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

DOI: 10.1016/j.tet.2018.01.023

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Tetrahedron p. 1002 - 1008 (2018)

Update date:2022-08-05

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Authors:

Hsueh, Nai-Chen

Chan, Chieh-Kai

Chang, Meng-Yang

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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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Tetrahedron

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BiI₃mediated difunctionalization of a-methylstyrenes, including

azidohydroxylation and azidoiodination

, b, *

Nai-Chen Hsueh ^a, Chieh-Kai Chan ^a, Meng-Yang Chang ^a

^aDepartment of Medicinal and Applied Chemistry, Kaohsiung Medical University, Kaohsiung 807, Taiwan

^bDepartment 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:

BiI₃mediated vicinal azidohydroxylation of

-methylstyrenes 1 with NaN₃in wet DMF affords

-azidoiodides 6 are also obtained by BiI₃mediated 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

carbon-azido/carbon-hydroxy (N₃eCCeOH) bond and carbon-azido/carbon-iodo (N₃eCCeI) under

water-controlled conditions.

Keywords:

Bismuth iodide

Azidohydroxylation

-methylstyrenes

-Azidoalcohols

1. Introduction

hydroxytriﬂuoromethylation (F₃CeCCeOH),^1kFe^3þcatalyzed acy-

loxyalkylation (ReCCeOCOR),^1lCu^þ/Mn^2þcyanophosphinoylation

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,¹including Ni^2þcatalyzed alkyl-

(NCeCCePOR₂)^1mand Cu^2þ/I^3þcatalyzed azidocyananation

(N₃eCCeCN).¹ⁿHowever, 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.^2aStuder and Zhang demonstrated

a TEMPONa-

mediated stereoselective radical azidooxygenation of alkenes

with a N₃-iodine(III) reagent.^2bLiang et al. reported a PhI(OAc)₂-

mediated metal-free three-component oxyazidation of alkenes,

TMSN₃and N-hydroxyphthalimide (NHPI).^2cChavan and Subbarao

described a (NH₄)₂Ce(NO₃)₆mediated azidoalkoxylation of oleﬁns

with NaN₃and alcohols.^2dJiao group investigated a MnBr₂-medi-

ated hydroxyazidation of oleﬁns with TMSN₃under open-vessel

condition.^2eYang and Lu explored a visible-light (LEDs)-promoted

aerobic hydroxyazidation of oleﬁns with TMSN₃.^2fFor 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

Pd^2þ/Cu^2þ

promoted

catalyzed

diarylation

(AreCCeAr),^1b

alkoxyhydroxylation

(HOeCCeOR),^1c-1dI^3þmediated diacetalation (ROCOeCCeOCOR),^1e

organocatalyst mediated bromohydroxylation (BreCCeOH),^1fBi^3þ

promoted hydroarylation (HeCCeAr),^1gSelect ﬂuoro mediated

aminoﬂuorination (FeCCeNHR),^1hEr^3þpromoted amino-

hydroxylation (HOeCCeNHR),¹ⁱI^ꢀ/S₂O₈^2ꢀmediated acet-

amidosulfenylation

(RSeCCeNHCOR),^1j

Cu^þ

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

N.-C. Hsueh et al. / Tetrahedron 74 (2018) 1002e1008

1003

Table 1

Reaction Conditions.^a

I , TBHP

TEMPO-Na

CH Cl

Me OH

Et N, DMSO

(Sudalai work)

NaN

(Studer work)

Me OMe

PhI(OAc)

(NH ) Ce(NO )

entry

2, azides

solvent

temp (^ꢁC)

time (h)

4a (%)^b

NHPI, (CH Cl)

MeOH

(Chavan work)

TMSN

NaN

2a, NaN₃

2b, LiN₃

DMF

MeCN

MeNO₂

DMSO

DMF

100

－

(Liang work)

reﬂux

Me OMe

Me OH

MnBr

blue LEDs

air, toluene

air, MeCN

then PPh

(Jiao work)

TMSN

then PPh

(Lu work)

－

Scheme 1. Synthetic routes for azidohydroxylation.

2c, TMSN₃

2a, NaN₃

－

cee

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-

Isolated yields.

No reaction.

Complex mixture.

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). BiI₃is a stable, commercially available solid that has been

underutilized in organic synthesis.^3,4BiI₃mediated 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/NaN₃combination 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 BiI₃mediated 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

methylstyrene 1 having an unsymmetrical oleﬁn motif, Sudalai,^2a

Studer,^2bLiang^2cand Chavan^2dshowed that oxidants promoted

carbon-azido and carbon-hydroxy bond formations with different

azido sources (NaN₃, TMSN₃and 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 NaN₃in 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

BiI (3a)

Me OH

NaN (2a)

1a-1l

wet DMF

4a-4j

(for 1a-1j)

5a-5b

(for 1k-1l)

Me OH

and DMSO (entries 8e9). For the azidohydroxylation of

-methyl-

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,

LiN₃gave only a 58% yield of 4a; however, there was no reaction for

4f (70%)

4g (81%)

4h (70%)

4i (72%)

4a, Y = H (82%)

4b, Y = F (80%)

4c, Y = NO (76%)

4d, Y = CF (75%)

4e, Y = Ph (73%)

MeO

Me OH

BiI (3a)

OMe

5a (67%)

Scheme 3. Synthesis of 4e5.

NaN (2a)

MeO

wet DMF

4j (43%)

5b (63%)

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

H O

BiI

C-2

for 1k-1l

DMF

dry DMF

for 1a-1b, 1d, 1f, 1h

wet DMF

H O

electronic effect of a Y substituent on the skeleton of

a-methyl-

styrenes 1, the electron-donating oxygenated group was inappro-

priate for the formation of 4.

for 1a-1j

With the results at hand, an anhydrous reaction condition was

examined next. Interestingly, when water was removed from the

BiI₃mediated reaction of 1 with NaN₃under 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 BiI₃and NaN₃in

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 Bi^3þcomplex 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,6Among 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

HN₃led to 4 via the ﬁve-membered ring transition state. The

releasing dioxybismuth iodide ion trapped excess H₂O to produce

Bi(OH)₃and 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 5.⁷The 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

I +

C-3

C-1

H O

I +

Bi(OH) + I

H O

work-up

Me OH

Bi(OH)

H O

N H

Scheme 5. Possible mechanisms.

Me OH

BiI (3a)

SPh

NaSPh (2d)

wet DMF

SPh

O N

1c, 1m

7a (26%)

for 1c

7b (61%)

for 1m

7b-1 (10%)

for 1m

Me OH

BiI (3a)

SO Ph

NaSO Ph (2e)

SO Ph

O N

wet DMF

1c, 1m

8a (49%)

for 1c

8b (77%)

for 1m

BiI (3a)

NaN (2a)

wet DMF

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)₃were

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 BiI₃mediated

hydroxysulfenylation of 1 with 2d, obvious variants were detected

in the distribution of different products. Furthermore, attempts to

produce BiI₃mediated 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-

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, BiI₃mediated 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).⁸Besides 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

BiI (3a)

NaN (2a)

1a-1b, 1d, 1f, 1h

and hydroxysulfonylation of

droxylation of styrene.

-methylstyrenes and the azidohy-

dry DMF

6a-6e

As an extension for vicinal difunctionalization of

-methylstyr-

ene, changing the promoter from BiI₃to I₂was 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 I₂activates 1g to afford

the iodonium ion intermediate. After intermolecular cross-

coupling of the resulting tertiary carbocation of 1g and another

F C

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 NaN₃in wet and dry DMF afford

b-azidoalcohols and

-azi-

doiodides in moderate to good yields. The plausible mechanisms

have been discussed and proposed. On the other hand, we also

described BiI₃mediated 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

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]^þcalcd for C₉H₁₂N₃O 178.0980, found 178.0985; ¹H NMR

(400 MHz, CDCl₃):

d 7.48e7.45 (m, 2H), 7.41e7.36 (m, 2H),

7.33e7.28 (m, 1H), 3.61 (d, J ¼ 12.4 Hz, 1H), 3.45 (d, J ¼ 12.0 Hz, 1H),

2.21 (br s, 1H), 1.60 (s, 3H); ¹³C NMR (100 MHz, CDCl₃):

d 144.62,

128.45 (2ꢂ), 127.48, 124.80 (2ꢂ), 74.54, 62.09, 27.08.

wet DMF

9a (64%)

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

H]^þcalcd for C₉H₁₁FN₃O 196.0886, found 196.0892; ¹H NMR

(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,

H O

162.09 (d, J ¼ 244.8 Hz), 140.41 (d,

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]^þcalcd for C₉H₁₁N₄O₃223.0831, found 223.0839; ¹H NMR

3. Conclusion

(400 MHz, CDCl₃):

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 BiI₃mediated vicinal azido-

hydroxylation and azidoiodination of substituted

(s, 3H); ¹³C NMR (100 MHz, CDCl₃):

151.97, 147.10, 126.06 (2ꢂ),

-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]^þcalcd 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):

7.64 (d, J ¼ 8.4 Hz, 2H), 7.58 (d, J ¼ 8.4 Hz, 2H),

H]^þcalcd for C₂₀H₂₁O₄325.1440, found 325.1438; ¹H NMR

(400 MHz, CDCl₃):

d 6.71e6.62 (m, 4H), 6.53 (s, 1H), 5.96 (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.

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]^þcalcd for C₁₅H₁₆N₃O 254.1293, found 254.1299; ¹H NMR

(400 MHz, CDCl₃):

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):

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]^þcalcd for C₂₄H₃₃O₆417.2277, 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):

153.68, 152.21 (2ꢂ), 149.99, 147.48,

H]^þcalcd 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):

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]^þcalcd for C₈H₁₀N₃O 164.0824, found 164.0823; ¹H NMR

(400 MHz, CDCl₃):

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):

140.66, 128.75 (2ꢂ), 128.34,

H]^þcalcd 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

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):

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.

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]^þcalcd for C₁₃H₁₄N₃O 228.1137, found 228.1135; ¹H NMR

Yield ¼ 76% (109 mg); Colorless oil; HRMS (ESI-TOF) m/z: [M þ

H]^þcalcd for C₉H₁₁IN₃287.9998, found 287.9990; ¹H NMR

(400 MHz, CDCl₃):

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.

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]^þcalcd 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]^þcalcd for C₉H₁₀FIN₃305.9904, 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.

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

(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,

162.26 (d, J ¼ 247.2 Hz), 136.56 (d, J ¼ 3.8 Hz),

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]^þcalcd for C₁₀H₁₀F₃IN₃355.9872, 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.

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]^þcalcd for C₉H₉Cl₂IN₃355.9218, found 355.9219; ¹H NMR

(400 MHz, CDCl₃):

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]^þcalcd for C₈H₁₀IN₄288.9950, found 288.9953; ¹H NMR

CDCl₃þ DMSO‑d₆):

7.93 (d, J ¼ 8.8 Hz, 2H), 7.60e7.58 (m, 2H),

(400 MHz, CDCl₃):

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):

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.

CDCl₃þ DMSO‑d₆):

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 CH₂Cl₂to

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, d_calcd¼ 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 1.190e26.026^ꢁ,

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 CH₂Cl₂to 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]^þcalcd for C₁₅H₁₄NO₂S 272.0745, found 272.0740; ¹H NMR

(400 MHz, CDCl₃):

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):

150.65, 148.28, 146.40, 141.28, 133.65, 130.31, 129.39 (2ꢂ),

V ¼ 1798.2(6) Å³, Z ¼ 8, d_calcd¼ 1.475 g/cm³, F(000) ¼ 1296, 2

q range

127.34 (4ꢂ), 123.89 (2ꢂ), 17.20.

2.547e26.359^ꢁ, 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]^þcalcd 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]^þcalcd for C₁₈H₂₀F₂IO 417.0527, found 417.0523;

(400 MHz, CDCl₃):

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):

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]^þcalcd 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,

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):

133.71, 128.96 (2ꢂ), 128.56 (2ꢂ), 128.52 (2ꢂ), 127.53 (2ꢂ), 122.34,

61.98.

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;

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;

The authors would like to thank the Ministry of Science and

Technology of the Republic of China for its ﬁnancial support (MOST

105-2113-M-037-001).

(d) Salvador JAR, Ppinto RMA, Silvestreb SM. Mini-Reviews Org Chem . 2009;6:

241e274;

Appendix A. Supplementary data

(e) Krabbe SW, Mohan RS. Top Curr Chem . 2012;311:45e68;

(f) Ollevier T. Org Biomol Chem . 2013;11:2740e2755;

(g) Ondet P, Lemiere G, Dunach E. Eur J Org Chem . 2017;2017:761e780;

(h) Abnerjee B. ChemistrySelect . 2017;2:6744e6757;

Supplementary data related to this article can be found at

https://doi.org/10.1016/j.tet.2018.01.023.

(i) Ollevier T. Bismuth-mediated Organic Reactions . Springer; 2012;

(j) Mohan R. Nat Chem . 2010;2, 336-336;

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

DOI: 10.1016/j.tet.2018.01.023

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