1) afforded 6a-6e.
4.2.8. 1-Azido-2-pyridin-4-ylpropan-2-ol (4h)
Yield ¼ 70% (62 mg); Colorless solid; mp ¼ 103e105 ꢁC (recrys-
tallized from hexanes and EtOAc); HRMS (ESI-TOF) m/z: [M þ H]þ
calcd for C8H11N4O 179.0933, found 179.0938; 1H NMR (400 MHz,
CDCl3):
d
8.42 (d, J ¼ 6.4 Hz, 2H), 7.39 (d, J ¼ 6.4 Hz, 2H), 5.15 (br s,
1H), 3.47 (d, J ¼ 12.4 Hz, 1H), 3.40 (d, J ¼ 12.4 Hz, 1H), 1.54 (s, 3H);
13C NMR (100 MHz, CDCl3):
73.60, 61.18, 26.48.
d
155.16, 148.83 (2ꢂ), 120.51 (2ꢂ),
4.2.9. 1-Azido-2-naphthalen-2-yl-propan-2-ol (4i)
4.3.1. (2-Azido-1-iodo-1-methylethyl)benzene (6a)
Yield ¼ 72% (82 mg); Colorless oil; HRMS (ESI-TOF) m/z: [M þ
H]þ calcd for C13H14N3O 228.1137, found 228.1135; 1H NMR
Yield ¼ 76% (109 mg); Colorless oil; HRMS (ESI-TOF) m/z: [M þ
H]þ calcd for C9H11IN3 287.9998, found 287.9990; 1H NMR
(400 MHz, CDCl3):
d
7.95 (d, J ¼ 2.0 Hz, 1H), 7.86 (d, J ¼ 8.8 Hz, 2H),
(400 MHz, CDCl3):
d 7.46e7.39 (m, 4H), 7.36e7.32 (m, 1H), 3.51 (d,
7.86e7.83 (m, 1H), 7.54e7.47 (m, 3H), 3.72 (d, J ¼ 12.4 Hz, 1H), 3.56
J ¼ 14.4 Hz, 1H), 3.48 (d, J ¼ 14.4 Hz, 1H), 1.89 (s, 3H); 13C NMR
(d, J ¼ 12.4 Hz, 1H), 2.41 (br s, 1H), 1.69 (s, 3H); 13C NMR (100 MHz,
(100 MHz, CDCl3):
25.16, 17.68.
d
140.73, 128.79 (2ꢂ), 128.27, 125.60 (2ꢂ), 65.07,
CDCl3):
d 141.99, 133.14, 132.60, 128.26, 128.19, 127.54, 126.32,
126.14, 123.76, 122.99, 74.74, 62.01, 27.18.
4.2.10. 2-Azido-1-methyl-1,2,3,4-tetrahydronaphthalen-1-ol (4j)
Yield ¼ 43% (44 mg); Colorless oil; HRMS (ESI-TOF) m/z: [M þ
H]þ calcd for C11H14N3O 204.1137, found 204.1133; 1H NMR
4.3.2. 1-(2-Azido-1-iodo-1-methylethyl)-4-fluorobenzene (6b)
Yield ¼ 68% (104 mg); Colorless oil; HRMS (ESI-TOF) m/z: [M þ
H]þ calcd for C9H10FIN3 305.9904, found 305.9910; 1H NMR
(400 MHz, CDCl3):
(d, J ¼ 8.0 Hz, 1H), 3.74 (dd, J ¼ 3.6, 12.0 Hz, 1H), 2.96e2.92 (m, 2H),
2.40 (br s,1H), 2.20e2.13 (m,1H),1.96e1.85 (m,1H),1.49 (s, 3H); 13
NMR (100 MHz, CDCl3): 141.68, 133.79, 128.24, 27.43, 126.64,
126.10, 74.26, 67.67, 27.51, 25.83, 25.26.
d
7.59 (d, J ¼ 8.8 Hz, 1H), 7.27e7.19 (m, 2H), 7.08
(400 MHz, CDCl3): d 7.44e7.39 (m, 2H), 7.11e7.05 (m, 2H), 3.49 (d,
J ¼ 10.4 Hz, 1H), 3.45 (d, J ¼ 10.4 Hz, 1H), 1.88 (s, 3H); 13C NMR
C
(100 MHz, CDCl3):
127.47 (d, J ¼ 8.3 Hz, 2ꢂ), 115.55 (d, J ¼ 21.2 Hz, 2ꢂ), 64.55, 25.07,
d
162.26 (d, J ¼ 247.2 Hz), 136.56 (d, J ¼ 3.8 Hz),
d
17.43.

N.-C. Hsueh et al. / Tetrahedron 74 (2018) 1002e1008
1007
4.3.3. 1-(2-Azido-1-iodo-1-methylethyl)-4-trifluoromethylbenzene
(6c)
Yield ¼ 73% (130 mg); Colorless oil; HRMS (ESI-TOF) m/z: [M þ
H]þ calcd for C10H10F3IN3 355.9872, found 355.9879; 1H NMR
(400 MHz, CDCl3):
7.67 (d, J ¼ 8.4 Hz, 2H), 7.57 (d, J ¼ 8.4 Hz, 2H),
3.51 (s, 2H), 1.91 (s, 3H); 13C NMR (100 MHz, CDCl3):
144.88,
4.5. A representative synthetic procedure of compounds 8a and 8b
is as follows
BiI3 (354 mg, 0.6 mmol) was added to a stirred solution of 1c and
1m (0.5 mmol) in DMF (5 mL) at 25 ꢁC. The reaction mixture was
stirred at 25 ꢁC for 15 min. A solution of NaSO2Ph (2e, 98 mg,
0.6 mmol) in H2O (0.5 mL) was added to the reaction mixture at
25 ꢁC. Then, the reaction mixture was stirred at reflux for 2 h. The
reaction mixture was cooled to 25 ꢁC and the solvent was
concentrated. The residue was diluted with water (10 mL) and the
mixture was extracted with CH2Cl2 (3 ꢂ 20 mL). The combined
organic layers were washed with brine, dried, filtered and evapo-
rated to afford crude product under reduced pressure. Purification
on silica gel (hexanes/EtOAc ¼ 8/1e4/1) afforded 8a and 8b.
d
d
130.36 (q, J ¼ 31.9 Hz), 126.10 (2ꢂ), 125.69 (q, J ¼ 3.8 Hz, 2ꢂ), 123.80
(d, J ¼ 270.6 Hz), 64.71, 25.05, 16.47.
4.3.4. 4-(2-Azido-1-iodo-1-methylethyl)-1,2-dichlorobenzene (6d)
Yield ¼ 70% (124 mg); Colorless oil; HRMS (ESI-TOF) m/z: [M þ
H]þ calcd for C9H9Cl2IN3 355.9218, found 355.9219; 1H NMR
(400 MHz, CDCl3):
d
7.52 (d, J ¼ 2.4 Hz, 1H), 7.46 (d, J ¼ 8.4 Hz, 1H),
7.25 (dd, J ¼ 2.4, 8.4 Hz, 1H), 3.45 (br s, 2H), 1.87 (s, 3H); 13C NMR
(100 MHz, CDCl3):
d 141.20, 132.92, 132.44, 130.62, 127.91, 125.05,
64.23, 24.93, 16.44.
4.5.1. 1-Benzenesulfonyl-2-(4-nitrophenyl)propan-2-ol (8a)
Yield ¼ 49% (79 mg); Colorless solid; mp ¼ 131e133 ꢁC (recrys-
tallized from hexanes and EtOAc); HRMS (ESI-TOF) m/z: [M þ H]þ
calcd for C15H16NO5S 322.0749, found 322.0749; 1H NMR (400 MHz,
4.3.5. 4-(2-Azido-1-iodo-1-methylethyl)pyridine (6e)
Yield ¼ 51% (73 mg); Colorless oil; HRMS (ESI-TOF) m/z: [M þ
H]þ calcd for C8H10IN4 288.9950, found 288.9953; 1H NMR
CDCl3 þ DMSO‑d6):
d
7.93 (d, J ¼ 8.8 Hz, 2H), 7.60e7.58 (m, 2H),
(400 MHz, CDCl3):
d
8.64 (d, J ¼ 6.4 Hz, 2H), 7.32 (d, J ¼ 6.4 Hz, 2H),
7.51e7.46 (m, 3H), 7.36e7.32 (m, 2H), 3.80 (d, J ¼ 14.8 Hz, 1H), 3.66
3.47 (s, 2H), 1.86 (s, 3H); 13C NMR (100 MHz, CDCl3):
d
150.33 (2ꢂ),
(d, J ¼ 14.4 Hz, 1H), 3.59 (br s, 1H), 1.62 (s, 3H); 13C NMR (100 MHz,
149.83, 120.50 (2ꢂ), 64.24, 24.79, 15.38.
CDCl3 þ DMSO‑d6):
d
152.43, 146.32, 140.13, 133.13, 128.64 (2ꢂ),
127.40 (2ꢂ), 126.05 (2ꢂ), 122.70 (2ꢂ), 72.12, 65.94, 30.19. Single-
crystal X-Ray diagram: crystal of compound 8a was grown by
slow diffusion of EtOAc into a solution of compound 8a in CH2Cl2 to
yield colorless prisms. The compound crystallizes in the monoclinic
crystal system, space group C 2/c, a ¼ 35.682(6) Å, b ¼ 5.6994(9) Å,
c ¼ 14.278(2) Å, V ¼ 2783.9(8) Å3, Z ¼ 8, dcalcd ¼ 1.533 g/cm3,
4.4. A representative synthetic procedure of compounds 7a, 7b and
7b-1 is as follows
BiI3 (3a, 354 mg, 0.6 mmol) was added to a stirred solution of 1c
and 1m (0.5 mmol) in DMF (5 mL) at 25 ꢁC. The reaction mixture
was stirred at 25 ꢁC for 15 min. A solution of NaSPh (2d, 79 mg,
0.6 mmol) in H2O (0.5 mL) was added to the reaction mixture at
25 ꢁC. Then, the reaction mixture was stirred at reflux for 2 h. The
reaction mixture was cooled to 25 ꢁC and the solvent was
concentrated. The residue was diluted with water (10 mL) and the
mixture was extracted with CH2Cl2 (3 ꢂ 20 mL). The combined
organic layers were washed with brine, dried, filtered and evapo-
rated to afford crude product under reduced pressure. Purification
on silica gel (hexanes/EtOAc ¼ 8/1e4/1) afforded 7a, 7b and 7b-1.
F(000) ¼ 1344,
R1 ¼0.0382, wR2 ¼ 0.0834.
2q R indices (all data)
range 1.190e26.026ꢁ,
4.5.2. 1-Benzenesulfonyl-2-(4-chlorophenyl)propan-2-ol (8b)
Yield ¼ 77% (119 mg); Colorless solid; mp ¼ 77e79 ꢁC (recrys-
tallized from hexanes and EtOAc); HRMS (ESI-TOF) m/z: [M þ H]þ
calcd for C15H16ClO3S 311.0509, found 311.0518; 1H NMR (400 MHz,
CDCl3):
d 7.40e7.34 (m, 3H), 7.22e7.19 (m, 2H), 7.05e7.02 (m, 2H),
6.92e6.88 (m, 2H), 4.76 (s, 1H), 3.60 (d, J ¼ 14.8 Hz, 1H), 3.45 (d,
J ¼ 14.4 Hz, 1H), 1.47 (s, 3H); 13C NMR (100 MHz, CDCl3):
d 142.75,
4.4.1. 2-(4-Nitrophenyl)-1-phenylsulfanylpropene (7a)
139.60, 132.80, 132.24, 128.48 (2ꢂ), 127.52 (2ꢂ), 126.96 (2ꢂ), 125.95
(2ꢂ), 71.94, 65.96, 29.98. Single-crystal X-Ray diagram: crystal of
compound 8a was grown by slow diffusion of EtOAc into a solution
of compound 8a in CH2Cl2 to yield colorless prisms. The compound
crystallizes in the orthorhombic crystal system, space group P b c a,
a ¼ 15.1722(16) Å, b ¼ 11.7576(14) Å, c ¼ 15.6862(19) Å,
Yield ¼ 26% (35 mg); Colorless oil; HRMS (ESI-TOF) m/z: [M þ
H]þ calcd for C15H14NO2S 272.0745, found 272.0740; 1H NMR
(400 MHz, CDCl3):
d
8.20 (d, J ¼ 8.8 Hz, 2H), 7.97 (d, J ¼ 8.4 Hz, 2H),
7.67e7.63 (m, 1H), 7.59 (d, J ¼ 8.0 Hz, 2H), 7.53 (d, J ¼ 8.8 Hz, 2H),
6.65 (d, J ¼ 1.2 Hz, 1H), 2.57 (d, J ¼ 1.2 Hz, 3H); 13C NMR (100 MHz,
CDCl3):
d
150.65, 148.28, 146.40, 141.28, 133.65, 130.31, 129.39 (2ꢂ),
V ¼ 1798.2(6) Å3, Z ¼ 8, dcalcd ¼ 1.475 g/cm3, F(000) ¼ 1296, 2
q range
127.34 (4ꢂ), 123.89 (2ꢂ), 17.20.
2.547e26.359ꢁ, R indices (all data) R1 ¼0.0315, wR2 ¼ 0.0699.
4.4.2. 2-(4-Chlorophenyl)-1-phenylsulfanylpropan-2-ol (7b)
Yield ¼ 61% (85 mg); Colorless oil; HRMS (ESI-TOF) m/z: [M þ
H]þ calcd for C15H16ClOS 279.0610, found 279.0613; 1H NMR
4.5.3. 2,4-Bis-(3-fluorophenyl)-5-iodo-4-methylpentan-2-ol (9a)
A solution of I2 (152 mg, 0.6 mmol) in H2O (0.5 mL) was added to
a solution of 1g (68 mg, 0.5 mmol) in wet DMF (5 mL) at 25 ꢁC. The
reaction mixture was stirred at 25 ꢁC for 10 min. Then, the reaction
mixture was stirred at reflux for 2 h. The reaction mixture was
cooled to 25 ꢁC and the solvent was concentrated. The residue was
diluted with water (10 mL) and the mixture was extracted with
CH2Cl2 (3 ꢂ 20 mL). The combined organic layers were washed with
brine, dried, filtered and evaporated to afford crude product under
reduced pressure. Purification on silica gel (hexanes/EtOAc ¼ 8/
1e4/1) afforded 9a. Yield ¼ 64% (133 mg); Colorless oil; HRMS (ESI-
TOF) m/z: [M þ H]þ calcd for C18H20F2IO 417.0527, found 417.0523;
(400 MHz, CDCl3):
d
7.36 (d, J ¼ 8.4 Hz, 2H), 7.33e7.30 (m, 2H), 7.27
(d, J ¼ 8.4 Hz, 2H), 7.23e7.18 (m, 3H), 3.50 (d, J ¼ 13.6 Hz, 1H), 3.32
(d, J ¼ 13.6 Hz, 1H), 2.91 (br s, 1H), 1.59 (s, 3H); 13C NMR (100 MHz,
CDCl3):
d
144.67, 136.03, 132.90, 130.22 (2ꢂ), 128.97 (2ꢂ), 128.30
(2ꢂ), 126.59, 126.38 (2ꢂ), 73.70, 49.54, 29.38.
4.4.3. 2-(4-Chlorophenyl)-1-phenylsulfanylpropan-2-ol (7b-1)
Yield ¼ 10% (13 mg); Colorless oil; HRMS (ESI-TOF) m/z: [M þ
H]þ calcd for C15H14ClS 261.0505, found 261.0509; 1H NMR
(400 MHz, CDCl3):
7.48e7.43 (m, 2H), 7.21 (br s, 4H), 5.58 (s, 1H), 5.21 (s, 1H), 4.23 (s,
2H); 13C NMR (100 MHz, CDCl3):
138.29, 137.19, 135.46, 134.01,
d
7.80e7.77 (m, 2H), 7.61e7.56 (m, 1H),
1H NMR (400 MHz, CDCl3):
d 7.25e7.20 (m, 2H), 7.06e7.03 (m, 1H),
7.01e6.98 (m, 2H), 6.94e6.83 (m, 3H), 3.29 (d, J ¼ 12.4 Hz, 1H), 3.26
(d, J ¼ 12.0 Hz, 1H), 2.49 (d, J ¼ 14.8 Hz, 1H), 2.22 (d, J ¼ 14.8 Hz, 1H),
2.03 (br s, 1H), 1.25 (s, 3H), 1.14 (s, 3H); 13C NMR (100 MHz, CDCl3):
d
133.71, 128.96 (2ꢂ), 128.56 (2ꢂ), 128.52 (2ꢂ), 127.53 (2ꢂ), 122.34,
61.98.
d
162.85 (d, J ¼ 244.1 Hz), 162.77 (d, J ¼ 244.1 Hz), 151.42 (d,

1008
N.-C. Hsueh et al. / Tetrahedron 74 (2018) 1002e1008
2. Selected examples on vicinal azidohydroxylation of olefins, for I2/TBHP/NaN3,
see: (a) Prasad PK, Reddi RN, Sudalai A. Chem Commun. 2015;51:10276e10279.
For TEMPO-Na/NaN3, see;
(b) Zhang A, Studer A. Org Lett. 2013;15:4548e4551. For PhI(OAc)2/TMSN3, see;
(c) Xia X-F, Gu Z, Liu W, et al. J Org Chem. 2015;80:290e295. For (NH4)2Ce(NO3)
6/NaN3, see;
J ¼ 6.0 Hz), 146.57 (d, J ¼ 6.8 Hz), 129.74 (d, J ¼ 8.3 Hz), 129.58 (d,
J ¼ 8.3 Hz), 121.35 (d, J ¼ 3.0 Hz), 120.84 (d, J ¼ 3.1 Hz), 113.92 (d,
J ¼ 21.2 Hz), 113.09 (d, J ¼ 22.0 Hz), 112.68 (d, J ¼ 22.8 Hz), 77.11 (d,
J ¼ 1.5 Hz), 62.79, 51.16, 37.70 (d, J ¼ 1.5 Hz), 31.85, 29.66 (d,
J ¼ 3.7 Hz), 29.27.
(d) Chavan SP, Subbarao YT. Tetrahedron Lett. 1999;40:5073e5074. For MnBr2/
TMSN3, see;
(e) Sun X, Li X, Song S, Zhu Y, Liang Y-F, Jiao N. J Am Chem Soc. 2015;137:
6059e6066. For LEDs/TMSN3, see;
Acknowledgments
(f) Yang B, Lu Z. ACS Catal. 2017;7:8362e8365.
3. For reviews on Bi(III) salts mediated reactions, see: (a) Postel M, Dunach E. Coord
Chem Rev. 1996;155:127e144;
(b) Leonard NM, Wieland LC, Mohan RS. Tetrahedron. 2002;58:8373e8397;
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The authors would like to thank the Ministry of Science and
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graphic data for this paper. This data can be obtained free of charge via www.
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