Indium-Catalyzed Reductive Dithioacetalization of Carboxylic Acids with Dithiols: Scope, Limitations, and Application to Oxidative Desulfurization

Article abstract of DOI:10.1021/acs.joc.7b00170

In this study an InI₃-TMDS (1,1,3,3-tetramethyldisiloxane) reducing system effectively catalyzed the reductive dithioacetalization of a variety of aromatic and aliphatic carboxylic acids with 1,2-ethanedithiol or 1,3-propanedithiol leading to the one-pot preparation of either 1,3-dithiolane derivatives or a 1,3-dithiane derivative. Also, the intact indium catalyst continuously catalyzed the subsequent oxidative desulfurization of an in situ formed 1,3-dithiolane derivative, which led to the preparation of the corresponding aldehydes.

Full text of DOI:10.1021/acs.joc.7b00170

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Article
Indium-Catalyzed Reductive Dithioacetalization of Carboxylic Acids with
Dithiols: Scope, Limitations, and Application to Oxidative Desulfurization
Kota Nishino, Kohei Minato, Takahiro Miyazaki, Yohei Ogiwara, and Norio Sakai
J. Org. Chem., Just Accepted Manuscript • DOI: 10.1021/acs.joc.7b00170 • Publication Date (Web): 21 Mar 2017
Downloaded from http://pubs.acs.org on March 25, 2017
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Indium-Catalyzed Reductive Dithioacetalization of Carboxylic Acids with Dithiols:
Scope, Limitations, and Application to Oxidative Desulfurization
Kota Nishino, Kohei Minato, Takahiro Miyazaki, Yohei Ogiwara, and Norio Sakai*
Department of Pure and Applied Chemistry, Faculty of Science and Technology, Tokyo University of
Science (RIKADAI), Noda, Chiba 278–8510, Japan
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E–mail: sakachem@rs.noda.tus.ac.jp
Abstract
In this study an InI3-TMDS (1,1,3,3-tetramethyldisiloxane) reducing system effectively catalyzed the
reductive dithioacetalization of a variety of aromatic and aliphatic carboxylic acids with
1,2-ethanedithiol or 1,3-propanedithiol leading to the one-pot preparation of either 1,3-dithiolane
derivatives or a 1,3-dithiane derivative. Also, the intact indium catalyst continuously catalyzed the
subsequent oxidative desulfurization of an in-situ formed 1,3-dithiolane derivative, which led to the
preparation of the corresponding aldehydes.
Introduction
Dithioacetals have been utilized as a protecting group for carbonyl compounds, such as aldehydes and
ketones, and as a masked acyl anion equivalent in synthetic conversions.1 Both general and classic
methods of dithioacetals have been widely achieved via a main group metal catalyst- or a transition
metal catalyst-promoted condensation of carbonyl compounds with thiols or dithiols.2,3,4 Also,
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dithioacetalization has been in continuous development via either a metal catalyst-free system using
HCl gas,5a PTSA,5b SO2,5c SOCl2-SiO2,5d HClO4-SiO2,5e I2,5f NBS,5g glycerol,5h or by a solid-phase
synthesis.5i Most of the carbonyl compounds employed in these reactions have been limited to
aldehydes and ketones, and no extensive study has been focused on the dithioacetalization of a
carboxylic acid in the presence of a thiol. To convert a carboxylic acid to a dithioacetal, it is necessary
to add a reducing agent to the reaction system. Carboxylic acids generally tolerates to a typical
reducing reagent due to the formation of a carboxylate anion after deprotonation. Hence, the
development of a simple and practical procedure for the reductive dithioacetalization of a carboxylic
acid has been highly desired.
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Thus far, the only example has been reported by Kim and co-workers wherein a direct
dithioacetalization of carboxylic acids via the treatment with either thexylphenylthioborane or
1,3,2-dithiaborinane-dimethyl sulfide in the presence of SnCl2 was developed. That procedure, however,
used a borane as a reducing agent, which required the in-situ formation of an activated borane
intermediate and a stoichiometric amount of SnCl2 to complete the desired dithioacetalization.6 On the
other hand, we found an interesting result, in which a reducing system composed of an indium(III)
catalyst with TMDS as a reducing agent efficiently catalyzed the condensation of carboxylic acids with
1,2-ethanedithiol leading to the direct preparation of 1,3-dithiolane (dithioacetal) derivatives.7,8
However, in the previous work, only three examples of 1,3-dithiolane derivatives could be prepared.
The details are unclear concerning the reactivity of carboxylic acids with a variety of functional groups.
Thus, we report herein the full details of a series of direct dithioacetalizations of carboxylic acids,
involving re-examinations of the reaction conditions, the scope and limitations of carboxylic acids, and
functional group tolerance. Also, we disclose an interesting application, wherein a one-pot conversion
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from an aromatic carboxylic acid into an aromatic aldehyde was achieved via a procedure that
combined the previously mentioned reducing catalytic system with a subsequent oxidation step.
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Results and discussion
On the basis of our previous work,7 when dithioacetalization of p-toluic acid with 1,2-ethanedithiol
was re-examined with 5 mol % of InI3, which has a stronger Lewis acidity than InBr3 (83%), under
same conditions involving TMDS (Si-H: 6 equiv) and 1,2-dichloroethane, the desired protection was
completed within 20 h to produce 1,3-dithiolane 1 in an 82% yield (entries 1 and 2 in Table 1). To
establish milder conditions for the dithioacetalization, the same reaction was conducted at 60 ˚C.
However, contrary to our expectation, a decrease in the product yield was observed (entry 3). In
contrast, a reaction with chloroform at 60 ˚C showed a high solvent effect (entry 4). Interestingly, when
the dithioacetalization was carried out in toluene, a remarkable increase in the reaction rate was
observed, and a series of the dithioacetalization was completed within 2 h to isolate 80% of thioacetal 1
after a common column purification (entry 5). The effect of a hydrosilane was then investigated.
Consequently, with the exception of PhMe2SiH, other hydrosilanes, such as PhSiH3, Ph2MeSiH, Et3SiH,
and (EtO)3SiH, were ineffective for the dithioacetalization, which led to a decrease in the yield of 1
(entries 6-10). Also, the use of 4 equiv (per a carboxylic acid) of TMDS showed a similar effect and
produced 1 in a relatively excellent yield (entry 11). On the other hand, when an equivalent of TMDS
was decreased to 2 equiv, the progress of the protection was remarkably hindered, leading to a rather
low yield of 1 (entry 12). Finally, the results shown in entry 11 were regarded as optimal conditions for
the dithioacetalization of a carboxylic acid.
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TABLE 1. Examinations of the reaction conditionsa
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entry
InX3
hydrosilane
solvent
temp
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time
(h)
yield
(%)b
(Si-H)
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2
InBr3
InI3
InI3
InI3
InI3
InI3
InI3
InI3
InI3
InI3
InI3
InI3
TMDS (6)
TMDS (6)
TMDS (6)
TMDS (6)
TMDS (6)
PhSiH3 (6)
PhMe2SiH (6)
Ph2MeSiH (6)
Et3SiH (6)
(EtO)3SiH (6)
TMDS (4)
TMDS (2)
1,2-DCEc
1,2-DCE
1,2-DCE
CHCl3
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2
(83)
82
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toluene
toluene
toluene
toluene
toluene
toluene
toluene
toluene
92 (80)
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a
Standard conditions: p-toluic acid (0.5 mmol), 1,2-ethanedithiol (0.6 mmol), an indium compound
(0.025 mmol), a hydrosilane (Si-H: 1-3 mmol) and solvent (2 mL).
b GC (Isolated) yield.
c 1,2-DCE = 1,2-dichloroethane.
Then, to extend the generality of the present dithioacetalization, the examinations were conducted
with a variety of aromatic aldehydes under the optimal conditions, and the results are summarized in
Table 2. Carboxylic acids either with a methyl group or without a substituent were converted to the
corresponding 1,3-dithiolane derivatives 2-5 in relatively good yields (entries 1-4). Also, carboxylic
acids with an oxygen-containing substituent, such as methoxy and phenoxy groups, produced
1,3-dithiolane derivatives 6 and 7 in practical yields (entries 5 and 6). In the cases with an ortho-methyl
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and a para-methoxy group, no formation of by-products was observed. In contrast, the substrates with a
nitrogen-containing group, such as an N,N-dimethyl amino group or an unsubstituted amino group, led
to a considerable decrease in the yields of each 1,3-dithiolane derivative (entries 7 and 8). On the other
hand, when benzoic acid derivatives with a moderate electron-deficient group, such as a halogen and a
trifluoromethyl group, were used under the optimal conditions, the corresponding 1,3-dithiolane
derivatives 10-12 were obtained in good yields (entries 9-11). For a carboxylic acid derived from a
benzoic acid ester, the reducing system similarly worked on the ester C=O double bond to produce a
mixture of 1,3-dithiolane 13 and bis(1,3-dithiolanyl)benzene derivative 13’ (entry 12). However, when
an aromatic carboxylic acid with a strong electron-deficient group, such as a cyano group, was
employed, the expected 1,3-dithiolnae was obtained in a rather low yield (entry 13), and the most
starting materials remained with no formation of a reduction product from the cyano group. Regardless
of the substituted position, when naphthoic acids were treated under these reducing conditions, the
corresponding dithioacetalization effectively proceeded to yield 1,3-dithiolanes 15 and 16 in 67 and
59% yields (entries 14 and 15). Gratifyingly, dithioacetalization was applied to an electron-rich
heterocyclic compound, which finally afforded the furan ring-substituted 1,3-dithiolane 17 in a
moderate yield (entry 16). Unfortunately, a carboxylic acid with a pyridine ring involved a more basic
nitrogen atom did not undertake the expected dithioacetalization, which led to the formation of a
complicated mixture (entry 17). Generally, it seems that the basic functional groups containing a
nitrogen or an oxygen atom would coordinate to the indium catalyst, which led to the decrease in the
catalytic activity (entries 5, 7, 8, 13, 16 and 17). When p-toluic acid was also reacted with
1,3-propanedithiol under the same conditions, 2-(4-methylphenyl)-1,3-dithiane (19) was obtained in a
high yield (entry 18).
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TABLE 2. Substrate scope of aromatic carboxylic acidsa
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entry
product
yield
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entry
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yield
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Isolated yield. InI3 (10mol %), 120 ˚C (bath temperature). A complex mixture. 80 ˚C (bath
temperature). e InI3 (10 mol %). f 120 ˚C (bath temperature).
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Next, we attempted the dithioacetalization of various aliphatic carboxylic acids (Table 3). For
example, dithioacetalization of 3-phenylpropionic acid proceeded cleanly to produce the corresponding
dithioacetal 20 in an 82% yield. Also, a conjugate carboxylic acid afforded a good yield of a mixture
(1 : 4) of the desired 1,3-dithiolane 21 and an over-reduced 1,3-dithiolane 20 with a reduced double
bond. When the carboxylic acid with an alkyne moiety was treated under the optimal conditions, the
corresponding dithiolane 22 was produced in a 45% yield. Interestingly, the dithioacetalization of fatty
acids, such as 10-undecenoic acid and oleic acid, efficiently produced 1,3-dithiolanes 23 and 24 in
excellent yields. Both terminal and internal alkene moieties were tolerated to the reducing system, and
the cis-geometry of oleic acid has remained the same stereochemistry. Moreover, the reductive
dithioacetalization of bulky carboxylic acids with a branched carbon next to the carbonyl moiety, such
as 9-fluorenecarboxylic acid and 2-phenylbutylic acid yielded the expected 1,3-dithiolanes 25 and 26 in
good yields.
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TABLE 3. Substrate scope of aliphatic carboxylic acidsa
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a Isolated yield. b Determined by NMR.
Using the optimal conditions (Scheme 1), we also examined the dithioacetalization of other
carbonyl compounds, such as an acyl chloride and an ester, with identical oxidation numbers for the
central carbon as well as a carboxylic acid. For example, when the reaction was carried out with an acyl
chloride, the corresponding dithioacetal was obtained in a relatively low yield. On the other hand,
dithioacetalization of an ester under the same conditions proceeded cleanly to form 1,3-dithiolane 1 in a
high yield as shown in entry 11, Table 1.
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SCHEME 1. Applications to dithioacetalization of other carbonyl compounds
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To test the utility of this procedure, a one-pot conversion of aromatic carboxylic acids into
aromatic aldehydes was attempted (Scheme 2). On the basis of previous reports on the desulfurization
of a dithioacetal with the combination of a promoter as a metal catalyst and an economical and
readily-available oxidizing agent, H2O2 (hydrogen peroxide),1f,9 the oxidative desulfurization of
1,3-dithiolane 1 as a model reaction was examined. Consequently, the oxidizing system involving InI3
(10 mol %), KI (10 mol %) and H2O2 aqueous solution (4 equiv), efficiently undertook the expected
desulfurization of 1 to yield the corresponding aldehyde, p-tolualdehyde in a good yield (eq 1 in
Scheme 2). Moreover, it was proved that the oxidative conversion even occurred without the addition
of KI. Hence, when the one-pot conversion of p-toluic acid into p-tolualdehyde was practically carried
out using only the further addition of H2O2 after the first step, the effective desulfurization smoothly
took place to give the desired aldehyde in a 79% yield (eq 2 in Scheme 2). It was implied that the
indium catalyst remained intact after the first reduction step, and promoted the second oxidation step.10
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SCHEME 2. Conversion to an aldehyde via oxidative desulfurization of 1,3-dithiolane 1
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Scheme 3 shows a plausible reaction path for the dithioacetalization of carboxylic acids. Initially,
silyl ester A was formed through the reaction between a starting carboxylic acid and a hydrosilane
involving the generation of hydrogen gas.7 Then, silyl ester A, which was activated by an indium
catalyst, was reduced again by another molecule of a hydrosilane to produce the corresponding silyl
acetal B. The silyl acetal was subsequently substituted by one side of an in-situ generated thiosilane
moiety of a dithiol to form O,S-acetal intermediate C.11,12 After that, the other side of the thiosilane in
intermediate C undertook intramolecular cyclization, which finally led to the production of the desired
dithioacetal.
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SCHEME 3. Plausible reaction pathway for the dithioacetalization of carboxylic acids
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Conclusions
We have demonstrated that unlike conventional dithioacetalization of carbonyl compounds, such as
aldehydes and ketones, the present reducing system composed of a toluene solution of InI3 and TMDS
achieved the direct and effective conversion of aromatic and aliphatic carboxylic acids with a variety of
functional groups into the corresponding 1,3-dithiolanes and 1,3-dithiane. Also, we described how this
reducing system could be applied to the similar conversion of an acyl chloride and an ester. Moreover,
the indium catalyst that remained intact to successfully catalyze the subsequent oxidative
desulfurization of the formed 1,3-dithiolanes, leading to the production of the corresponding aldehydes.
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Experimental Section
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General methods. All reactions were carried out under a N2 atmosphere, unless otherwise noted.
Toluene was freshly distilled from a Na-benzophenone solution. All indium compounds, aromatic
carboxylic acids, aliphatic carboxylic acids and dithiols are commercially available and were used
without further purification. Hydrosilanes were also used without further purification. Column
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chromatography was also performed using silica gel. H NMR spectra were measured at 500 MHz
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using tetramethylsilane as an internal standard (0.00 ppm). C NMR spectra were measured at 125
MHz using the center peak of chloroform (77.0 ppm).
General procedure for the synthesis of 1,3-dithiolanes: To a freshly distilled toluene solution (1.0
mL) in a screw-capped test tube under a N2 atmosphere were successively added a magnetic stirrer bar,
an aromatic or aliphatic carboxylic acid (0.5 mmol), 1,2-ethanedithiol (0.60 mmol, 54 mg), InI3 (0.025
mmol, 23 mg), and TMDS (1.0 mmol, 1.3 x 102 ꢀL). The test tube was sealed with a cap that contained
a PTFE septum and was heated to 60 °C for 2 h. After the reaction, the resultant mixture was quenched
with a saturated NaOH aqueous solution (3 mL). The aqueous layer was extracted with ethyl acetate (3
mL x 3). The combined organic phase was dried over anhydrous Na2SO4, filtered, and then evaporated
under reduced pressure. The crude material was purified by silica gel column chromatography (hexane
as an eluent,) to give the corresponding 1,3-dithiolane, and, if necessary, further purified by a
Preparative HPLC (chloroform as an eluent).
General procedure for the one-pot conversion of a carboxylic acid to an aldehyde: To a freshly
distilled toluene solution (2.0 mL) in a screw-capped test tube under a N2 atmosphere were successively
added a magnetic stirrer bar, p-toluic acid (1.0 mmol, 136 mg), 1,2-ethanedithiol (1.20 mmol, 108 mg),
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InI3 (0.05 mmol, 46 mg), and TMDS (2.0 mmol, 2.6 x 102 ꢀL). The test tube was sealed with a cap that
contained a PTFE septum, and was heated to 60 °C for 2 h. After 2 h, H2O2 (30% aqueous solution, 4
mmol, 0.5 mL) was added and stirred at room temperature for 16 h. After the reaction, the resultant
mixture was quenched using a saturated Na2S2O3 aqueous solution (3 mL). The mixture was filtered
and extracted with ethyl acetate (3 mL x 3). The combined organic phase was determined the quantity
of p-tolualdehyde by gas chromatography.
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2- (p-Tolyl)-1,3-dithiolane (1).12 80% yield (78 mg); a white solid; mp 58-59 °C; H NMR (500 MHz,
CDCl3) δ 2.33 (s, 3H), 3.32-3.38 (m, 2H), 3.47-3.54 (m, 2H), 5.63 (s, 1H), 7.12 (d, J = 8.0 Hz, 2H),
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7.41 (d, J = 8.0 Hz, 2H); C NMR (125 MHz, CDCl3) δ 21.1, 40.2, 56.1, 127.8, 129.2, 137.1, 137.9;
MS (EI): 196 (M+); HRMS (FAB-Magnetic Sector): Calcd for C10H12S2: 196.0381, Found: 196.0378.
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2-(m-Tolyl)-1,3-dithiolane (2).13 68% yield (133 mg); a colorless oil; H NMR (500 MHz, CDCl3) δ
2.34 (s, 3H), 3.32-3.37 (m. 2H), 3.47-3.52 (m, 2H), 5.61 (s, 1H), 7.07 (d, J = 7.5 Hz, 1H), 7.19 (dd, J =
7.5, 8.0 Hz, 1H), 7.31 (d, J = 8.0 Hz, 1H), 7.34 (s, 1H); 13C NMR (125 MHz, CDCl3) δ 21.3, 40.2, 56.2,
125.0, 128.3, 128.5, 128.8, 138.1, 140.1; MS (EI): 196 (M+); HRMS (EI-Quadrupole): Calcd for
C10H12S2: 196.0381, Found: 196.0378.
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2-(o-Tolyl)-1,3-dithiolane (3). 46% yield (90 mg); a colorless oil; H NMR (500 MHz, CDCl3) δ 2.42
(s, 3H), 3.32-3.38 (m, 2H), 3.46-3.52 (m, 2H), 5.87 (s, 1H), 7.12 (d, J = 7.5 Hz, 1H), 7.14-7.17 (m, 1H),
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7.19-7.22 (m, 1H), 7.79 (d, J = 7.0 Hz, 1H); C NMR (125 MHz, CDCl3) δ 19.7, 39.7, 52.8, 126.4,
127.6, 127.7, 130.3, 135.7, 137.9; MS (EI): 196 (M+); HRMS (EI-Quadrupole): Calcd for C10H12S2:
196.0381, Found: 196.0377.
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2-(3,5-Dimethylphenyl)-1,3-ditholane (4). 90% yield (189 mg); a colorless oil; H NMR (500 MHz,
CDCl3) δ 2.29 (s, 6H), 3.28-3.34 (m, 2H), 3.45-3.51 (m, 2H), 5.58 (s, 1H), 6.88 (s, 1H), 7.12-7.13 (m,
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2H); C NMR (125 MHz, CDCl3) δ 21.2, 40.1, 56.2, 125.6, 129.7, 137.9, 139.9; MS (EI): 210 (M+);
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HRMS (EI-Quadrupole): Calcd for C11H14S2: 210.0537, Found: 210.0533.
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2-Phenyl-1,3-dithiolane (5).12 78% yield (142 mg); a colorless oil; H NMR (500 MHz, CDCl3) δ
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3.32-3.36 (m, 2H), 3.45-3.51 (m, 2H), 5.63 (s, 1H), 7.23-7.32 (m, 3H), 7.50-7.53 (m, 2H); C NMR
(125 MHz, CDCl3) δ 40.2, 56.2, 127.9, 128.0, 128.4, 140.2; MS (EI): 182 (M+); HRMS
(EI-Quadrupole): Calcd for C9H10S2: 182.0224, Found: 182.0220.
2-(4-Methoxyphenyl)-1,3-dithiolane (6).12 49% yield (104 mg); a white solid; mp 60-61 °C; 1H NMR
(500 MHz, CDCl3) δ 3.33-3.36 (m, 2H), 3.49-3.53 (m, 2H), 3.80 (s, 3H), 5.64 (s, 1H), 6.84 (d, J = 8.5
Hz, 2H), 7.45 (d, J = 8.5 Hz, 2H); 13C NMR (125 MHz, CDCl3) δ 40.2, 55.3, 56.0, 113.8, 129.1, 131.7,
159.3; MS (EI): 212 (M+); HRMS (EI-Quadrupole): Calcd for C10H12OS2: 212.0330, Found: 212.0337.
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2-(3-Phenoxyphenyl)-1,3-dithiolane (7). 77% yield (211 mg); a colorless oil; H NMR (500 MHz,
CDCl3) δ 3.31-3.36 (m, 2H), 3.44-3.49 (m, 2H), 5.59 (s, 1H), 6.87-6.89 (m, 1H), 7.01 (d, J = 7.5 Hz,
2H), 7.11 (t, J = 7.5 Hz, 1H), 7.21 (s, 1H), 7.25-7.28 (m, 2H), 7.34 (td, J = 8.0, 1.0 Hz, 2H); 13C NMR
(125 MHz, CDCl3) δ 40.2, 55.7, 118.1, 118.4, 118.9, 122.6, 123.3, 129.7, 142.7, 156.9, 157.2; MS (EI):
274 (M+),; HRMS (EI-Quadrupole): Calcd for C15H14OS2: 274.0486, Found: 274.0481.
2-(4-N,N-Dimethylaminophenyl)-1,3-dithiolane (8).12 29% yield (65 mg); a white solid; mp
105-106 °C; 1H NMR (500 MHz, CDCl3) δ 2.94 (s, 6H), 3.31-3.36 (m, 2H), 3.47-3.52 (m, 2H), 5.65 (s,
1H), 6.66 (d, J = 8.5 Hz, 2H), 7.40 (d, J = 8.5 Hz, 2H); 13C NMR (125 MHz, CDCl3) δ 40.1, 40.5, 56.6,
112.3, 126.6, 128.8, 150.4; MS (EI): 225 (M+); HRMS (EI-Quadrupole): Calcd for C11H15NS2:
225.0646, Found: 225.0647.
2-(4-Chlorophenyl)-1,3-dithiolane (10).12 65% yield (140 mg) ; a white solid; mp 58-59 °C; 1H NMR
(500 MHz, CDCl3) δ 3.30-3.37 (m, 2H), 3.44-3.50 (m, 2H), 5.58 (s, 1H), 7.27 (d, J = 8.5 Hz, 2H), 7.45
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(d, J = 8.5 Hz, 2H); C NMR (125 MHz, CDCl3) δ 40.2, 55.4, 128.5, 129.3, 133.6, 139.0; MS (EI):
216 (M+), 218 (M++2); HRMS (EI-Quadrupole): Calcd for C9H9S2Cl: 215.9834, Found: 215.9826.
2-(4-Iodophenyl)-1,3-dithiolane (11). 63% yield (194 mg); a white solid; mp 92-93 °C; 1H NMR (500
MHz, CDCl3) δ 3.32-3.38 (m, 2H), 3.45-3.51 (m, 2H), 5.55 (s, 1H), 7.26 (d, J = 8.5 Hz, 2H), 7.63 (d, J
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= 8.5 Hz, 2H); C NMR (125 MHz, CDCl3) δ 40.3, 55.6, 93.4, 129.8, 137.5, 140.3; MS (EI): 308
(M+); HRMS (EI-Quadrupole): Calcd for C9H9S2I: 307.9191, Found: 307.9189.
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2-(3-Trifluoromethylphenyl)-1,3-dithiolane (12). 85% yield (213 mg); a colorless oil; H NMR (500
MHz, CDCl3) δ 3.35-3.41 (m, 2H), 3.48-3.55(m, 2H), 5.65 (s, 1H), 7.43 (t, J = 7.5 Hz, 1H), 7.52 (d, J =
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7.5 Hz, 14H), 7.70 (d, J = 7.5 Hz, 1H), 7.79 (s, 1H); C NMR (125 MHz, CDCl3) δ 40.3, 55.5, 123.9
(q, JC-F = 271.2 Hz), 124.8 (q, JC-F = 3.75 Hz) (overlap x 2), 128.9, 130.8 (q, JC-F = 32.5 Hz), 131.4 (d,
JC-F = 1.3 Hz), 141.9; MS (EI): 250 (M+); HRMS (EI-Quadrupole): Calcd for C10H9S2F3: 250.0098,
Found: 250.0087.
2-(4-(Methoxycarbonyl)phenyl)-1,3-dithiolane (13).14 33% yield (87 mg: 13/13’ = 3:2); a white
solid; 1H NMR (500 MHz, CDCl3) δ 3.34-3.41 (m, 2 H), 3.48-3.53 (m, 2 H), 3.91 (s, 3 H), 5.64 (s, 1 H),
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7.58 (d, J = 8.0 Hz, 2 H), 7.98 (d, J = 8.0 Hz, 2 H); C NMR (125 MHz, CDCl3) δ 40.3, 55.1, 55.5,
127.9, 129.7, 129.8, 146.0, 166.6; MS (EI): 240 (M+); HRMS (EI-Quadrupole): Calcd for C11H12O2S2:
240.0279, Found: 240.0280.
Bis(1,3-dithiolanyl)benzene (13’).12 33% yield (87 mg: 13/13’ = 3:2); a white solid; H NMR (500
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MHz, CDCl3) δ 3.34-3.41 (m, 4 H), 3.48-3.53 (m, 4 H), 5.62 (s, 2 H), 7.46 (s, 4 H); C NMR (125
MHz, CDCl3) δ 40.2, 55.8, 128.1, 140.2; MS (EI): 286 (M+); HRMS (EI-Quadrupole): Calcd for
C12H14S4: 285.9979, Found: 285.9987.
2-(4-Cyanophenyl)-1,3-dithiolane (14). 9% yield (21 mg); a white solid; mp 53-55 °C; 1H NMR (500
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MHz, CDCl3) δ 3.38-3.42 (m, 2H), 3.47-3.52 (m, 2H), 5.61 (s, 1H), 7.60 (d, J = 8.5 Hz, 2 H), 7.62 (d, J
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= 8.5 Hz, 2H); C NMR (125 MHz, CDCl3) δ 40.4, 55.2, 111.6, 118.6, 128.7, 132.3, 146.5; MS (EI):
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207 (M+); HRMS (EI-Quadrupole): Calcd for C10H9NS2: 207.0176, Found: 207.0182.
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2-(2-Naphtyl)-1,3-dithiolane (15).15 67% yield (155 mg); a white solid; mp 140-142 °C; H NMR
(500 MHz, CDCl3) δ 3.38-3.44 (m, 2H), 3.53-3.59 (m, 2H), 5.82 (s, 1H), 7.45-7.49 (m, 2H), 7.69 (dd, J
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= 8.5, 1.5 Hz, 1H), 7.79-7.83 (m, 3H), 7.89 (s, 1H); C NMR (125 MHz, CDCl3) δ 40.4, 56.5, 125.9,
126.2, 126.3, 126.5, 127.6, 127.9, 128.6, 132.9, 133.1, 137.6; MS (EI): 232 (M+); HRMS
(EI-Quadrupole): Calcd for C13H12S2: 232.0381, Found: 232.0383.
2-(1-Naphtyl)-1,3-dithiolane (16). 59% yield (137 mg); a colorless oil; 1H NMR (500 MHz, CDCl3) δ
3.35-3.40 (m, 2 H), 3.42-3.48 (m, 2H), 6.41 (s, 1H), 7.42-7.45 (m, 1H), 7.49-7.46 (m, 1H), 7.54 (td, J =
8.5, 1.5 Hz, 1H), 7.75 (d, J = 8.5 Hz, 1H), 7.84 (d, J = 8.5 Hz, 1H), 8.01 (d, J = 7.5 Hz, 1H), 8.16 (d, J
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= 8.5 Hz, 1H); C NMR (125 MHz, CDCl3) δ 39.6, 52.7, 123.2, 124.7, 125.3, 125.7, 126.2, 128.5,
128.8, 131.0, 133.8, 135.5; MS (EI): 232 (M+); HRMS (EI-Quadrupole): Calcd for C13H12S2: 232.0381,
Found: 232.0389.
2-(2-Furyl)-1,3-dithiolane (17).12 43% yield (74 mg); a colorless oil; H NMR (500 MHz, CDCl3) δ
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3.28-3.34 (m, 2H), 3.40-3.46 (m, 2H), 5.63 (s, 1H), 6.27-6.30 (m, 2H), 7.36 (m, 1H); C NMR (125
MHz, CDCl3) δ 39.1, 47.4, 107.0, 110.3, 142.6, 154.2; MS (EI): 172 (M+); HRMS (EI-Quadrupole):
Calcd for C7H8OS2: 172.0017, Found: 172.0018.
2-(p-Tolyl)-1,3-dithiane (19).16 77% yield (162 mg); a white solid; mp 82-83 °C ;1H NMR (500 MHz,
CDCl3) δ 1.88-1.96 (m, 1H), 2.15-2.17 (m, 1H), 2.33 (s, 3H), 2.88-2.92 (m, 2H), 5.14 (s, 1H), 7.15 (d,
J = 7.5 Hz, 2H), 7.36 (d, J = 7.5 Hz, 1H); 13C NMR (125 MHz, CDCl3) δ 21.2, 25.1, 32.1, 51.2, 127.6,
129.4, 136.1, 138.3; MS (EI): 210 (M+); HRMS (EI-Quadrupole): Calcd for C11H14S2: 210.0537,
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Found: 210.0539.
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2-(2-Phenylethyl)-1,3-dithiolane (20).13 82% yield (172 mg); a colorless oil; H NMR (500 MHz,
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CDCl3) δ 2.11-2.15 (m, 2H), 2.78 (t, J = 7.5 Hz, 2H), 3.18-3.29 (m, 4H), 4.44 (t, J = 7.0 Hz, 1H),
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7.19-7.20 (m, 3H), 7.27-7.30 (m, 2H); C NMR (125 MHz, CDCl3) δ 35.2, 38.4, 41.1, 52.8, 126.0,
128.4, 128.5, 140.8; MS (EI): 210 (M+); HRMS (EI-Quadrupole): Calcd for C11H14S2: 210.0537,
Found: 210.0545.
2-(2-Phenylethylene)-1,3-dithiolane (21).12 90% yield (170 mg, 20/21 = 1:4); a colorless oil; 1H NMR
(20+21, 500 MHz, CDCl3) δ 2.10 -2.14 (m, 2H), 2.77 (t, J = 7.5 Hz, 2H), 3.16-3.20 (m, 2H), 3.21-3.25
(m. 2H), 3.26-3.32 (m, 2H), 3.34-3.37 (m, 2H), 4.43 (t, J = 7.0 Hz, 1H), 5.22 (d, J = 9 Hz, 1H), 6.21
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(dd, J = 9, 16 Hz, 1H), 6.50 (d, J = 16 Hz, 1H), 7.18-7.21 (m, 12H), 7.22-7.24 (m, 2H); C NMR
(20+21,125 MHz, CDCl3) δ 35.2, 38.3, 40.0, 41.0, 52.7, 54.4, 126.0, 126.3, 126.6, 127.8, 128.36,
128.44, 128.5, 129.0, 130.1, 136.0, 140.8; MS (EI): 208 (M+); HRMS (EI-Quadrupole): Calcd for
C11H12S2: 208.0380, Found: 208.0388.
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2-(2-Phenylethynyl)-1,3-dithiolane (22). 45% yield (93 mg); a colorless oil; H NMR (500 MHz,
CDCl3) δ 3.35-3.40 (m, 2H), 3.49-3.54 (m, 2H), 5.37 (s, 1H), 7.28-7.30 (m, 3H), 7.41-7.43 (m, 2H);
13C NMR (125 MHz, CDCl3) δ 39.4, 40.3, 84.2, 88.0, 122.5, 128.1, 128.4, 131.6; MS (EI): 206 (M+);
HRMS (EI-Quadrupole): Calcd for C11H10S2: 206.0224, Found: 206.0233.
2-(9-Decenyl)-1,3-dithiolane (23).12 95% yield (231 mg); a colorless oil; 1H NMR (500 MHz, CDCl3)
δ 1.28 (m, 8H), 1.37-1.43 (m, 4H), 1.79-1.84 (m, 2H), 2.01-2.06 (m, 2H), 3.16-3.27 (m, 4H), 4.46 (td, J
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= 7.0, 2.5 Hz, 1H), 4.91-4.94 (m, 1H), 4.97-5.01 (m, 1H), 5.76-5.84 (m, 1H); C NMR (125 MHz,
CDCl3) δ 28.8, 29.0, 29.1, 29.24, 29.27, 29.31, 33.7, 38.3, 39.3, 53.7, 114.1, 139.1; MS (EI): 244 (M+);
HRMS (EI-Quadrupole): Calcd for C13H24S2: 244.1319, Found: 244.1299.
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2-(9Z-Octadecenyl)-1,3-dithiolane (24). 98% yield (335 mg); a colorless oil; H NMR (500 MHz,
CDCl3) δ 0.88 (t, J = 7.0 Hz, 3H), 1.27-1.29 (m, 20H), 1.40-1.46 (m, 2H), 1.79-1.84 (m, 2H), 1.99-2.03
(m, 4H), 3.17-3.27 (m, 4H), 4.47 (t, J = 7.0 Hz, 1H), 5.33-5.36 (m, 2H); 13C NMR (125 MHz, CDCl3) δ
14.1, 22.7, 27.16, 27.21, 29.16, 29.18 (overlap x 2), 29.32, 29.34, 29.5 (overlap x 2), 29.7, 29.8, 31.9,
38.3, 39.3, 53.8, 129.8, 130.0; MS (EI): 342(M+); HRMS (EI-Quadrupole): Calcd for C20H38S2:
342.2415, Found: 342.2418.
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9-Fluorenyl-1,3-dithiolane (25). 78% yield (211 mg); a white solid; mp 80-81 °C ; H NMR (500
MHz, CDCl3) δ 3.03-3.11 (m, 4H), 4.33 (d, J = 4.5 Hz, 1H), 5.33 (d, J = 4.5 Hz, 1H), 7.29 (td, J = 7.5,
1.0 Hz, 2H), 7.40 (td, J = 7.5, 1.0 Hz, 2H), 7.75 (d, J = 7.5 Hz, 2H), 7.84 (d, J = 7.5 Hz, 2H); 13C NMR
(125 MHz, CDCl3) δ 39.1, 52.3, 56.9, 119.7, 125.4, 126.8, 127.9, 141.8, 144.5; MS (EI): 270 (M+);
HRMS (EI-Quadrupole): Calcd for C16H14S2: 270.0537, Found: 270.0529.
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2-(1-Phenylpropyl)-1,3-dithiolane (26). 98% yield (220 mg); a colorless oil; H NMR (500 MHz,
CDCl3) δ 0.75 (t, J = 7.0 Hz, 3H), 1.69-1.75 (m, 1H), 1.98-2.04 (m, 1H), 2.72 (ddd, J = 12.0, 8.5, 4.0
Hz, 1H), 3.03-3.18 (m, 4H), 4.79 (d, J = 8.5 Hz, 1H), 7.21-7.25 (m, 3H), 7.29-7.32 (m, 2H); 13C NMR
(125 MHz, CDCl3) δ 12.0, 28.5, 38.4, 38.5, 55.6, 59.9, 126.8, 128.1, 128.4, 142.3; MS (EI): 224 (M+);
HRMS (EI-Quadrupole): Calcd for C12H16S2: 224.0694, Found: 224.0687.
Supporting Information
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Copies of the H and C NMR spectra of the chlorinated products produced by this method. This
material is available free of charge via the Internet at http://pubs.acs.org.
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Acknowledgement
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This work was partially supported by JSPS KAKENHI Grant Number JP25410120. The authors deeply
thank Shin-Etsu Chemical Co., Ltd., for the gift of hydrosilanes.
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References and Notes
(1) For example, see: (a) Corey, E. J.; Seebach, D. Angew. Chem. Int. Ed. 1965, 4, 1077-1078. (b)
Seebach, D.; Corey, E. J. J. Org. Chem. 1975, 40, 231-237. (c) Seebach, D. Angew. Chem. Int. Ed.
1979, 18, 239-258. (d) Bulman Page, P. C.; van Niel, M. B.; Prodger, J. C. Tetrahedron 1989, 45,
7643-7677. (e) Yus, M.; Nájera, C.; Foubelo, F. Tetrahedron 2003, 59, 6147-6212 and the
references cited therein. (f) Greene, T. W.; Wuts, P. G. M. Protective groups in Organic Synthesis,
3rd ed.; John Wiley and Sons; New York, 1999.
(2) For selected examples with a main group metal catalyst, see: (a) Muthusamy, S.; Babu, S. A.;
Gunanathan, C. Tetrahedron Lett. 2001, 42, 359-362 and the references cited therein. (b)
Muthusamy, S.; Arulananda Babu, S.; Gunanathan, C. Tetrahedron 2002, 58, 7897-7901 and the
references cited therein. (c) Madabhushi, S.; Mallu, K. K. R.; Chinthala, N.; Beeram, C. R.;
Vangipuram, V. S. Tetrahedron Lett. 2012, 53, 697-701 and the references cited therein.
(3) For selected examples with a transition metal catalyst, see: (a) Kumar, V.; Dev, S. Tetrahedron
Lett. 1983, 24, 1289-1292 and the references cited therein. (b) Chen, C.-T.; Lin, Y.-D.; Liu, C.-Y.
Tetrahedron 2009, 65, 10470-10476 and the references cited therein. (c) De, S. K. Adv. Synth.
Catal. 2005, 347, 673-676 and the references cited therein.
(4) Larock, R. C. Comprehensive Organic Transformations, 2nd ed., WILEY-VCH: New York, 1999.
(5) For example, see: (a) Ralls, J. W.; Dodson, R. M.; Riegel, B. J. Am. Chem. Soc. 1949, 71,
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yield.
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