Tungsten-Catalyzed Allylic Substitution with a Heteroatom Nucleophile: Reaction Development and Synthetic Applications

Article abstract of DOI:10.1021/acs.joc.0c01632

A tungsten-catalyzed allylic allylation of sodium sulfinate as the heteroatom nucleophile was developed. The reaction utilizes inexpensive and readily available (CH3CN)3W(CO)3 as a precatalyst and proceeds at 60 °C temperature in the presence of 2,2′-bipyridine and its derivatives as ligand. The synthetic utility of allylic sulfones as electrophile was further demonstrated through Suzuki-Miyaura cross-coupling as showcased by the formal synthesis of (±)-hinokiresinol.

Full text of DOI:10.1021/acs.joc.0c01632

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Tungsten-Catalyzed Allylic Substitution with a Heteroatom
Nucleophile: Reaction Development and Synthetic Applications
Yaoyao Xu,† Muhammad Salman,† Shahid Khan, Junjie Zhang, and Ajmal Khan*
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ABSTRACT: A tungsten-catalyzed allylic allylation of sodium
sulfinate as the heteroatom nucleophile was developed. The
reaction utilizes inexpensive and readily available (CH3CN)3W-
(CO)3 as a precatalyst and proceeds at 60 °C temperature in the
presence of 2,2′-bipyridine and its derivatives as ligand. The
synthetic utility of allylic sulfones as electrophile was further
demonstrated through Suzuki−Miyaura cross-coupling as showcased by the formal synthesis of ( )-hinokiresinol.
study will provide a direct approach to the regioselective
formation of branched allylic sulfones since they serve as
building blocks in various organic transformation and
pharmaceutical industry (Figure 1B).14,15 Herein, we report
our investigation from this study. The salient features of this
methodology are the cost-efficient and simple procedures, high
regioselectivity, and excellent functional-group tolerance for
both allylic electrophiles and sodium sulfinate. Furthermore,
the high reactivity of allylic sulfones as a new class of
electrophile16 to form biologically important compounds
through cross-coupling reactions is the special characteristic
of this catalytic system.
INTRODUCTION
■
Transition-metal-catalyzed allylic substitution reactions have
enjoyed widespread applications in organic synthesis over the
past 50 years. While palladium catalysis has always been a
choice in the vast majority of these reactions,1 other metal
catalysis has found application in selected cases. Catalysts
derived from other transition metals2 were relatively less
studied, but showed high regioselectivity, with iridium catalysis
being the most effective.3 The Trost group4,5 in 1983
discovered that (group 6 metals) molybdenum (Mo) and
tungsten (W) provided regiochemistry, which was comple-
mentary to palladium catalysis, with Mo and W affording a
branched product compared to that derived from Pd catalysis.
Further significant contributions to this area have been
reported by the groups of Moberg,6 Hughes,7 Pfaltz,8 and
others,9 realizing transformations with only carbon-based
nucleophiles. In addition, very recently, we have disclosed
the first general example of Mo-catalyzed allylic substitution to
form a tetrasubstituted C−S bond, demonstrating the
prospects of group 6 metal catalysis in the context of
carbon−heteroatom bond formation chemistry.10 On the
other hand, since its discovery, studies into the corresponding
catalysis with tungsten (W) have remained underdeveloped for
decades. In contrast to the potential advantages of W catalysis,
which include inherent similarity to the versatile Mo (and Pd)
catalysts, literature reports on W-catalyzed allylic substitution
revealed only a few examples with carbon nucleophiles (Figure
1A, left),11 with the allylic substitution of heteroatom
nucleophiles remaining unknown (Figure 1A, right).12 There-
fore, given the utility of the branched, α-substituted vinylated
heteroatom compounds and the difficulty of accessing them by
conventional methods, development of such reactions would
be highly important.
RESULTS AND DISCUSSION
■
To develop a catalytic reaction, we used allyl acetate (1a) and
2a as the test reaction in tetrahydrofuran (THF) at 60 °C. We
found that W(CO)6 failed to catalyze the reaction (Table 1,
entry 1). Similarly, (CH3CN)3W(CO)3 led to a slow reaction
(entry 2). Based on literature reports and our recent work,10
the use of a stronger σ-donor-type ligand such as bipyridine17
is to facilitate opening a coordination site on the tungsten,
which leads to a significant improvement (entry 3). A more
general reaction resulted when allylic carbonate (1b), a slightly
better leaving group, was replaced for 1a (entry 4). To further
investigate the role of leaving group on allylic electropile,
substrate 1c was able to provide the desired branched product
in a comparatively high yield (entry 5). By changing the
reaction medium from THF to EtOH, the reaction efficiency
was remarkably improved and the expected branched product
Received: July 9, 2020
Published: August 17, 2020
Considering these circumstances, our interest in group 6
metal catalysis10,13 arose from a need to find a novel W-
catalyzed allylic substitution reaction to form carbon−
heteroatom bond with characteristic synthetic utility. This
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A

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Figure 1. Limitations in W-catalyzed allylic alkylation (A), current work (B).
a
Table 1. Optimization of the Reaction Parameters
b
c
entry
conditions
1a, W(CO)6/THF
1a, (CH3CN)3W(CO)3/THF
b/l
yield (%)
1
2
d
<5
3
4
5
6
7
8
9
10
11
12
13
14
15
1a, (CH3CN)3W(CO)3/L1/THF
1b, (CH3CN)3W(CO)3/L1/THF
1c, (CH3CN)3W(CO)3/L1/THF
1c, (CH3CN)3W(CO)3/L1/EtOH
1c, (CH3CN)3W(CO)3/L1/iPrOH
1c, (CH3CN)3W(CO)3/L1/toluene
1c, (CH3CN)3W(CO)3/L1/CH2Cl2
1c, (CH3CN)3W(CO)3/L2/EtOH
1c, (CH3CN)3W(CO)3/L3/EtOH
1c, (CH3CN)3W(CO)3/L4/EtOH
1c, (CH3CN)3W(CO)3/L5/EtOH
1c, (CH3CN)3W(CO)3/L6/EtOH
1c, (CH3CN)3W(CO)3/L7/EtOH
1c, (CH3CN)3W(CO)3/L1/EtOH
1c, without W or ligand
10:1
10:1
10:1
>20:1
>19:1
15
22
32
91
45
<10
<10
87
95
65
20
d
d
>20:1
>20:1
>20:1
15:1
d
<10
<10
36
d
d
16
17
>20:1
a
Reaction conditions: W catalyst (10 mol %), ligand (15 mol %), 1a−c (0.2 mmol), PhSO2Na 2a (0.30 mmol), solvent (1.0 mL, 0.2 M), 60 °C, 24
b
c
d
1
h. Branched-to-linear ratio was determined by H NMR of crude reaction mixture. Isolated yields. The reaction was performed at room
temperature (25 °C).
3ca was obtained in 91% isolated yield with excellent branched
regioselectiviy (entry 6). Subtle changes on the solvent,
however, had a negative effect on the reaction to occur,
consistently providing lower yields if any (entries 7−9). A
further evaluation of ligands revealed that 6,6′-dimethyl-2,2′-
bipyridine (L2) decreases the efficiency, while 4,4′-di-tert-
butyl-2,2′-bipyridine (L3) demonstrated superior performance
to all of the ligands utilized (entries 10−15). The reaction was
also performed at room temperature, providing excellent
regioselectivity albeit with a reasonable decrease in perform-
ance (entry 16). As expected, control experiments supported
that all of the catalyst components (W and ligand) were
necessary for the reaction to proceed (entry 17).
The substrate scope of the W-catalyzed allylic sulfonylation
with respect to allylic electrophile is summarized in Table 2.
Branched allyl carbonates with alkyl substituents (entries, 1−
6) afforded branched products in excellent yield and
regioselectivity, irrespective of the size of the alkyl group
(1c−h). Allylic electrophiles with unsubstituted or substituted
group on the phenyl ring were successfully employed in the
B
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a
Table 2. Reaction Scope with Respect to Allylic Electrophiles
b
c
entry
1
R3
Ph
b/l
yield (%)
1
2
3
4
5
6
7
8
R1 = CH2CH2Ph (1c)
R1 = CH3CH2CH2 (1d)
R1 = Cy (1e)
R1 = CH2(CH2)7CH3 (1f)
R1 = CH2CH2CHCH2 (1g)
R1 = Cl(CH2)2CH2 (1h)
R1 = Ph (1i)
>20:1
>20:1
9:1
95 (3ca)
Ph
Ph
Ph
Ph
Ph
Ph
Ph
Ph
Ph
Ph
Ph
87 (3da)
56 (3ea)
89 (3fa)
91 (3ga)
82 (3ha)
84 (3ia)
82 (3ja)
92 (3ka)
76 (3la)
81 (3ia)
85 (3ka)
89 (3ob)
72 (3pb)
>20:1
>20:1
>20:1
>19:1
>19:1
>19:1
>19:1
>19:1
>19:1
>19:1
10:1
R1 = 4-ClC6H4 (1j)
R1 = 4-MeOC6H4 (1k)
R2 = Me (1l)
9
10
11
12
13
14
R2 = Ph (1m)
R2 = 4-MeOC6H4 (1n)
R2 = PhCH2CH2 (1o)
R2 = Cy (1p)
p-tol
p-tol
a
Reaction conditions: W catalyst (10 mol %), ligand L3 (15 mol %), 1 (0.2 mmol), R3SO2Na (2a or 2b) (0.30 mmol), EtOH (1.0 mL, 0.2 M), 60
b
c
1
°C, 24 h. Branched-to-linear ratio was determined by H NMR of crude reaction mixture. Isolated yields.
a
Table 3. Reaction Scope with Respect to Sulfinate Nucleophile
b
c
entry
1
2
3
b/l
yield (%)
1
2
3
4
5
6
7
8
1c
1c
1c
1c
1c
1c
1c
1c
1c
1c
1c
1c
1i
1i
1i
1i
1i
1i
1i
2b (R2 = 4-MeC6H4)
2c (R2 = 4-MeOC6H4)
2d (R2 = 4-ClC6H4)
2e (R2 = 4-FC6H4)
2f (R2 = 2,4-MeOC6H3)
2g (R2 = 2-MeO, 5-BrC6H3)
2h (R2 = 2-naphthyl)
2i (R2 = 2,3-dihydrobenzofuryl)
2j (R2 = 2-thienyl)
2k (R2 = Me)
2l (R2 = Et)
2m (R2 = cyclopropyl)
2b (R2 = 4-MeC6H4)
2c (R2 = 4-MeOC6H4)
2d (R2 = 4-ClC6H4)
2e (R2 = 4-FC6H4)
2n (R2 = 4-CNC6H4)
2o (R2 = 4-NO2C6H4)
2p (R2 = 3-BrC6H4)
3ob
3cc
3cd
3ce
3cf
3cg
3ch
3ci
3cj
3ck
3cl
3cm
3ib
3ic
3id
3ie
>20:1
>20:1
>19:1
>19:1
>20:1
>20:1
>19:1
>19:1
>19:1
>20:1
>20:1
>20:1
>19:1
>19:1
>19:1
>19:1
>19:1
>19:1
>19:1
94
92
89
85
90
86
94
92
85
78
82
76
87
90
86
78
80
81
86
9
10
11
12
13
14
15
16
17
18
19
3in
3io
3ip
a
Reaction conditions: W catalyst (10 mol %), ligand L3 (15 mol %), 1 (0.2 mmol), R2SO2Na 2 (0.30 mmol), EtOH (1.0 mL, 0.2 M), 60 °C, 24 h.
b
c
1
Branched-to-linear ratio was determined by H NMR of crude reaction mixture. Isolated yields.
desired C−S bond formation (entries 7−9). Linear allyl
carbonates with methyl (1l) or phenyl (1m) groups exclusively
afforded the branched product (entries 10 and 11), suggesting
a negligible decrease in yield. Allyl carbonate containing a 4-
methoxyphenyl (1n), PhCH2CH2 (1o), or cyclohexyl (1p)
group produced the products in a high yield while maintaining
the excellent regioselectivity (entries 12−14).
withdrawing and electron-donating substituents on the
aromatic ring underwent sulfonylation in high yield and
absolute regioselectivity (entries 1−6). The sulfinate salt with
bulky naphthyl (2h), 2,3-dihydrobenzofuryl (2i), and 2-thienyl
(2j) as nucleophile also afforded satisfactory results (entries
7−9). Alkyl-substituted sodium sulfinates also returned the
desired branched product in high yields (entries 10−12).
Various sulfinate salts with different electronic nature were
coupled with phenyl allylic carbonate (1i) in good yield with
The substrate scope with respect to sulfinate nucleophile is
summarized in Table 3. Sulfinate salt with both electron-
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Figure 2. Formal synthesis of ( )-hinokiresinol. Reaction conditions: (a) Ni(cod)2 (10 mol %) BrettPhos (12 mol %), 3ka (0.2 mmol), 4 (0.2
mmol), NaOEt (2.2 equiv), PhMe (0.2 M), 24 h, 80 °C. (b) 3ka (0.2 mmol), 4 (0.4 mmol), [{PdCl(allyl)}2] (5 mol %), SIPr·HCl (10 mol %),
NaOH (3 equiv), dioxane/H2O = 5:3, 120 °C, 15 h.
Scheme 1. Attempted Asymmetric W-Catalyzed Allylic Sulfonylation
excellent regioselectivity (entries 13−19). Of particular note,
in almost all cases, the reactions proceeded with excellent
branched regioselectivity (>19:1).
proceeds at a mild temperature, affording the allyl sulfones
with excellent regioselectivity, good to excellent yields, and
good functional-group tolerance, thus providing ample
opportunities for further derivatization. Through the desulfi-
native cross-coupling of allylic sulfone 3ka, we were able to
achieve the formal synthesis of ( )-hinokiresinol (as presented
in Figure 2). Investigations of enantioselective reactions and
extension of current catalyst system to other nucleophiles are
currently ongoing in our lab and will be reported in due course.
Due to their ambiphilic nature, (allylic) sulfones have
attracted special attention in allylic substitution and in Suzuki
cross-coupling reactions.16 Therefore, we decided to utilize
allyl sulfone 3ka in Suzuki−Miyaura cross-coupling to achieve
formal synthesis of the ( )-hinokiresinol natural product.18
For this purpose, synthesis of 3ka was performed on a large
scale (5.0 mmol) under standard conditions and isolated in
89% yield (1.3 g) without any loss in regioselectivity, which
proved the practical use of the current protocol.19 As illustrated
in Figure 2, exposure of allylic sulfone 3ka to boronic acid 4
(1.1 equiv) under previously reported conditions16 produces
compound 5, which could be converted to ( )-hinokiresinol
through the known procedures reported by Carreira and co-
workers.18b Furthermore, we invision that this approach could
find significant utility in the target-directed synthesis of other
related compounds containing gem-diarylalkyl group,20 which
would have proven challenging to prepare via more conven-
tional approaches.
EXPERIMENTAL SECTION
■
Preparative column chromatography was performed according to the
Still method. Solvents for the chromatography are listed as volume/
volume ratios. High-resolution mass spectra (HRMS) were performed
at Instrumental Analysis Center of Xi’an Jiao Tong University using a
QTOF microspectrometer. Proton nuclear magnetic resonance (1H
NMR) spectra were recorded with a Varian Mercury Plus 400 (400
MHz) spectrometer. Chemical shifts are reported in delta (δ) units,
parts per million (ppm) downfield from tetramethylsilane or ppm
relative to the center of the singlet at 7.26 ppm for deuteriochloro-
form. Coupling constants are reported in hertz (Hz). Carbon-13
nuclear magnetic resonance (13C NMR) spectra were recorded with a
Varian Gemini 400 (100 MHz) spectrometer. Chemical shifts are
reported in delta (δ) units, ppm relative to the center of the triplet at
77.0 ppm for deuteriochloroform. 13C NMR spectra were routinely
run with broad-band decoupling. High-performance liquid chroma-
tography (HPLC) was performed with FuLi Instruments spectrom-
eters using a chiralcel OD-H column. Optical rotations were
measured on an SGW-1 polarimeter. W(CO)6, (CH3CN)3W(CO)3,
and bipyridine compounds were purchased from Energy Chemicals
and Aladin/Sigma-Aldrich companies and used as received. Allylic
carbonates were synthesized according to the previously reported
procedure.21 Sodium sulfinates were prepared according to a method
reported in the literature.22 All other chemicals were used as received
from commercial resources.
To investigate the potential application of this newly
developed methodology in asymmetric synthesis of allylic
sulfone, a preliminary study on chiral ligand screening was
probed. One result with the chiral ligand (R)-L8, the branched
allylic sulfone (R)-3ia was obtained with 62% of isolated yield,
excellent branched regioselectivity (>19:1), and a promising
35.5% enantiomeric excess (ee), as shown in Scheme 1.19
CONCLUSIONS
■
In summary, a relatively mild (tungsten) W-catalyzed
sulfonylation of both linear and α-branched allylic electrophiles
has been developed. By modifying the sodium sulfinate, a
variety of allylic sulfones can be obtained using a simple and
inexpensive catalyst system. This operationally simple reaction
Synthesis and Characterization of Allylic Carbonates. Allylic
carbonates 1 were synthesized according to the previously reported
D
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procedures.21 All characterization data are in accordance with the
literature. New substrates have been fully characterized.
3H), 5.62 (dt, J = 9.6, 17.2 Hz, 1H), 5.11 (d, J = 10.0 Hz, 1H), 4.76
(d, J = 17.2 Hz, 1H), 3.46 (t, J = 7.2 Hz, 1H), 2.23−2.09 (m, 2H),
1.82−1.58 (m, 4H), 1.30−0.95 (m, 5H); 13C{1H} NMR (100 MHz,
CDCl3) δ 143.3, 136.7, 133.2, 130.5, 128.1, 119.2, 74.6, 43.1, 30.8,
30.6, 26.9, 26.6, 26.3. HRMS (ESI) m/z: [M + Na]+ calcd for
C15H20O2SNa 287.1082; found 287.1076.
tert-Butyl Dodec-1-en-3-yl Carbonate (1f). Obtained as a
colorless oil (85% yield, 1.3 g); 1H NMR (400 MHz, CDCl3) δ
5.77 (ddd, J = 17.2, 10.4, 7.2 Hz, 1H), 5.25 (d, J = 17.2 Hz, 1H), 5.21
(d, J = 10.4 Hz, 1H), 4.78 (t, J = 7.2 Hz, 1H), 1.77−1.73 (m, 2H),
1.42 (s, 9H), 1.24−1.10 (m, 14H), 0.85 (t, J = 6.4 Hz, 3H); 13C{1H}
NMR (100 MHz, CDCl3) δ 151.9, 137.1, 115.4, 83.6, 79.0, 36.0, 31.9,
29.8, 29.5, 29.3, 27.8, 25.2, 22.6, 14.0. HRMS (ESI) m/z: [M + Na]+
calcd for C17H32O3Na 307.2249; found 307.2241.
tert-Butyl (6-Chlorohex-1-en-3-yl) Carbonate (1h). Obtained as a
colorless oil (80% yield, 1.4 g); 1H NMR (400 MHz, CDCl3) δ 5.99−
5.92 (m, 1H), 5.17−5.11 (m, 2H), 4.69 (t, J = 7.2 Hz, 1H), 3.52−
3.47 (m, 2H), 1.93−1.75 (m, 4H), 1.42 (s, 9); 13C{1H} NMR (100
MHz, CDCl3) δ 151.7, 136.7, 115.8, 82.8, 79.7, 44.9, 30.7, 27.7, 27.0.
HRMS (ESI) m/z: [M + Na]+ calcd for C11H19ClO3Na: 257.0920;
found 257.0914.
tert-Butyl (1-(4-Chlorophenyl)allyl) Carbonate (1j). Obtained as
colorless oil (70% yield, 1.1 g); 1H NMR (400 MHz, CDCl3) δ 7.38−
7.31 (m, 4H), 6.06−5.97 (m, 2H), 5.36−5.26 (m, 2H), 1.49 (s, 9);
13C{1H} NMR (100 MHz, CDCl3) δ 152.6, 137.2, 135.7, 134.0,
128.7, 128.4, 117.6, 82.6, 78.4, 27.7. HRMS (ESI) m/z: [M + Na]+
calcd for C14H17ClO3Na 291.0764; found 291.0758.
(Dodec-1-en-3-ylsulfonyl)benzene (3fa). Prepared from 1f and 2a
by following the general procedure. Purification was performed with
flash column chromatography (PE/EA = 20:1) on silica gel to obtain
the title compound as a colorless oil in 89% yield (54.9 mg); 1H NMR
(400 MHz, CDCl3) δ 7.82−7.80 (m, 2H), 7.63−7.61 (m, 1H), 7.52−
7.49 (m, 2H), 5.60 (dt, J = 9.6, 17.2 Hz, 1H), 5.34 (d, J = 10.0 Hz,
1H), 4.90 (d, J = 17.2 Hz, 1H), 3.47 (t, J = 7.2 Hz, 1H), 1.95−1.86
(m, 2H), 1.30−1.23 (m, 14H), 0.88 (t, J = 6.4 Hz, 3H); 13C{1H}
NMR (100 MHz, CDCl3) δ 135.4, 134.8, 133.5, 130.8, 128.3, 120.4,
69.5, 33.8, 31.9, 29.9, 29.5, 29.4, 29.3, 23.7, 22.7, 14.1. HRMS (ESI)
m/z: [M + Na]+ calcd for C18H28O2SNa 331.1708; found 331.1702.
(Hepta-1,6-dien-3-ylsulfonyl)benzene (3ga). Prepared from 1g
and 2a by following the general procedure. Purification was
performed with flash column chromatography (PE/EA = 20:1) on
silica gel to obtain the title compound as a colorless oil in 91% yield
(43.0 mg); 1H NMR (400 MHz, CDCl3) δ 7.83−7.81 (m, 2H),
7.64−7.61 (m, 1H), 7.53−7.50 (m, 2H), 5.81−5.75 (m, 1H), 5.65−
5.59 (m, 1H), 5.37 (d, J = 6.8 Hz, 1H), 5.34 (d, J = 10.0 Hz, 1H),
4.98 (d, J = 6.8 Hz, 1H), 5.92 (d, J = 17.0 Hz, 1H), 3.53 (t, J = 7.2 Hz,
1H), 2.08−1.96 (m, 4H); 13C{1H} NMR (100 MHz, CDCl3) δ 135.6,
135.3, 135.1, 133.6, 130.8, 128.4, 120.7, 115.3, 69.2, 31.1, 29.4.
HRMS (ESI) m/z: [M + Na]+ calcd for C13H16O2SNa 259.0769;
found 259.0764.
((6-Chlorohex-1-en-3-yl)sulfonyl)benzene (3ha). Prepared from
1h and 2a by following the general procedure. Purification was
performed with flash column chromatography (PE/EA = 20:1) on
silica gel to obtain the title compound as a colorless oil in 82% yield
(42.4 mg); 1H NMR (400 MHz, CDCl3) δ 7.83−7.81 (m, 2H),
7.65−7.62 (m, 1H), 7.54−7.51 (m, 2H), 5.65 (dt, J = 10.0, 17.2 Hz,
1H), 5.37 (d, J = 10.0 Hz, 1H), 5.07 (d, J = 17.2 Hz, 1H), 4.47−4.42
(m, 1H), 3.53 (t, J = 4.4 Hz, 2H), 2.15−2.02 (m, 2H), 1.83−1.69 (m,
2H); 13C{1H} NMR (100 MHz, CDCl3) δ 137.0, 134.3, 133.7, 130.8,
128.4, 120.9, 68.7, 43.4, 31.9, 30.4. HRMS (ESI) m/z: [M + Na]+
calcd for C12H15ClO2SNa 281.0379; found 281.0371.
tert-Butyl (1-(4-Methoxyphenyl)allyl) Carbonate (1k). Obtained
1
as a colorless oil (72% yield, 1.2 g); H NMR (400 MHz, CDCl3) δ
7.33 (d, J = 8.4 Hz, 2H), 7.12 (d, J = 8.4 Hz, 2H), 5.99−5.91 (m,
1H), 5.28 (d, J = 17.2 Hz, 1H), 5.14 (d, J = 10.0 Hz, 1H), 5.10 (t, J =
7.2 Hz, 1H), 3.79 (s, 3H), 1.54 (s, 9); 13C{1H} NMR (100 MHz,
CDCl3) δ 156.6, 150.2, 140.1, 139.9, 127.3, 121.1, 115.0, 83.4, 74.4,
55.3, 27.5. HRMS (ESI) m/z: [M + Na]+ calcd for C15H20O4Na
287.1259; found 287.1251.
General Procedure for W-Catalyzed Allylic Sulfonylation of
α-Substituted Allylic Carbonate 1 with Sodium Sulfinate 2. To
an oven-dried screw-cap reaction tube equipped with a magnetic stir
bar, (CH3CN)3W(CO)3 (10 mol %), bipyridine ligand (L3) (15 mol
%), allylic carbonate 1 (0.2 mmol), and sodium sulfinate 2 (0.3
mmol) were added. The reaction tube was sealed with a rubber
septum, then evacuated and backfilled with nitrogen. Anhydrous
ethanol (0.2 M, 1 mL) was added via a syringe. The resulting mixture
was stirred at 60 °C for 24 h. The reaction mixture was cooled to
room temperature, and the residue was purified by flash column
chromatography on silica gel to afford the pure allylic sulfone 3.
((5-Phenylpent-1-en-3-yl)sulfonyl)benzene (3ca). Prepared from
1c and 2a by following the general procedure. Purification was
performed with flash column chromatography (PE/EA = 20:1) on
silica gel to obtain the title compound as a colorless oil in 95% yield
((1-Phenylallyl)sulfonyl)benzene (3ia).21f Prepared from 1i and 2a
by following the general procedure. Purification was performed with
flash column chromatography (PE/EA = 10:1) on silica gel to obtain
the title compound as a white solid in 84% yield (43.4 mg); NMR
spectra of the obtained product were consistent with the reported
one.1f 1H NMR (400 MHz, CDCl3) δ 7.64−7.62 (m, 2H), 7.59−7.55
(m, 1H), 7.44−7.40 (m, 2H), 7.32−7.22 (m, 5H), 6.32 (dt, J = 9.6,
17.2 Hz, 1H), 5.46 (d, J = 10.0 Hz, 1H), 5.31 (d, J = 17.2 Hz, 1H),
4.69 (d, J = 8.8 Hz, 1H); 13C{1H} NMR (100 MHz, CDCl3) δ 137.4,
133.8, 132.1, 129.7, 129.3, 129.2, 128.8, 128.6, 123.5, 75.6. HRMS
(ESI) m/z: [M + Na]+ calcd for C15H14O2SNa 281.0612; found
281.0604.
1
(54.42 mg); H NMR (400 MHz, CDCl3) δ 7.81−7.79 (m, 2H),
7.64−7.60 (m, 1H), 7.53−7.50 (m, 2H), 7.29−7.25 (m, 2H), 7.22−
7.18 (m, 1H), 7.13−7.10 (m, 2H), 5.67 (dt, J = 9.6, 17.2 Hz, 1H),
5.37 (d, J = 10.0 Hz, 1H), 5.07 (d, J = 17.2 Hz, 1H), 3.49 (t, J = 7.2
Hz, 1H), 2.82−2.75 (m, 1H), 2.57−2.40 (m, 2H), 2.02−1.93 (m,
1H); 13C{1H} NMR (100 MHz, CDCl3) δ 141.3, 135.1, 133.6, 130.8,
129.8, 129.4, 128.5, 128.4, 126.6, 124.2, 69.3, 32.5, 28.6. HRMS (ESI)
m/z: [M + Na]+ calcd for C17H18O2SNa 309.0925; found 309.0917.
(Hex-1-en-3-ylsulfonyl)benzene (3da). Prepared from 1d and 2a
by following the general procedure. Purification was performed with
flash column chromatography (PE/EA = 20:1) on silica gel to obtain
the title compound as a colorless oil in 87% yield (39.0 mg); 1H NMR
(400 MHz, CDCl3) δ 7.74−7.71 (m, 2H), 7.57−7.53 (m, 1H), 7.46−
7.42 (m, 2H), 5.60 (dt, J = 9.6, 17.2 Hz, 1H), 5.30 (d, J = 10.0 Hz,
1H), 5.00 (d, J = 17.2 Hz, 1H), 3.42 (t, J = 7.2 Hz, 1H), 1.95−1.86
(m, 2H), 1.51−1.26 (m, 2H), 0.91 (t, J = 7.4 Hz, 3H); 13C{1H} NMR
(100 MHz, CDCl3) δ 136.9, 135.4, 133.5, 130.8, 128.3, 120.3, 69.6,
35.3, 16.6, 14.1. HRMS (ESI) m/z: [M + Na]+ calcd for
C12H16O2SNa 247.0769; found 247.0761.
1-Chloro-4-(1-(phenylsulfonyl)allyl)benzene (3ja). Prepared from
1j and 2a by following the general procedure. Purification was
performed with flash column chromatography (PE/EA = 10:1) on
silica gel to obtain the title compound as a white solid in 82% yield
(48.0 mg); 1H NMR (400 MHz, CDCl3) δ 7.66−7.60 (m, 2H),
7.58−7.55 (m, 1H), 7.42−7.40 (m, 2H), 7.34−7.24 (m, 4H), 6.31
(dt, J = 10.0, 17.2 Hz, 1H), 5.50 (d, J = 10.0 Hz, 1H), 5.36 (d, J =
17.2 Hz, 1H), 4.69 (d, J = 8.4 Hz, 1H); 13C{1H} NMR (100 MHz,
CDCl3) δ 139.1, 135.7, 131.7, 130.7, 129.7, 129.1, 129.0, 128.8, 128.7,
124.1, 75.8. HRMS (ESI) m/z: [M + Na]+ calcd for C15H13ClO2SNa
315.0222; found 315.0214.
1-Methoxy-4-(1-(phenylsulfonyl)allyl)benzene (3ka).21f Prepared
from 1k and 2a by following the general procedure. Purification was
performed with flash column chromatography (PE/EA = 10:1) on
silica gel to obtain the title compound as a white solid in 92% yield
(53.1 mg); NMR spectra of the obtained product were consistent
with the reported one.1f 1H NMR (400 MHz, CDCl3) δ 7.64−7.59
(m, 2H), 7.57−7.55 (m, 1H), 7.44−7.42 (m, 2H), 7.15 (d, J = 9.0 Hz,
((1-Cyclohexylallyl)sulfonyl)benzene (3ea). Prepared from 1e and
2a by following the general procedure. Purification was performed
with flash column chromatography (PE/EA = 20:1) on silica gel to
obtain the title compound as a colorless oil in 56% yield (29.6 mg);
1H NMR (400 MHz, CDCl3) δ 7.72−7.69 (m, 2H), 7.58−7.49 (m,
E
https://dx.doi.org/10.1021/acs.joc.0c01632
J. Org. Chem. XXXX, XXX, XXX−XXX

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Article
2H), 6.82 (d, J = 9.0 Hz, 2H), 6.27 (dt, J = 17.0, 9.0 Hz, 1H), 5.43 (d,
J = 9.6 Hz, 1H), 5.27 (d, J = 17.0 Hz, 1H), 4.64 (d, J = 9.0 Hz, 1H),
3.79 (s, 3H); 13C{1H} NMR (100 MHz, CDCl3) δ 160.2, 133.7,
131.1, 129.7, 129.3, 129.2, 128.8, 128.6, 123.5, 114.2, 75.1, 55.4.
HRMS (ESI) m/z: [M + Na]+ calcd for C16H16O3SNa 311.0718;
found 311.0712.
7.30−7.09 (m, 7H), 5.67 (dt, J = 10.0, 17.2 Hz, 1H), 5.38 (d, J = 10.0
Hz, 1H), 5.07 (d, J = 17.0 Hz, 1H), 3.50−3.44 (m, 1H), 2.83−2.76
(m, 1H), 2.58−2.41 (m, 2H), 2.02−1.93 (m, 1H); 13C{1H} NMR
(100 MHz, CDCl3) δ 167.0, 166.7, 164.5, 164.2, 139.9, 132.1, 132.0,
130.9, 130.8, 130.0, 128.6, 128.5, 128.4, 126.4, 124.4, 116.6, 116.3,
116.2, 116.0, 69.1, 32.2, 28.3. HRMS (ESI) m/z: [M + Na]+ calcd for
C17H17FO2SNa 327.0831; found 327.0824.
2,4-Dimethoxy-1-((5-phenylpent-1-en-3-yl)sulfonyl)benzene
(3cf). Prepared from 1c and 2f by following the general procedure.
Purification was performed with flash column chromatography (PE/
EA = 20:1) on silica gel to obtain the title compound as a white solid
in 90% yield (62.4 mg); 1H NMR (400 MHz, CDCl3) δ 7.42 (dd, J =
2.2, 8.8 Hz, 1H), 7.29−7.18 (m, 4H), 7.12−7.10 (m, 2H), 6.94 (d, J =
8.4 Hz, 1H), 5.69 (dt, J = 10.0, 17.2 Hz, 1H), 5.39 (d, J = 10.0 Hz,
1H), 5.12 (d, J = 17.0 Hz, 1H), 3.95 (s, 3H), 3.89 (s, 3H), 3.50−3.44
(m, 1H), 2.81−2.75 (m, 1H), 2.57−2.49 (m, 1H), 2.45−2.36 (m,
1H), 2.02−1.92 (m, 1H); 13C{1H} NMR (100 MHz, CDCl3) δ 153.2,
148.8, 140.0, 130.2, 128.9, 128.5, 128.4, 126.3, 123.9, 123.3, 111.3,
110.3, 69.1, 56.2, 56.1, 32.3, 28.5. HRMS (ESI) m/z: [M + Na]+ calcd
for C19H22O4SNa 369.1136; found 369.1128.
(But-3-en-2-ylsulfonyl)benzene (3la). Prepared from 1l and 2a by
following the general procedure. Purification was performed with flash
column chromatography (PE/EA = 20:1) on silica gel to obtain the
1
title compound as a colorless oil in 76% yield (29.8 mg); H NMR
(400 MHz, CDCl3) δ 7.87−7.79 (m, 2H), 7.67−7.61 (m, 1H), 7.56−
7.50 (m, 2H), 5.81 (ddd, J = 17.5, 10.4, 7.6 Hz, 1H), 5.26 (d, J = 10.4
Hz, 1H), 5.10 (d, J = 17.2 Hz, 1H), 3.75−3.69 (m, 1H), 1.45 (d, J =
7.2 Hz, 3H); 13C{1H} NMR (100 MHz, CDCl3) δ 136.4, 133.5,
130.2, 128.8, 128.4, 121.5, 63.7, 12.5. HRMS (ESI) m/z: [M + Na]+
calcd for C10H12O2SNa 219.0456; found 219.0448.
1-Methyl-4-((5-phenylpent-1-en-3-yl)sulfonyl)benzene (3ob).21f
Prepared from 1o and 2b by following the general procedure.
Purification was performed with flash column chromatography (PE/
EA = 20:1) on silica gel to obtain the title compound as a colorless oil
1
in 89% yield (53.5 mg); H NMR (400 MHz, CDCl3) δ 7.68−7.66
4-Bromo-1-methoxy-2-((5-phenylpent-1-en-3-yl)sulfonyl)-
benzene (3cg). Prepared from 1c and 2g by following the general
procedure. Purification was performed with flash column chromatog-
raphy (PE/EA = 20:1) on silica gel to obtain the title compound as a
(m, 2H), 7.34−7.18 (m, 5H), 7.13−7.08 (m, 2H), 5.66 (dt, J = 10.0,
17.2 Hz, 1H), 5.37 (d, J = 10.0 Hz, 1H), 5.08 (d, J = 17.2 Hz, 1H),
3.50−3.44 (m, 1H), 2.81−2.74 (m, 1H), 2.68−2.47 (m, 2H), 2.43 (s,
3H), 2.00−1.90 (m, 1H); 13C{1H} NMR (100 MHz, CDCl3) δ 144.5,
140.0, 134.3, 130.2, 129.4, 129.2, 128.5, 128.4, 126.3, 124.0, 69.0,
32.3, 28.4, 21.6. HRMS (ESI) m/z: [M + Na]+ calcd for
C18H20O2SNa 323.1082; found 323.1076.
1
white solid in 86% yield (68.0 mg); H NMR (400 MHz, CDCl3) δ
7.99 (d, J = 1.2 Hz, 1H), 7.63 (dd, J = 1.2, 8.8 Hz, 1H), 7.33−7.12
(m, 5H), 6.82 (d, J = 8.8 Hz, 1H), 5.72 (dt, J = 10.0, 17.2 Hz, 1H),
5.35 (d, J = 10.0 Hz, 1H), 5.14 (d, J = 17.0 Hz, 1H), 4.05−3.99 (m,
1H), 3.73 (s, 3H), 2.88−2.81 (m, 1H), 2.60−2.50 (m, 1H), 2.36−
2.28 (m, 1H), 2.15−2.05 (m, 1H); 13C{1H} NMR (100 MHz,
CDCl3) δ 156.1, 140.1, 137.9, 136.9, 133.4, 128.5, 128.4, 126.2, 123.7,
121.0, 113.7, 112.8, 66.3, 56.2, 32.0, 27.7. HRMS (ESI) m/z: [M +
Na]+ calcd for C18H19BrO3SNa 417.0136; found 417.0128.
1-((1-Cyclohexylallyl)sulfonyl)-4-methylbenzene (3pb).21f Pre-
pared from 1p and 2b by following the general procedure. Purification
was performed with flash column chromatography (PE/EA = 20:1)
on silica gel to obtain the title compound as a colorless oil in 72%
yield (40.1 mg); 1H NMR (400 MHz, CDCl3) δ 7.59−7.56 (m, 2H),
7.19 (d, J = 8.0 Hz, 2H), 5.75 (dt, J = 10.0, 17.2 Hz, 1H), 5.12 (d, J =
10.0 Hz, 1H), 5.72 (d, J = 17.2 Hz, 1H), 3.18−3.15 (m, 1H), 2.34 (s,
3H), 2.24−2.02 (m, 2H), 1.90−1.65 (m, 4H), 1.37−1.32 (m, 2),
1.20−1.02 (m, 3H); 13C{1H} NMR (100 MHz, CDCl3) δ 143.3,
135.8, 129.0, 128.8, 128.4, 123.7, 75.7, 36.7, 32.1, 28.8, 26.5, 26.1,
26.0, 21.7. HRMS (ESI) m/z: [M + Na]+ calcd for C15H20O2SNa
287.1082; found 287.1074.
2-((5-Phenylpent-1-en-3-yl)sulfonyl)naphthalene (3ch). Prepared
from 1c and 2h by following the general procedure. Purification was
performed with flash column chromatography (PE/EA = 20:1) on
silica gel to obtain the title compound as a white solid in 94% yield
1
(63.3 mg); H NMR (400 MHz, CDCl3) δ 8.38 (s, 1H), 8.01−7.93
(m, 2H), 7.81−7.77 (m, 1H), 7.68−7.62 (m, 2H), 7.27−7.16 (m,
3H), 7.12−7.05 (m, 3H), 5.72 (dt, J = 10.0, 17.2 Hz, 1H), 5.36 (d, J =
10.0 Hz, 1H), 5.07 (d, J = 17.0 Hz, 1H), 3.61−3.56 (m, 1H), 2.83−
2.75 (m, 1H), 2.58−2.45 (m, 2H), 2.08−1.98 (m, 1H); 13C{1H}
NMR (100 MHz, CDCl3) δ 140.6, 135.0, 132.2, 131.0, 129.7, 129.5,
129.3, 129.1, 128.5, 128.4, 127.9, 127.6, 127.5, 126.3, 126.2, 123.0,
69.0, 34.7, 28.4. HRMS (ESI) m/z: [M + Na]+ calcd for
C21H20O2SNa 359.1082; found 359.1076.
1-Methoxy-4-((5-phenylpent-1-en-3-yl)sulfonyl)benzene (3cc).
Prepared from 1c and 2c by following the general procedure.
Purification was performed with flash column chromatography (PE/
EA = 20:1) on silica gel to obtain the title compound as a colorless oil
1
in 92% yield (58.2 mg); H NMR (400 MHz, CDCl3) δ 7.73−7.70
(m, 2H), 7.29−7.24 (m, 2H), 7.22−7.18 (m, 1H), 7.13−7.11 (m,
2H), 6.98−6.95 (m, 2H), 5.67 (dt, J = 10.0, 17.2 Hz, 1H), 5.37 (d, J =
10.0 Hz, 1H), 5.09 (d, J = 17.2 Hz, 1H), 3.88 (s, 3H), 3.49−3.43 (m,
1H), 2.81−2.74 (m, 1H), 2.57−2.39 (m, 2H), 2.02−1.90 (m, 1H);
13C{1H} NMR (100 MHz, CDCl3) δ 163.6, 140.1, 131.4, 130.4,
128.8, 128.5, 128.4, 126.3, 123.9, 114.0, 69.2, 55.6, 32.3, 28.5. HRMS
(ESI) m/z: [M + Na]+ calcd for C18H20O3SNa 339.1031; found
339.1024.
6-((5-Phenylpent-1-en-3-yl)sulfonyl)-2,3-dihydrobenzofuran
(3ci). Prepared from 1c and 2i by following the general procedure.
Purification was performed with flash column chromatography (PE/
EA = 20:1) on silica gel to obtain the title compound as a white solid
1
in 92% yield (60.4 mg); H NMR (400 MHz, CDCl3) δ 7.70−7.56
(m, 2H), 7.30−7.26 (m, 2H), 7.22−7.18 (m, 1H), 7.14−7.10 (m,
2H), 6.83 (d, J = 8.4 Hz, 1H), 5.68 (dt, J = 10.0, 17.2 Hz, 1H), 5.39
(d, J = 10.0 Hz, 1H), 5.12 (d, J = 17.0 Hz, 1H), 4.69 (t, J = 8.8 Hz,
2H), 3.49−3.43 (m, 1H), 3.26 (t, J = 8.8 Hz, 2H), 2.82−2.74 (m,
1H), 2.56−2.39 (m, 2H), 1.99−1.90 (m, 1H); 13C{1H} NMR (100
MHz, CDCl3) δ 164.6, 140.1, 130.9, 130.4, 128.7, 128.5, 128.4, 128.1,
126.2, 123.9, 109.3, 72.3, 69.2, 32.3, 28.9, 28.6. HRMS (ESI) m/z: [M
+ Na]+ calcd for C19H20O3SNa 351.1031; found 351.1023.
1-Chloro-4-((5-phenylpent-1-en-3-yl)sulfonyl)benzene (3cd).
Prepared from 1c and 2d by following the general procedure.
Purification was performed with flash column chromatography (PE/
EA = 20:1) on silica gel to obtain the title compound as a colorless oil
1
in 89% yield (57.1 mg); H NMR (400 MHz, CDCl3) δ 7.74−7.70
(m, 2H), 7.52−7.47 (m, 2H), 7.25−7.19 (m, 3H), 7.05−6.98 (m,
2H), 5.67 (dt, J = 10.0, 17.2 Hz, 1H), 5.39 (d, J = 10.0 Hz, 1H), 5.08
(d, J = 17.0 Hz, 1H), 3.50−3.44 (m, 1H), 2.83−2.76 (m, 1H), 2.58−
2.44 (m, 2H), 2.02−1.93 (m, 1H); 13C{1H} NMR (100 MHz,
CDCl3) δ 140.4, 138.9, 135.7, 130.6, 129.6, 129.5, 128.5, 128.4, 126.3,
124.5, 69.0, 34.6, 28.4. HRMS (ESI) m/z: [M + Na]+ calcd for
C17H17ClO2SNa 343.0535; found 343.0527.
2-((5-Phenylpent-1-en-3-yl)sulfonyl)thiophene (3cj). Prepared
from 1c and 2j by following the general procedure. Purification was
performed with flash column chromatography (PE/EA = 20:1) on
silica gel to obtain the title compound as a colorless oil in 85% yield
(49.7 mg); 1H NMR (400 MHz, CDCl3) δ 7.71 (dd, J = 1.2, 5.2 Hz,
1H), 7.60 (dd, J = 1.2, 5.2 Hz, 1H), 7.30−7.27 (m, 2H), 7.23−7.19
(m, 1H), 7.15−7.12 (m, 3H), 5.73 (dt, J = 10.0, 17.2 Hz, 1H), 5.44
(d, J = 10.0 Hz, 1H), 5.19 (d, J = 17.0 Hz, 1H), 3.00−3.54 (m, 1H),
2.83−2.77 (m, 1H), 2.60−2.45 (m, 2H), 2.05−1.96 (m, 1H);
13C{1H} NMR (100 MHz, CDCl3) δ 139.9, 138.0, 135.2, 134.2,
1-Fluoro-4-((5-phenylpent-1-en-3-yl)sulfonyl)benzene (3ce). Pre-
pared from 1c and 2e by following the general procedure. Purification
was performed with flash column chromatography (PE/EA = 20:1)
on silica gel to obtain the title compound as a colorless oil in 85%
yield (51.7 mg); 1H NMR (400 MHz, CDCl3) δ 7.82−7.79 (m, 2H),
F
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Article
129.9, 128.6, 128.4, 127.6, 126.4, 124.4, 70.1, 32.3, 28.7. HRMS (ESI)
m/z: [M + Na]+ calcd for C15H16O2S2Na 315.0489; found 315.0481.
(3-(Methylsulfonyl)pent-4-en-1-yl)benzene (3ck). Prepared from
1c and 2k by following the general procedure. Purification was
performed with flash column chromatography (PE/EA = 20:1) on
silica gel to obtain the title compound as a colorless oil in 78% yield
(35.0 mg); 1H NMR (400 MHz, CDCl3) δ 7.34−7.17 (m, 5H), 5.87
(dt, J = 10.0, 17.2 Hz, 1H), 5.58 (d, J = 10.0 Hz, 1H), 5.44 (d, J =
17.2 Hz, 1H), 3.46−3.40 (m, 1H), 2.89−2.83 (m, 1H), 2.82 (s, 3H),
2.63−2.44 (m, 2H), 2.08−1.99 (m, 1H); 13C{1H} NMR (100 MHz,
CDCl3) δ 139.8, 131.3, 128.6, 128.5, 126.4, 124.1, 67.7, 38.1, 32.0,
27.0. HRMS (ESI) m/z: [M + Na]+ calcd for C12H16O2SNa
247.0769; found 247.0763.
(3-(Ethylsulfonyl)pent-4-en-1-yl)benzene (3cl). Prepared from 1c
and 2l by following the general procedure. Purification was performed
with flash column chromatography (PE/EA = 20:1) on silica gel to
obtain the title compound as a colorless oil in 82% yield (39.1 mg);
1H NMR (400 MHz, CDCl3) δ 7.34−7.17 (m, 5H), 5.85 (dt, J = 10.0,
17.2 Hz, 1H), 5.54 (d, J = 10.0 Hz, 1H), 5.40 (d, J = 17.0 Hz, 1H),
3.49−3.43 (m, 1H), 2.97 (dd, J = 11.6, 19.2 Hz, 2H), 2.88−2.81 (m,
1H), 2.62−2.43 (m, 2H), 2.10−2.01 (m, 1H), 1.33 (t, J = 7.6 Hz,
3H); 13C{1H} NMR (100 MHz, CDCl3) δ 139.9, 131.4, 128.6, 128.4,
126.4, 121.1, 65.5, 44.5, 32.1, 26.8, 6.0. HRMS (ESI) m/z: [M + Na]+
calcd for C13H18O2SNa 261.0925; found 261.0916.
(3-(Cyclopropylsulfonyl)pent-4-en-1-yl)benzene (3cm). Prepared
from 1c and 2m by following the general procedure. Purification was
performed with flash column chromatography (PE/EA = 20:1) on
silica gel to obtain the title compound as a white colorless oil in 76%
yield (38.1 mg); 1H NMR (400 MHz, CDCl3) δ 7.33−7.17 (m, 5H),
5.87 (dt, J = 10.0, 17.2 Hz, 1H), 5.54 (d, J = 10.0 Hz, 1H), 5.44 (d, J
= 17.0 Hz, 1H), 3.51−3.45 (m, 1H), 2.87−2.80 (m, 1H), 2.62−2.55
(m, 1H), 2.52−2.43 (m, 1H), 2.40−2.34 (m, 1H), 2.12−2.02 (m,
1H), 1.31−1.22 (m, 2H), 1.03−0.94 (m, 2H); 13C{1H} NMR (100
MHz, CDCl3) δ 140.1, 131.0, 128.5, 128.4, 126.3, 123.7, 67.2, 32.1,
27.6, 27.4, 4.8, 4.6. HRMS (ESI) m/z: [M + Na]+ calcd for
C14H18O2SNa 273.0925; found 273.0916.
silica gel to obtain the title compound as a yellow solid in 78% yield
(43.1 mg); 1H NMR (400 MHz, CDCl3) δ 7.64−7.61 (m, 2H),
7.33−7.23 (m, 5H), 7.12−7.07 (m, 2H), 6.31 (dt, J = 10.0, 17.2 Hz,
1H), 5.49 (d, J = 10.0 Hz, 1H), 5.35 (d, J = 17.2 Hz, 1H), 4.68 (d, J =
9.2 Hz, 1H); 13C{1H} NMR (100 MHz, CDCl3) δ 167.0, 164.5,
133.2, 133.1, 132.1, 132.0, 131.9, 129.6, 129.0, 128.9, 128.7, 124.0,
116.0, 115.8, 75.8. HRMS (ESI) m/z: [M + Na]+ calcd for
C15H13FO2SNa 299.0518; found 299.0512.
4-((1-Phenylallyl)sulfonyl)benzonitrile (3in). Prepared from 1i and
2n by following the general procedure. Purification was performed
with flash column chromatography (PE/EA = 10:1) on silica gel to
obtain the title compound as a white solid in 80% yield (56.3 mg); 1H
NMR (400 MHz, CDCl3) δ 7.75−7.70 (m, 4H), 7.36−7.29 (m, 3H),
7.25−7.22 (m, 2H), 6.30 (dt, J = 10.0, 17.2 Hz, 1H), 5.53 (d, J = 10.0
Hz, 1H), 5.42 (d, J = 17.2 Hz, 1H), 4.71 (d, J = 9.2 Hz, 1H); 13C{1H}
NMR (100 MHz, CDCl3) δ 141.5, 132.3, 131.1, 129.9, 129.6, 129.3,
128.9, 128.2, 124.6, 117.3, 117.1, 75.7. HRMS (ESI) m/z: [M + Na]+
calcd for C16H13NO2SNa 306.0565; found 306.0558.
1-Nitro-4-((1-phenylallyl)sulfonyl)benzene (3io). Prepared from
1i and 2o by following the general procedure. Purification was
performed with flash column chromatography (PE/EA = 10:1) on
silica gel to obtain the title compound as a white solid in 81% yield
(49.1 mg); 1H NMR (400 MHz, CDCl3) δ 8.26 (d, J = 8.8 Hz, 2H),
7.82 (d, J = 8.8 Hz, 2H), 7.36−7.24 (m, 5H), 6.32 (dt, J = 10.0, 17.2
Hz, 1H), 5.54 (d, J = 10.0 Hz, 1H), 5.39 (d, J = 17.2 Hz, 1H), 4.74
(d, J = 9.2 Hz, 1H); 13C{1H} NMR (100 MHz, CDCl3) δ 150.7,
143.0, 130.7, 129.7, 129.4, 128.9, 128.1, 124.8, 123.7, 118.2, 75.8.
HRMS (ESI) m/z: [M + Na]+ calcd for C15H13NO4SNa 326.0463;
found 326.0455.
1-Bromo-3-((1-phenylallyl)sulfonyl)benzene (3ip). Prepared from
1i and 2p by following the general procedure. Purification was
performed with flash column chromatography (PE/EA = 10:1) on
silica gel to obtain the title compound as a yellow oil in 86% yield
(58.0 mg); 1H NMR (400 MHz, CDCl3) δ 7.75 (s, 1H), 7.69 (d, J =
8.0 Hz, 1H), 7.55 (d, J = 8.0 Hz, 1H), 7.36-7.24 (m, 6H), 6.31 (dt, J =
10.0, 17.2 Hz, 1H), 5.50 (d, J = 10.0 Hz, 1H), 5.35 (d, J = 17.2 Hz,
1H), 4.69 (d, J = 9.2 Hz, 1H); 13C{1H} NMR (100 MHz, CDCl3) δ
138.9, 136.6, 132.1, 131.5, 130.0, 129.7, 129.1, 128.7, 128.6, 127.8,
124.2, 122.7, 75.7. HRMS (ESI) m/z: [M + Na]+ calcd for
C15H13BrO2SNa 358.9717; found 358.9709.
1-Methyl-4-((1-phenylallyl)sulfonyl)benzene (3ib).21f Prepared
from 1i and 2b by following the general procedure. Purification was
performed with flash column chromatography (PE/EA = 10:1) on
silica gel to obtain the title compound as a white solid in 87% yield
(47.4 mg); 1H NMR (400 MHz, CDCl3) δ 7.50 (d, J = 8.4 Hz, 2H),
7.32−7.23 (m, 7H), 6.30 (dt, J = 10.0, 17.2 Hz, 1H), 5.45 (d, J = 10.0
Hz, 1H), 5.30 (d, J = 17.2 Hz, 1H), 4.67 (d, J = 9.2 Hz, 1H), 2.40 (s,
3H); 13C{1H} NMR (100 MHz, CDCl3) δ 144.5, 134.2, 132.1, 129.7,
129.3, 129.2, 128.8, 128.6, 123.5, 75.6, 21.6. HRMS (ESI) m/z: [M +
Na]+ calcd for C16H16O2SNa 295.0769; found 295.0762.
1-Methoxy-4-((1-phenylallyl)sulfonyl)benzene (3ic). Prepared
from 1i and 2c by following the general procedure. Purification was
performed with flash column chromatography (PE/EA = 10:1) on
silica gel to obtain the title compound as a white solid in 90% yield
(51.9 mg); 1H NMR (400 MHz, CDCl3) δ 7.52 (d, J = 8.8 Hz, 2H),
7.33−7.22 (m, 5H), 6.87 (d, J = 8.8 Hz, 2H), 6.31 (dt, J = 10.0, 17.2
Hz, 1H), 5.45 (d, J = 10.0 Hz, 1H), 5.31 (d, J = 17.2 Hz, 1H), 4.66
(d, J = 9.2 Hz, 1H), 3.84 (s, 3H); 13C{1H} NMR (100 MHz, CDCl3)
δ 163.6, 132.4, 131.4, 129.7, 129.4, 128.7, 128.5, 123.4, 113.8, 75.8,
55.6. HRMS (ESI) m/z: [M + Na]+ calcd for C16H16O3SNa
311.0718; found 311.0718.
1-Chloro-4-((1-phenylallyl)sulfonyl)benzene (3id). Prepared from
1i and 2d by following the general procedure. Purification was
performed with flash column chromatography (PE/EA = 10:1) on
silica gel to obtain the title compound as a white solid in 86% yield
(50.4 mg); 1H NMR (400 MHz, CDCl3) δ 7.56 (d, J = 8.0 Hz, 2H),
7.64−7.23 (m, 7H), 6.30 (dt, J = 10.0, 17.2 Hz, 1H), 5.49 (d, J = 10.0
Hz, 1H), 5.35 (d, J = 17.2 Hz, 1H), 4.68 (d, J = 9.2 Hz, 1H); 13C{1H}
NMR (100 MHz, CDCl3) δ 140.4, 135.6, 131.7, 130.7, 129.7, 129.1,
128.9, 128.8, 128.7, 124.1, 75.7. HRMS (ESI) m/z: [M + Na]+ calcd
for C15H13ClO2SNa 315.0222; found 315.0214.
Scale-up Experiment and Synthesis of ( )-Hinokiresinol.
Scale-up Experiment. To an oven-dried 100 mL round-bottom flask
equipped with a magnetic stir bar, (CH3CN)3W(CO)3 (145.5 mg, 10
mol %), 4,4′-di-tert-butyl-2,2′-bipyridine ligand (L3) (201.3 mg, 15
mol %), allylic carbonate 1k (1.32 g, 5.0 mmol), and sodium
benzenesulfinate 2a (1.23 g, 7.5 mmol) were added. The reaction
flask was sealed with a rubber septum, then evacuated and backfilled
with nitrogen. Anhydrous ethanol (0.2 M, 25 mL) was added via a
syringe. The resulting mixture was stirred at 60 °C for 24 h. The
reaction mixture was cooled to room temperature and concentrated.
The obtained crude mixture was purified by flash column
chromatography on silica gel to afford the pure allylic sulfone 3ka
in 89% (1.3 g) isolated yield. The branched-to-linear ratio is 19:1.
Synthesis of ( )-Hinokiresinol. Condition A. Following the
literature procedure16a by Crudden and co-workers, with some
modifications: under nitrogen environment, to an oven-dried screw-
cap reaction tube equipped with a magnetic stir bar, Ni(cod)2 (10 mol
%), BrettPhos (12 mol %), and NaOEt (2.2 equiv) were added. Then,
allylic sulfone 3ka (0.2 mmol), boronic acid 4 (1.0 equiv), and
toluene (0.2 M) were also added. The reaction tube was capped,
sealed, and stirred at 80 °C for 20 h. After completion, the reaction
mixture was cooled to room temperature and then diluted with
EtOAc and saturated aqueous NH4Cl (0.2 mL) was added. The
reaction mixture was then filtered and washed with EtOAc. The
obtained residue was concentrated and purified by flash column
chromatography on silica gel to afford pure 5 as a colorless oil (15.6
mg, 24%).
1-Fluoro-4-((1-phenylallyl)sulfonyl)benzene (3ie). Prepared from
1i and 2e by following the general procedure. Purification was
performed with flash column chromatography (PE/EA = 10:1) on
Condition B. By following the literature procedure,16b to an oven-
dried screw-cap reaction tube (10 mL) with a magnetic stir bar,
[PdCl(allyl)]2 (3.7 mg, 5 mol %), SIPr·HCl (8.5 mg, 10 mol %), dry
G
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J. Org. Chem. XXXX, XXX, XXX−XXX

The Journal of Organic Chemistry
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Article
dioxane (0.5 mL), and 1M NaOHaq (0.6 mL, 0.6 mmol) were added
at room temperature under the nitrogen atmosphere. After stirring for
30 min, allylic sulfone 3ka (57.67 mg, 0.2 mmol), boronic acid 4
(71.2 mg, 0.4 mmol), and dry dioxane (0.5 mL) were added. The
reaction tube was sealed and was stirred at 120 °C for 15 h. The
reaction mixture was cooled to room temperature and then diluted
with EtOAc, and saturated aqueous NH4Cl (0.2 mL) was added. The
mixture was filtered and washed with EtOAc. The obtained residue
was concentrated and purified by flash column chromatography on
silica gel to afford pure 5 as a colorless oil (18 mg, 32%). This
compound can be converted to ( )-hinokiresinol by following the
reported literature procedures.18b 1H NMR (400 MHz, CDCl3): δ =
7.36−7.31 (m, 2H), 7.22−7.17 (m, 2H), 6.92−6.83 (m, 4H), 6.39 (d,
J = 16.0 Hz, 1H), 6.27 (dd, J = 16.0, 6.8 Hz, 1H), 6.11 (ddd, J = 17.1,
10.2, 6.8 Hz, 1H), 5.17 (dt, J = 10.2, 1.6 Hz, 1H), 5.14 (dt, J = 17.1,
1.6 Hz, 1H), 4.18 (t, J = 6.8 Hz, 1H), 3.82 (s, 3H), 3.80 (s, 3H);
13C{1H} NMR (100 MHz, CDCl3): δ 158.7, 158.1, 140.5, 134.7,
130.1, 130.0, 129.8, 129.1, 127.4, 115.2, 113.8, 55.1, 51.6. HRMS
(ESI) m/z: [M + Na]+ calcd for C13H18O3SNa 277.0869; found
277.0871. The overall spectroscopic data are in complete agreement
with assigned structures and fully consistent with the reported
literature.18b
Muhammad Salman − Department of Applied Chemistry,
School of Science and Xi’an Key Laboratory of Sustainable
Energy Material Chemistry, Xi’an Jiao Tong University, Xi’an
710049, P. R. China
Shahid Khan − Department of Applied Chemistry, School of
Science and Xi’an Key Laboratory of Sustainable Energy
Material Chemistry, Xi’an Jiao Tong University, Xi’an 710049,
P. R. China
Junjie Zhang − Department of Applied Chemistry, School of
Science and Xi’an Key Laboratory of Sustainable Energy
Material Chemistry, Xi’an Jiao Tong University, Xi’an 710049,
P. R. China
Complete contact information is available at:
https://pubs.acs.org/10.1021/acs.joc.0c01632
Author Contributions
†Y.X. and M.S. contributed equally to this work.
Notes
The authors declare no competing financial interest.
W-Catalyzed Asymmetric Allylic Sulfonylation. As described in
Scheme 1 of the main text, allylic sulfonylation of 1m with (R)-L8 as a
chiral ligand occurred in 35.5% ee. Further studies including
evaluation of other reaction parameters and chiral ligands are
currently in progress.
ACKNOWLEDGMENTS
■
This work was supported by the “Fundamental Research
Funds for Central Universities” (No. 1191329135), Key
Laboratory Construction Program of Xi’an Municipal Bureau
of Science and Technology (No. 201805056ZD7CG40), and
the starting fund of Xi’an Jiao Tong University (No.
7121182002). The instrumental analysis center of Xi’an Jiao
Tong University is acknowledged for analytical assistance.
EXPERIMENTAL PROCEDURE
■
To an oven-dried screw-cap reaction tube equipped with a magnetic
stirrer, (CH3CN)3W(CO)3 (7.8 mg, 10 mol %), (R)-L8 as the chiral
ligand (6.7 mg, 15 mol %), allylic carbonate 1m (38.44 mg, 0.2
mmol), and sodium benzenesulfinate 2a (49.25 mg, 0.3 mmol) were
added. The reaction tube was sealed with a rubber septum, then
evacuated and backfilled with nitrogen. Anhydrous ethanol (0.2 M, 1
mL) was added via a syringe. The resulting mixture was stirred at 60
°C for 24 h. The reaction mixture was cooled to room temperature,
and the residue was purified by flash column chromatography on silica
gel to afford the pure allylic sulfone (R)-3ia with 62% isolated yield.
The branched-to-linear ratio was determined to be 10:1. Analytical
data of the pure (R)-3ia product are similar to the corresponding
racemate 3ia. Enantiomeric excess of (R)-3ia was determined by
HPLC analysis.21f HPLC conditions: Chiralcel OD-H column, 254
REFERENCES
■
(1) For reviews on Pd-catalysis, see: (a) Trost, B. M.; Vranken, D. L.
Asymmetric Transition Metal-Catalyzed Allylic Alkylations. Chem.
Rev. 1996, 96, 395−422. (b) Trost, B. M. Pd Asymmetric Allylic
Alkylation (AAA). A Powerful Synthetic Tool. Chem. Pharm. Bull.
2002, 50, 1−14. (c) Trost, B. M.; Crawley, M. L. Asymmetric
Transition-Metal-Catalyzed Allylic Alkylations: Applications in Total
Synthesis. Chem. Rev. 2003, 103, 2921−2944.
(2) For selected reviews on transition metal-catalyzed allylic
substitution, see: (a) Lu, Z.; Ma, S. Matal-Catalyzed Enantioselective
Allylation in Asymmetric Synthesis. Angew. Chem., Int. Ed. 2008, 47,
258−297. (b) Cheng, Q.; Tu, H.-F.; Zheng, C.; Qu, J.-P.; Helmchen,
G.; You, S.-L. Iridium-Catalyzed Asymmetric Allylic Substitution
Reactions. Chem. Rev. 2019, 119, 1855−1969. and references therein.
(3) For selected reviews on Ir-catalysis, see: (a) Hartwig, J. F.;
Stanley, L. M. Mechanisticallyl Driven Development of Iridium
Catalysts for Asymmetric Allylic Substitution. Acc. Chem. Res. 2010,
43, 1461−1475. (b) Reference 2b.
(4) For initial work on molybdenum, see: (a) Trost, B. M.; Lautens,
M. Molybdenum catalysts for allylic alkylation. J. Am. Chem. Soc.
1982, 104, 5543−5545. For initial work on tungsten, see: (b) Trost,
B. M.; Hung, M.-H. Tungsten-catalyzed allylic alkylations. New
avenues for selectivity. J. Am. Chem. Soc. 1983, 105, 7757−7759.
(5) For other selected examples reported by Trost and co-workers,
see: (a) Trost, B. M. Pd- and Mo-Catalyzed Asymmetric Allylic
Alkylation. Org. Process Res. Dev. 2012, 16, 185−194. (b) Trost, B. M.;
Hachiya, I. Asymmetric Molybdenum-Catalyzed Alkylations. J. Am.
Chem. Soc. 1998, 120, 1104−1105. (c) Trost, B. M.; Dogra, K.
Synthesis of Novel Quaternary Amino Acids Using Molybdenum-
Catalyzed Asymmetric Allylic Alkylation. J. Am. Chem. Soc. 2002, 124,
7256−7257. (d) Trost, B. M.; Zhang, Y. Mo-Catalyzed Regio-,
Diastereo-, and Enantioselective Allylic Alkylation of 3-Aryloxindoles.
J. Am. Chem. Soc. 2007, 129, 14548−14549. (e) Trost, B. M.; Zhang,
Y. Catalytic Double Stereoinduction in Asymmetric Allylic Alkylation
of Oxindoles. Chem. - Eur. J. 2010, 16, 296−303. (f) Trost, B. M.;
Miller, J. R.; Hoffman, C. M. A Highly Enantio- and Diastereoslective
nm; flow rate: 1 mL/min; i-PrOH/hexanes: 1/9; tminor: 10.87 min;
25
t
major: 11.72 min; 35.5% ee. [α]D = 19.5 (c = 0.52, CHCl3).
ASSOCIATED CONTENT
* Supporting Information
The Supporting Information is available free of charge at
https://pubs.acs.org/doi/10.1021/acs.joc.0c01632.
■
sı
Spectral data of all prepared compounds with copies of
1H, 13C NMR spectra and HPLC chromatograms (PDF)
AUTHOR INFORMATION
Corresponding Author
■
Ajmal Khan − Department of Applied Chemistry, School of
Science and Xi’an Key Laboratory of Sustainable Energy
Material Chemistry, Xi’an Jiao Tong University, Xi’an 710049,
P. R. China; orcid.org/0000-0002-2415-7534;
Email: ajmalkhan@xjtu.edu.cn
Authors
Yaoyao Xu − Department of Applied Chemistry, School of
Science and Xi’an Key Laboratory of Sustainable Energy
Material Chemistry, Xi’an Jiao Tong University, Xi’an 710049,
P. R. China
H
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Article
Molybdenum-Catalyzed Asymmetric Allylic Alkylation of Cyanoest-
ers. J. Am. Chem. Soc. 2011, 133, 8165−8167.
Medicinal Chemistry. Curr. Top. Med. Chem. 2016, 16, 1200−1216.
(d) Scott, K. A.; Njardarson, J. T. Analysis of US FDA-Approved
Drugs Containing Sulfur Atoms. Top. Curr. Chem. 2018, 376, 5.
(15) For selected examples on the synthesis of allylic sulfone via
transition metal-catalyzed allylic substitution, see: (a) Jegelka, M.;
Plietker, B. Selective C-S Bond Formation via Fe-Catalyzed Allylic
Substitution. Org. Lett. 2009, 11, 3462−3465. (b) Ueda, M.; Hartwig,
J. F. Iridium-catalyzed Regio- and Enantioselective Allylic Substitution
with Aromatic and Aliphatic Sulfinates. Org. Lett. 2010, 12, 92−94.
(c) Wu, X.-S.; Chen, Y.; Li, M.-B.; Zhou, M.-G.; Tian, S.-K. Direct
Substitution of Primary Allylic Amines with Sulfinate Salts. J. Am.
Chem. Soc. 2012, 134, 14694−14697. (d) Ma, X.-T.; Dai, R.-H.;
Zhang, J.; Gu, Y.; Tian, S.-K. Catalytic Stereospecific Substitution of
Enantioenriched Allylic Alcohols with Sodium Sulfinates. Adv. Synth.
Catal. 2014, 356, 2984−2988. (e) Cai, A.; Kleij, A. W. Regio- and
Enantioselective Preparation of Chiral Allylic Sulfones Featuring
Elusive Quaternary Stereocenters. Angew. Chem., Int. Ed. 2019, 58,
14944−14949. and references therein.
(16) For selected examples on sulfone as electrophile in Suzuki
cross-coupling, see: (a) Ariki, Z. T.; Maekawa, Y.; Nambo, M.;
Crudden, C. M. Preparation of Quaternary Centers via Nickel-
Catalyzed Suzuki-Miyaura Cross-Coupling of Tertiary Sulfones. J. Am.
Chem. Soc. 2018, 140, 78−81. (b) Nambo, M.; Crudden, C. M.
Modular Synthesis of Triarylmethanes through Palladium-Catalyzed
Sequential Arylation of Methyl Phenyl Sulfone. Angew. Chem., Int. Ed.
2014, 53, 742−746. (c) Nambo, M.; Crudden, C. M. Recent
Advances in the Synthesis of Triarylmethanes by Transition Metal
Catalysis. ACS Catal. 2015, 5, 4734−4742. For selected examples on
sulfone as electrophile in allylic substitutions, see: (d) Trost, B. M.;
Merlic, C. A. Geminal alkylation: substitutions of allyl sulfones.
Regiocontrol via molybdenum catalysis. J. Org. Chem. 1990, 55,
1127−1129. (e) Takizawa, K.; Sekino, T.; Sato, S.; Yoshino, T.;
Kojima, M.; Matsunaga, S. Cobalt-Catalyzed Allylic Alkylation
Enabled by Organophotoredox Catalysis. Angew. Chem., Int. Ed.
2019, 58, 9199−9203.
(6) For selected examples, see: (a) Belda, O.; Moberg, C.
Molybdenum-Catalyzed Asymmetric Allylic Alkylations. Acc. Chem.
Res. 2004, 37, 159−167. (b) Moberg, C. Molybdenum-Catalyzed and
Tungsten-Catalyzed Enantioselective Allylic Substitutions. Top.
Organomet. Chem. 2011, 38, 209−234. (c) Del Litto, R. D.;
Benessere, V.; Ruffo, F.; Moberg, C. Carbohydrate-Based Pyridine-
2-carboxamides for Mo-Catalyzed Asymmetric Allylic Alkylations.
Eur. J. Org. Chem. 2009, 9, 1352−1356.
(7) (a) Hughes, D. L.; Palucki, M.; Yasuda, N.; Reamer, R. A.;
Reider, P. J. Solvent-Dependent Dynamic Kinetic Asymmetric
Transformation/Kinetic Resolution in Molybdenum-catalyzed Asym-
metric Allylic Alkylation. J. Org. Chem. 2002, 67, 2762−2768.
(b) Trost, B. M.; Dogra, K.; Hachiya, I.; Emura, T.; Hughes, D. L.;
Krska, S.; Reamer, R. A.; Palucki, M.; Yasuda, N.; Reider, P. J.
Designed Ligands as Probes for the Catalytic Binding Mode in Mo-
Catalyzed Asymmetric Allylic Alkylation. Angew. Chem., Int. Ed. 2002,
41, 1929−1932.
(8) (a) Lloyd-Jones, G. C.; Pfaltz, A. Chiral Phosphanodihydrox-
anzoles in Asymmetric Catalysis: Tungsten-Catalyzed Allylic Sub-
stitution. Angew. Chem. 1995, 34, 462−464. (b) Glorius, F.;
Neuburger, M.; Pfaltz, A. Highly Enantio- and Regioselective Allylic
Alkylations Catalyzed by Chiral [Bis(dihydrooxazole)]molybdenum
Complexes. Helv. Chim. Acta 2001, 84, 3178−3196. (c) Lehmann, J.;
Lloyd-Jones, G. C. Regiocontrol and Stereoselectivity in Tungsten-
Bipyridine Catalysed Allylic Alkylation. Tetrahedron 1995, 51, 8863−
8874.
(9) For other examples, see: (a) Malkov, A. V.; Gouriou, L.; Lloyd-
Jones, G. C.; Stary, I.; Langer, V.; Spoor, P.; Vinader, V.; Kocovsky, P.
Asymmetric Allylic Substitution Catalyzed by C1-Symmetrical
Complexes of Molybdenum: Structural Requirements of the Ligand
and the Stereochemical Course of the Reaction. Chem. - Eur. J. 2006,
12, 6910−6929. (b) Krska, S. W.; Hughes, D. L.; Reamer, R. A.;
Mathre, D. J.; Sun, Y. The Unusual Role of CO Transfer in
Molybdenum-Catalyzed Asymmetric Alkylations. J. Am. Chem. Soc.
2002, 124, 12656−12657. (c) Ozkal, E.; Pericas, M. A. A
Bis(Triazolecarboxamido) Ligand for Enantio- and Regioselective
Molybdenum-Catalyzed Asymmetric Allylic Alkylation Reactions.
Adv. Synth. Catal. 2014, 356, 711−717.
(17) For reviews on the use of bipyridine type ligands, see; (a) Kaes,
C.; Katz, A.; Hosseini, M. W. Bipyridine: The Most Widely Used
Ligand. A Review of Molecules Comprising at Least Two 2,2′-
Bipyridine Units. Chem. Rev. 2000, 100, 3553−3590. (b) Chelucci,
G.; Thummel, R. P. Chiral 2,2′-Bipyridine, 1,10-Phenanthrolines, and
2,2′:6′,2″-Terpyridines: Synthesis and Applications in Asymmetric
Homogeneous Catalysis. Chem. Rev. 2002, 102, 3129−3170.
(18) For previous synthesis, see: (a) Lassen, P. R.; Skytte, D. M.;
Hemmingsen, L.; Nielsen, S. F.; Freedman, T. B.; Nafie, L. A.;
Christensen, S. B. Structure and Absolute Configuration of Nyasol
and Hinokiresinol via Synthesis and Vibrational Circular Dichroism
Spectroscopy. J. Nat. Prod. 2005, 68, 1603−1609. (b) Hamilton, J. Y.;
Sarlah, D.; Carreira, E. M. Iridium-Catalyzed Enantioselective Allylic
Vinylation. J. Am. Chem. Soc. 2013, 135, 994−997.
(10) Salman, M.; Xu, Y.; Khan, S.; Zhang, J.; Khan, A. Regioselective
molybdenum-catalyzed allylic substitution of tertiary allylic electro-
philes: methodology development and applications. Chem. Sci. 2020,
11, 5481−5486.
(11) Tungsten catalyzed allylic substitutions are limited to the few
reports available in literature with stabilized carbon nucleophiles to
form C-C bond; see: refs 4b and 8
(12) To the best of our knowledge, there is no report available in
literature on the use of heteroatom nucleophile to form carbon-
heteroatom bond in W-catalyzed allylic substitution.
(19) See Experimental Section.
(13) (a) Khan, A.; Zhao, H.; Zhang, M.; Khan, S.; Zhao, D. Regio-
and Enantioselective Synthesis of Sulfone-Bearing Quaternary Carbon
Stereocenters via Pd-Catalyzed Allylic Substitution. Angew. Chem., Int.
Ed. 2020, 59, 1340−1345. (b) Khan, A.; Zhang, J.; Khan, S. Palladium
nano-particles as a recyclable catalyst for C-O bond formation under
solvent free conditions. Green Chem. 2020, 22, 4116−4120.
(c) Zhang, M.-N.; Khan, S.; Zhang, J.; Khan, A. Palladium
nanoparticles as efficient catalyst for C-S bond formation reactions.
RSC Adv. 2020, 10, 31022−31026.
(14) For the application of sulfone in organic synthesis, see:
(a) Fuchs, P. L.; Braish, T. F. Multiply Convergent Synthesis via
Conjugate-addition Reactions to Cycloalkenyl Sulfones. Chem. Rev.
1986, 86, 903−917. (b) Peters, B. K.; Zhou, T.; Rujirawanich, J.;
Cadu, A.; Singh, T.; Rabten, W.; Kerdphon, S.; Andersson, P. W. An
Enantioselective Approach to the Preparation of Chiral Sulfones by Ir-
Catalyzed asymmetric Hydrogenation. J. Am. Chem. Soc. 2014, 136,
16557−16562. For the application of sulfone in drugs and bioactive
compounds, see: (c) Feng, M.; Tang, B.; Liang, S. H.; Jiang, X. Sulfur
Containing Scaffolds in Drugs: Synthesis and Application in
(20) For the synthesis of other related gem-diarylalkyl compounds,
see: (a) Goswami, G.; Chauhan, N.; Mal, A.; Das, S.; Das, M.; Ghorai,
M. K. Synthesis of 3,3-Diaryl/Heteroarylpropylamines via Nucleo-
philic Ring Opening of Activated Azetidines with Arenes and
Heteroarenes: New Synthetic Route to ( )-Tolterodine. ACS
Omega 2018, 3, 17562−17572. (b) Qu, J.; Helmchen, G. Applications
of Iridium-Catalyzed Asymmetric Allylic Substitution Reactions in
Target-Oriented Synthesis. Acc. Chem. Res. 2017, 50, 2539−2555.
(c) Polet, D.; Rathgeb, X.; Falciola, C. A.; Langlois, J.-B.; Hajjaji, S. E.;
Alexakis, A. Enantioselective Iridium-Catalyzed Allylic Arylation.
Chem. - Eur. J. 2009, 15, 1205−1216.
(21) (a) Zhang, P.; Brozek, L. A.; Morken, J. P. Pd-Catalyzed
Enantioselective Allyl-Allyl Cross-Coupling. J. Am. Chem. Soc. 2010,
132, 10686−10688. (b) Roberts, J. P.; Lee, C. Allylic Etherification
via Ir(I)/Zn(II) Bimetallic Catalysis. Org. Lett. 2005, 7, 2679−2682.
(c) Trost, B. M.; Fraisse, P. L.; Ball, Z. T. A Stereospecific
Ruthenium-Catalyzed Allylic Alkylation. Angew. Chem., Int. Ed. 2002,
41, 1059−1061. (d) Yatsumonji, Y.; Ishida, Y.; Tsubouchi, A.;
Takeda, T. Nickel(0) Triethyl Phosphite Complex-Catalyzed Allylic
I
https://dx.doi.org/10.1021/acs.joc.0c01632
J. Org. Chem. XXXX, XXX, XXX−XXX

The Journal of Organic Chemistry
pubs.acs.org/joc
Article
Substitution with Retention of Regio- and Stereochemistry. Org. Lett.
2007, 9, 4603−4606. (e) R eference 16e. (f) Reference 15b.
(22) Du, B.; Qian, P.; Wang, Y.; Mei, H.; Han, J.; Pan, Y. Cu-
Catalyzed Deoxygenative C2-Sulfonylation Reaction of Quinoline N-
Oxides with Sodium Sulfinate. Org. Lett. 2016, 18, 4144−4147.
J
https://dx.doi.org/10.1021/acs.joc.0c01632
J. Org. Chem. XXXX, XXX, XXX−XXX