Mechanistic Studies on the Generation and Properties of Superelectrophilic Singlet Carbenes from Bis(perfluoroalkanesulfonyl)bromonium Ylides

Article abstract of DOI:10.1021/acs.joc.6b00142

Pyrolysis of bis(perfluoroalkanesulfonyl)bromonium ylides in various olefins results in highly stereospecific formation of cyclopropanes via unimolecular decomposition. Product analysis, kinetic study, substituent effects, and theoretical study revealed the generation of singlet bis(perfluoroalkanesulfonyl)carbenes stabilized by intramolecular coordination of sulfonyl oxygen.

Full text of DOI:10.1021/acs.joc.6b00142

Article
pubs.acs.org/joc
Mechanistic Studies on the Generation and Properties of
Superelectrophilic Singlet Carbenes from
Bis(perfluoroalkanesulfonyl)bromonium Ylides
,
†
‡
‡
‡
‡
‡
Kazunori Miyamoto,* Susumu Iwasaki, Ryusuke Doi, Taiga Ota, Yufuko Kawano, Junpei Yamashita,
‡
§
‡
∥
,∥
Yuuta Sakai, Norihiro Tada, Masahito Ochiai, Satoko Hayashi, Waro Nakanishi,*
,
†
and Masanobu Uchiyama*
†
Graduate School of Pharmaceutical Sciences, The University of Tokyo, 7-3-1 Hongo Bunkyo-ku, Tokyo 113-0033, Japan
Graduate School of Pharmaceutical Sciences, The University of Tokushima, 30-8 Shomachi, Tokushima 770-8505, Japan
Gifu Pharmaceutical University, 1-25-4, Daigaku-nishi, Gifu 501-1196, Japan
‡
§
∥
Department of Materials Science and Chemistry, Faculty of Systems Engineering, Wakayama University, 930 Sakaedani, Wakayama
640-8510, Japan
*
S Supporting Information
ABSTRACT: Pyrolysis of bis(perfluoroalkanesulfonyl)bromonium ylides in various olefins results in highly stereospecific
formation of cyclopropanes via unimolecular decomposition. Product analysis, kinetic study, substituent effects, and theoretical
study revealed the generation of singlet bis(perfluoroalkanesulfonyl)carbenes stabilized by intramolecular coordination of
sulfonyl oxygen.
INTRODUCTION
Scheme 1. Chemical Properties of Disulfonylcarbenes 1
■
Since the first report on the generation of carbene in 1903 by
Buchner and Feldmann, alkyl-, aryl-, acyl-, and heteroatom-
1
substituted carbenes have been widely used in synthetic organic
2
,3
chemistry as versatile one-carbon sources. In contrast, the
chemical properties of highly electron-deficient disulfonylcar-
benes with aryl or perfluoroalkyl substituents have been
essentially ignored, probably because of the lack of suitable
preparation methods and precursors. There have been only a
few studies on the reactivity of disulfonylcarbenes 1 (or their
metal carbenoids), which were generated by either photo-
3
chemical or transition metal-catalyzed decomposition of aryl-λ -
iodonium ylides or diazo compounds. Bis(phenylsulfonyl)-
4
copper carbenoid spontaneously degraded to afford thioperox-
oate 7, which serves as a good electrophilic trifluoromethylth-
iolating agent for enamines, allylsilanes, and pyrroles. A similar
type of oxygen atom migration of a nitro group has been well
established for singlet nitrocarbene 6, affording nitrosoformal-
carbene 1b (R = Ph) undergoes a variety of typical carbene5
reactions, such as cyclopropanation of electron-rich olefins,
electrophilic attack on noncharged tertiary N, P, As, and S
6
nucleophiles to give onium ylides, and C−H insertion reaction
11
7
dehyde 8.
into electron-rich aromatics (Scheme 1).
From the theoretical viewpoint, Sander and co-workers
reported that, because of the unusually large electron affinity
Most disulfonylcarbenes and metal carbenoids are converted
into thiosulfonate 4 (e.g., R = Ph), probably via unimolecular
decomposition of 1 through a facile [1,2]oxygen-shift from
sulfur to carbon with formation of dithiocarbonate S,S,S′-
(
EA) and high ionization potential (IP), extremely high
electrophilicity of the disulfonylcarbene 1a (R = H) is expected
4
a,8,9
trioxide 3 (Scheme 2).
This unique [1,2]oxygen shift has
1
0
been applied synthetically by Shibata and co-workers; in situ-
Received: January 22, 2016
generated benzoyl(trifluoromethylsulfonyl)carbene 5 and/or its
©
XXXX American Chemical Society
A
DOI: 10.1021/acs.joc.6b00142
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The Journal of Organic Chemistry
Article
Scheme 2. Properties of Disulfonylcarbenes 1
both in the singlet and triplet states, and it is a long-standing
issue which state is dominant (Scheme 1).
that no allylic C−H insertion products at all were observed
8
under these reaction conditions, suggesting the absence of the
3
Recently, we reported that bis(triflyl)bromonium ylide 9a (R
triplet state of carbene 1c ( 1c).
=
CF ) undergoes thermal intermolecular transylidation to
3
halobenzenes (ArX: X = I, Br, and Cl), yielding halonium
Scheme 5. Thermal Solvolysis of Bromonium Ylides 9 in cis-
and trans-Olefins
ylides, and we proposed that generation of active bis(triflyl)-
12
carbene 1c (R = CF ) was involved (Scheme 3). Here, we
3
Scheme 3. Unimolecular Decomposition of Halonium Ylides
9
and 10
report a chemical, kinetic, and theoretical examination of the
thermal generation of highly electron-deficient bis-
(
perfluoroalkanesulfonyl)carbenes from bis(perfluoroalkane-
sulfonyl)halonium ylides 9 and 10, and we discuss their spin
multiplicity.
RESULTS AND DISCUSSION
Thermal solvolysis of bromonium ylide 9a in monosubstituted
terminal alkenes as solvents afforded cyclopropane 11 and an
■
1
(
,2-S,O-addition products 12 with high chemoselectivity
Scheme 4). Ylide 9a is sparingly soluble in these olefins at
room temperature, but rapidly dissolves on heating at around
00 °C to give a pale yellow solution. Thermal solvolysis of
1
ylide 9a at 125 °C for 2 h in 1-octene and 1-decene (0.2 M)
afforded geminal bis(triflyl)cyclopropanes 11a and 11b,
respectively, with high selectivity (>97%) in good yield, along
with formation of a trace amount (1−2%) of 1,2-S,O-addition
products 12a and 12b (see also Scheme 5). It is noteworthy
Rates of thermal decomposition of bromonium ylide 9a were
measured spectrophotometrically in perfluorodecalin as a
solvent at temperatures in the range of 92−108 °C in the
presence and absence of 1-octene by monitoring the decrease
Scheme 4. Reaction of Bromonium Ylide 9a with Terminal Alkenes
B
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Article
of absorbance at 275 nm (Figure S1). The pseudo-first-order
rate constant kobs was obtained for each run, and the values for
at least triplicate runs were averaged (Table 1). Remarkably,
rate of phenylbromonium ylide 9c was decreased to about one-
tenth of that of p-(trifluoromethyl)phenylbromonium ylide 9a
(Table 1, entry 6), probably because of the decreased
3
nucleofugality of the unsubstituted phenyl-λ -bromanyl
4
−1
13
Table 1. Observed Rate Constants (10 k /s ) for Thermal
group. Introduction of p-methyl group 9d further slowed
obs
a
Decomposition of Bromonium Ylide 9 in Perfluorodecalin
down the thermal decomposition, whereas the electron-
withdrawing p-chloro group in 9e enhanced the rate of carbene
generation (entries 7 and 8). The Hammett plot showed an
temp (°C)
‡
1
-
ΔH /
excellent correlation of the relative rate factors with σp
‡
octene
kcal
ΔS /cal
3
−1
−1 −1
constants and gave a reasonable reaction constant, ρ = 1.9 (r
entry 10 M
92
100
104
108
mol
mol
K
1
4
=
1.0) (Figure 3). It should be noted that about 60−80 times
1
2
3
4
5
6
7
8
9
0.0
0.66
3.3
6.6
13
0.829
2.54
4.06
6.91
6.57
6.74
6.64
6.73
0.618
0.336
1.67
35.7
20.3
greater thermolysis rates were observed for chlorine(III)
+
−
analogue p-CF C H Cl −C Tf 10a (Table 1, entry 9) (Figure
3
6
4
2
+
−
S2), while iodine analogue p-CF C H l −C Tf did not
3
6
4
2
decompose at all even at 108 °C, probably reflecting differences
3
b
b
b
in leaving-group ability among λ -chloranyl, -bromanyl, and
0.0
0.0
0.0
0.0
1
5,16
-iodanyl groups.
To gain further mechanistic insight, thermal solvolysis of
bromonium ylide 9a in internal olefins with stereochemical
information was carried out (Scheme 5). The solvolysis in cis-4-
octene at 125 °C stereospecifically afforded cis-1,1-bis(triflyl)-
,
cd
68.5
144
29.6
12.0
aInitial concentration of ylide 9, 6.6 × 10−4 M. Thermal
b
decomposition of bromonium ylides 9c (R = H, R = CF , entry 6),
f
3
1
cyclopropane 11c as a major product in 43% yield. Careful H
9
d (R = Me, R = CF , entry 7), and 9e (R = Cl, R = CF , entry 8).
f 3 f 3
d
c
NMR analysis of the crude reaction mixture failed to detect
formation of the stereoisomeric trans-11c. On the other hand,
under similar conditions, the stereoisomeric trans-11c was
selectively produced in 43% yield in the thermal reaction in
trans-4-octene. These exclusive stereospecificities with retention
of olefin geometry were also observed in the thermolysis of
bis(nonafluorobutanesulfonyl)bromonium ylide 9b in cis- and
trans-4-octene, although the yields of the products 11d were
decreased to around one-third (12−14%) compared to those of
Chloronium ylide 10a was used instead of 9a. Rate constants
measured 84 and 76 °C are shown in Figure S2.
zero-order dependency on the thermal decomposition rate
constant at 108 °C was established for the substrate 1-octene,
indicating a reaction process in which the rate-limiting step
precedes the interaction of ylide 9a with the terminal olefin
1
2a
(
Figure 1). The large positive activation entropy (20.3 cal
11c, probably because of the increased steric demand of the
active carbene species. Comparable results were obtained from
the thermal cyclopropanation of cis- and trans-5-decene,
yielding cyclopropanes cis- and trans-11e, respectively. It should
be noted that yields and perfect stereoselectivity of these
products were not affected by the presence of radical
scavengers: thus, no formation of stereoisomeric trans-11c
was observed in thermolysis of 9a in cis-4-octene under air or in
the presence of 9,10-dihydroanthracene (Scheme S1). These
stereochemical evidence strongly support the idea that the
reactive carbene intermediates have singlet spin multiplicity
during the thermal decomposition of 9 in simple olefins, and
the cyclopropanation reaction is sufficiently faster than
2b,17
intersystem crossing to the carbene triplet state.
Remarkably, stereoselective trans-1,2-S,O-addition reactions
of perfluoroalkylthio R S and perfluoroalkylsulfinyloxy R S(O)
f
f
O groups to a double bond were also observed, along with the
stereospecific cyclopropanations: bromonium ylide 9a stereo-
selectively afforded syn-β-thiosulfinate ester 12c in 13% yield in
the reaction with cis-4-octene, whereas anti-12c was obtained in
1
2% yield when the trans olefin was employed. Unimolecular
Figure 1. Observed rate constants (104 kobs/s ) for thermal
decomposition of bromonium ylide 9a at 108 ± 0.1 °C in the
presence and absence of 1-octene in perfluorodecalin as a solvent.
−1
decomposition of bis(triflyl)carbene 1c to S-trifluoromethyl
thiosulfonate CF SO SCF 4, as shown in Scheme 2, followed
by electrophilic anti-addition to the double bond of the olefins
can reasonably explain the stereoselective formation of these
thiosulfinates 12.
and 1,2-S,O-addition was also observed in the reaction with
cyclic olefins such as cycloheptene, cyclooctene, cyclooctadiene
(Scheme 6), while cyclohexene afforded only a low yield of
anti-1,2-S,O-addition product (14%, not shown) with no
formation of the corresponding cyclopropane, probably because
3
2
3
−4
Initial concentration of ylide 9a, 6.6 × 10 M.
18,19
Competition between cyclopropanation
mol− K ) for thermal decomposition of ylide 9a is in good
agreement with the view that the cyclopropanation of 1-octene
proceeds via unimolecular rate-limiting generation of free
bis(triflyl)carbene 1c (Figure 2). Entries 6−8 illustrate the
electronic effects of para-substituents of bromonium ylides 9 on
the rate of thermal decomposition at 108 °C. The thermolysis
1
−1
7a,20−22
of its unstable nature under the conditions used.
In fact,
C
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Article
Figure 2. Activation parameter for thermal decomposition of 9a in perfluorodecalin.
Figure 3. Hammett plot of log k /log k vs σ constants in perfluorodecalin.
X
H
p
Scheme 6. Thermal Solvolysis of Bromonium Ylides 9a in
Cyclic Olefins
thermolysis of ylide 9a in methylenecyclopentane selectively
produced homoallyl disulfone 13 (73%), probably through
ring-opening of the initially formed labile intermediary
spirocyclopropane.
Further evidence for singlet nature of bis(triflyl)carbene 1c
was obtained by examination of the thermolysis in simple
arenes (Scheme 7). Thermal decomposition of bromonium
ylide 9a in toluene at 110 °C afforded a regioisomeric mixture
2
of Ar sp C−H insertion products 14, accompanied by only a
3
small amount of benzylic sp C−H insertion product 15 (2%).
Similarly, thermolysis in p-xylene and mesitylene having a
2
benzylic C−H bond selectively gave Ar sp C−H insertion
products 16 and 18. These isomeric distributions are quite
different from those observed for metal-carbenoids 20, which
showed much lower aromatic C−H/benzylic C−H bond
23
2
selectivities. The unusually high sp C−H selectivities are
probably due to the greater π-philicity of singlet carbene 1c.
Thus, electrophilic attack of 1c on the aromatic π system,
leading to formation of transient intermediates: norcaradiene
D
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The Journal of Organic Chemistry
Article
Scheme 7. Thermal Solvolysis of Bromonium Ylide 9a in Aromatic Hydrocarbons
−
1
2
1 and its equilibrium isomer cycloheptatriene 22, would
with an activation energy of 33.8 kcal mol . Interestingly,
metastable species 27 (MS) is still stabilized by the bromine
atom of PhBr. Finally, 27 (MS) ejects PhBr and generates the
constitute a major reaction pathway of the Ar C−H insertion
process (Scheme 7).
In marked contrast, solvolysis of bromonium ylide 9a in
unactivated hydrocarbons afforded C−H insertion products
2
electrophilicity of singlet bis(triflyl)carbene 1c toward even π-
lacking nucleophiles (Scheme 8). These C−H insertion
24
1
−1
carbene 1c with an energy gain of only 13.2 kcal mol ; the
resulting 1c would serve as the superelectrophilic carbene
active species for cyclopropanation of olefins and sp -selective
C−H insertion of arenes. It should be noted that the triplet
state of carbene 1c is energetically less favorable than the
singlet 1c by at least 6.8 kcal mol , which is consistent with
the experimental observation of perfect stereospecificity (see
1
2
3−25 in good to high yields, suggesting remarkably high
3
1
−1
Scheme 8. Thermal Solvolysis of Bromonium Ylide 9a in
Unactivated Hydrocarbons
26
also Table S1−S4, and Figure S3).
In conclusion, thermal decomposition of bromonium ylides
in olefins, arenes, and alkanes appears to be an efficient source
of highly electron-deficient singlet bis(perfluoroalkanesulfonyl)-
carbenes 1. The first-order kinetics, large positive activation
entropy for thermolysis of 9, substituent effects, and theoretical
calculations are all consistent with unimolecular rate-limiting
27
generation of intramolecularly stabilized carbenes 1. This is
probably due to the vastly enhanced nucleofugality of the aryl-
3
3
λ -bromanyl group compared to that of the aryl-λ -iodanyl
12a,16
group.
EXPERIMENTAL SECTION
■
General Information. IR spectra were recorded on a FT-IR
1
13
19
instrument. H NMR, C NMR, and F NMR spectra were obtained
on either a 300, 400, or 500 MHz spectrometer. Chemical shifts (δ)
are reported in parts per million (ppm) downfield from internal Me Si
4
products: alkyl- and arylbis(triflyl)methane have potential
synthetic value, because they can serve as strong Brϕnsted
or CFCl . Low mass spectra (MS) were measured on quadrupole-MS
3
with an EI probe. High-resolution MS were measured on TOF-MS
with an ESI probe. Preparative thin-layer chromatography (TLC) was
carried out on precoated plates of silica gel with fluorescent indicator
F254. Melting points were determined with melting points apparatus
and are uncorrected.
22b
acid catalysts for various organic transformations.
Further
studies on the C−H insertions are in progress.
Finally, we performed theoretical calculations on the thermal
decomposition of phenylbromonium ylide 9c at the MP2/6-
2
5
Substrates. Bromonium ylides 9a−e and chloronium ylide 10a
3
11G(d) level. These calculations indicate that the generation
of intramolecularly stabilized bis(triflyl)carbene 1c is plausible
Figure 4). The unimolecular decomposition proceeds as one
1
2
were prepared according to a literature method.
General Procedure for Thermal Reaction of Bromonium
(
Ylides 9a with Olefins. A Typical Example: Generation of
of the sulfonyl oxygen lone pairs approaches the low-lying C−
Br σ* orbital (26 (TS)), giving metastable species 27 (MS)
Bis(triflyl)carbene 1c (R = CF ) from Bromonium Ylide 9a in (E)-
3
4-Octene (Scheme 5). A suspension of bromonium ylide 9a (51 mg,
E
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The Journal of Organic Chemistry
Article
Figure 4. Energy profile for unimolecular decomposition of phenylbromonium ylide 9c based on ab initio calculations optimized at the MP2/6-
3
11G(d) (Br, S, N) and 6-31G(d, p) levels.
−
1 1
0
.10 mmol) in (E)-4-octene (0.5 mL) was heated rapidly to 135 °C
1392, 1211, 1111, 931, 852, 800, 752, 661, 611 cm ; H NMR (400
under argon and the resulting clear colorless solution was stirred for 1
h. After cooling, the yields of products were determined by H NMR
MHz, CDCl ) δ = 2.70 (dq, J = 5.8, 10.1 Hz, 1H), 2.41 (dd, J = 10.1,
3
1
6.6 Hz, 1H), 2.29 (dd, J = 10.1, 6.6 Hz, 1H), 2.05−1.95 (m, 1H),
1
3
(
1,1,2,2-tetrachloroethane as an internal standard). The reaction
1.89−1.78 (m, 1H), 1.58−1.22 (m, 8H), 0.90 (t, J = 6.5 Hz, 3H); C
1
mixture was purified by column chromatography (hexane:dichloro-
NMR (100 MHz, CDCl ) δ = 119.7 (q, J = 327.6 Hz), 119.4 (q,
3 CF
1
methane = 1:9) to yield cyclopropane trans-11c (17 mg, 43%) (R =
0
JCF = 327.6 Hz), 56.6, 34.6, 31.4, 29.0, 28.7, 26.3, 22.50, 22.46, 13.9;
F NMR (376 MHz, CDCl ) δ = −70.4 (s, 3F), −71.0 (s, 3F); MS
EI) m/z (relative intensity) 293 (5%), 123 (25), 96 (23), 93 (23), 83
48), 81 (79), 70 (90), 69 (100), 56 (96), 55 (96); HRMS (ESI,
positive) m/z calcd for C H F NaO S [(M + MeOH + Na) ]
45.0575, found 445.0554.
-(Trifluoromethylthio)octyl Trifluoromethanesulfinate (12a) (A
:1 Mixture of Diastereoisomers). Purification by preparative TLC
f
.5) and β-thiosulfinate ester anti-12c (4.2 mg, 12%) (R = 0.4).
19
f
3
trans-2,3-Dipropyl-1,1-bis(trifluoromethanesulfonyl)-
(
(
cyclopropane trans-(11c). Purification by preparative TLC (pen-
tane−dichloromethane 9:1); a colorless oil (15 mg); IR (neat) ν =
+
−
1
12 20
6
5 2
2
968, 2939, 2881, 1469, 1392, 1205, 1107, 974, 914, 665, 627 cm ;
4
1
H NMR (400 MHz, CDCl ) δ = 2.75−2.64 (m, 2H), 1.98−1.85 (m,
3
2
2
H), 1.82−1.68 (m, 2H), 1.51 (sext, J = 7.3 Hz, 4H), 1.01 (t, J = 7.3
1
1
3
1
Hz, 6H); C NMR (75 MHz, CDCl ) δ = 119.5 (q, J = 330.1 Hz),
3
CF
(pentane−dichloromethane 9:1); a colorless oil (12 mg); IR (neat) ν
2960, 2933, 2862, 1462, 1381, 1207, 1161, 1128, 951, 924, 777, 758,
07 cm ; H NMR (400 MHz, CDCl ) δ = 4.57 (dd, J = 10.3, 4.9 Hz,
6
2.7, 40.3, 28.8, 22.4, 13.7; 19F NMR (376 MHz, CDCl ) δ −70.3 (s,
F); MS (EI) m/z (relative intensity) 347 (12%, [(M − Pr) ]), 335
3
=
+
6
−1 1
6
1
1
3
(
7), 123 (11), 81 (100), 67 (52), 56 (82), 55 (61); HRMS (ESI,
H) and 4.43 (dd, J = 10.3, 7.0 Hz, 1H), 4.32 (dd, J = 10.3, 4.2 Hz,
H) and 4.16 (dd, J = 10.3, 7.0 Hz, 1H), 3.44−3.33 (m, 1H for both
+
positive) m/z calcd for C H F NaO S [(M + Na) ] 413.0292,
found 413.0303.
11
16
6
4 2
isomers), 1.90−1.78 (m, 1H for both isomers), 1.66−1.48 (m, 2H for
(1R*,2S*)-1-Propyl-2-(trifluoromethylthio)pentyl Trifluorometha-
both isomers), 1.47−1.23 (m, 7H for both isomers), 0.89 (t, J = 6.8
nesulfinate anti-(12c) (A 1:1 Mixture of Diastereoisomers).
Purification by preparative TLC (pentane−dichloromethane 9:1); a
colorless oil (5 mg); IR (neat) ν = 2966, 2939, 2879, 1468, 1385,
13
Hz, 3H for both isomers); C NMR (100 MHz, CDCl ) δ = 130.5 (q,
3
1
1
JCF = 304.7 Hz for both isomers), 122.8 (q, J = 336.3 Hz for both
isomers), 69.2 and 69.0, 44.7 and 44.5, 31.4 (both isomers), 30.9 and
CF
−1
1
1
201, 1120, 962, 864, 789, 756, 580 cm ; H NMR (400 MHz,
3
1
0.8, 28.6 (both isomers), 26.1 (both isomers), 22.5 (both isomers),
CDCl ) δ = 4.67−4.59 (m, 1H for both isomers), 3.30 (dt, J = 10.3,
3
3.9 (both isomers); 19F NMR (376 MHz, CDCl ) δ = −40.0 and
3
0
.0 Hz, 1H for both isomers), 1.94−1.22 (m, 8H for both isomers),
.97 (t, J = 7.2 Hz, 6H), 0.96 (t, J = 7.2 Hz, 3H), and 0.96 (t, J = 7.2
3
−
40.1 (s, 3F each), −78.56 and −78.58 (s, 3F each); MS (EI) m/z
+
13
1
(relative intensity) 213 (16%, [(M − CF SO ) ]), 129 (5), 115 (7),
Hz, 3H); C NMR (75 MHz, CDCl ) δ = 130.7 (q, J = 307.0 Hz
for both isomers), 122.7 (q, J = 335.7 Hz for both isomers), 87.2
and 87.0, 49.6, and 49.5 (q, J = 1.3 Hz each), 35.0 and 34.7, 31.2
and 30.1, 20.0 (for both isomers), 18.8 and 18.6, 13.6 and 13.4;
3
2
3
CF
1
111 (6), 69 (100), 57 (16), 55 (52); HRMS (ESI, positive) m/z calcd
CF
+
3
for C H F NaO S [(M + Na) ] 369.0394, found 369.0414.
10 16
6
2 2
CF
19
Elemental analysis (%), calculated for C H F O S ·1/2H O: C
F
10 16 6 2 2 2
3
3.80, H 4.82. Found: C 33.65, H 4.44. The structure of 12a was
determined by the comparison of spectral data with those of an
authentic sample, prepared from 1-octene according to the reported
NMR (376 MHz, CDCl ) δ = −40.27 and −40.32 (s, 3F each),
3
−
79.46 and −80.22 (s, 3F each); MS (EI) m/z (relative intensity) 213
+
(
18%, [(M − CF SO ) ]), 157 (10), 115 (16), 111 (14), 69 (100), 55
3
2
2
1
(
84); HRMS (ESI, positive) m/z calcd for C H F NaO S [(M +
procedure (Scheme S2).
10
16
6
2 2
+
Na) ] 369.0394, found 369.0389. Elemental analysis (%), calculated
for C H F O S ·1/2H O: C 33.80, H 4.82. Found: C 33.74, H 4.46.
The structure of anti-12c was determined by the comparison of
spectral data with those of an authentic sample, prepared from trans-4-
octene according to the reported procedure (Scheme S2).
-Hexyl-1,1-bis(trifluoromethanesulfonyl)cyclopropane (11a).
2-Octyl-1,1-bis(trifluoromethanesulfonyl)cyclopropane (11b).
Purification by preparative TLC (pentane−dichloromethane 9:1); a
pale yellow oil (14 mg); IR (neat) ν = 2929, 2860, 1468, 1439, 1392,
10
16
6
2
2
2
−1
1
1209, 1113, 856, 798, 752, 661, 611 cm ; H NMR (400 MHz,
CDCl ) δ = 2.70 (dq, J = 5.6, 10.0 Hz, 1H), 2.41 (dd, J = 10.0, 6.5 Hz,
1H), 2.29 (dd, J = 10.0, 6.5 Hz, 1H), 2.05−1.94 (m, 1H), 1.89−1.77
2
1
3
2
1
3
Purification by preparative TLC (pentane−dichloromethane 9:1); a
colorless oil (19 mg); IR (neat) ν = 2960, 2933, 2862, 1468, 1439,
(m, 1H), 1.58−1.22 (m, 12H), 0.89 (t, J = 6.8 Hz, 3H); C NMR
1
1
(100 MHz, CDCl ) δ = 119.7 (q, J = 327.6 Hz), 119.4 (q, J =
CF
3
CF
F
DOI: 10.1021/acs.joc.6b00142
J. Org. Chem. XXXX, XXX, XXX−XXX

The Journal of Organic Chemistry
Article
3
2
3
2
27.7 Hz), 56.6 (sept, 3JCF = 2.8 Hz), 34.6, 31.7, 29.2, 29.1, 29.03,
(ESI, positive) m/z calcd for C H F NaO S [(M + Na)+]
713.0100, found 713.0101.
17
16 18
4 2
9.0, 26.3, 22.6, 22.5, 14.0; 19F NMR (376 MHz, CDCl ) δ = −70.4 (s,
3
+
F), −71.0 (s, 3F); MS (EI) m/z (relative intensity) 418 (<1%, [M ]),
93 (5), 124 (12), 109 (17), 97 (26), 95 (30), 83 (33), 70 (81), 69
(1R*,2R*)-1-Propyl-2-(nonafluorobutylthio)pentyl Nonafluoro-
butanesulfinate syn-(12d) (A 1:1 Mixture of Diastereoisomers).
Purification by preparative TLC (hexane−dichloromethane 9:1); a
colorless oil (9 mg); IR (neat) ν = 2968, 2933, 2881, 1468, 1350,
(
88), 56 (100), 55 (74); HRMS (ESI, positive) m/z calcd for
+
C H F NaO S [(M + Na) ] 441.0605, found 441.0610. Elemental
analysis (%), calculated for C H F O S : C 37.32, H 4.82. Found: C
1
3
20
6
4 2
−1 1
1240, 1138, 1097, 1001, 920, 862, 796, 746, 731, 692 cm ; H NMR
13
20
6
4 2
3
7.62, H 4.75.
-(Trifluoromethylthio)decyl Trifluoromethanesulfinate (12b) (A
:1 Mixture of Diastereoisomers). Purification by preparative TLC
(400 MHz, CDCl
3
) δ = 4.63−4.55 (m, 1H for both isomers), 3.49
2
(ddd, J = 9.3, 5.1, 2.5 Hz, 1H) and 3.40 (ddd, J = 10.2, 4.3, 3.0 Hz),
1.99−1.29 (m, 8H for both isomers), 0.98 (t, J = 7.3 Hz, 6H) and 0.95
1
28
(t, J = 7.3 Hz, 6H); 13C NMR (125 MHz, CDCl ) δ = 86.1 and 85.4,
(
=
pentane−dichloromethane 9:1); a colorless oil (18 mg); IR (neat) ν
3
2929, 2858, 1466, 1379, 1209, 1161, 1128, 953, 922, 777, 758, 688,
47.5 and 47.4, 33.0 and 32.7, 32.6 and 31.9, 20.7 (for both isomers),
−1
1
19
6
1
1
07 cm ; H NMR (400 MHz, CDCl ) δ = 4.57 (dd, J = 10.4, 4.7 Hz,
H) and 4.43 (dd, J = 10.4, 7.1 Hz, 1H), 4.32 (dd, J = 10.4, 4.7 Hz,
H) and 4.16 (dd, J = 10.4, 6.6 Hz, 1H), 3.45−3.30 (m, 1H for both
18.8 and 18.7, 13.51 and 13.47, 13.33 and 13.27; F NMR (376 MHz,
3
CDCl ) δ = −81.3 (t, J = 9.3 Hz, 3F for both isomers), −81.5 (t, J =
3
9.3 Hz, 3F for both isomers), −84.6 and −86.0 (AB type, J = 234.9 Hz,
each 1F. Both signals appear as triplet, J = 12.7 Hz), −85.0 and −86.4
(AB type, J = 234.9 Hz, each 1F. Both signals appear as triplet, J = 12.7
Hz), −119.8 and −120.9 (AB type, J = 250.1 Hz, each 1F. Both signals
appear as triplet, J = 12.4 Hz), −120.3 (t, J = 12.4 Hz, 1F) and −120.4
(t, J = 12.4 Hz, 1F), −120.9 (m, 2F for both isomers), −122.4 (m, 2F
for both isomers), −125.9 (m, 2F for both isomers), −126.6 (m, 2F
isomers), 1.90−1.78 (m, 1 H for both isomers), 1.66−1.18 (m, 13 H
for both isomers), 0.89 (t, J = 6.7 Hz, 3H for both isomers); C NMR
13
1
(
100 MHz, CDCl ) δ = 130.5 (q, J = 305.1 Hz for both isomers),
3 CF
1
1
4
22.9 (q, J = 337.0 Hz for both isomers), 69.2 and 69.0, 44.7 and
4.5, 31.8 (both isomers), 30.9 and 30.8, 29.2 (both isomers), 29.1
CF
(
both isomers), 29.0 (both isomers), 26.2 (both isomers), 22.6 (both
19
isomers), 14.0 (both isomers); F NMR (376 MHz, CDCl ) δ =
for both isomers); MS (EI) m/z (relative intensity) 363 (10%, [(M −
3
+
−
40.02 and −40.05 (s, 3F each), −78.55 and −78.57 (s, 3F each); MS
C
4
F
9
SO
2
) ]), 307 (8), 265 (7), 111 (17), 69 (100), 55 (63); HRMS
+
+
(
EI) m/z (relative intensity) 241 (44%, [(M − CF SO ) ]), 115 (12),
(ESI, positive) m/z calcd for C16
669.0202, found 669.0211. Elemental analysis (%), calculated for
: C 29.73, H 2.49. Found: C 29.86, H 2.75.
trans-2,3-Dipropyl-1,1-bis(nonafluorobutanesulfonyl)-
H F18NaO S [(M + Na) ]
16 2 2
3
2
9
7 (39), 83 (77), 69 (79), 55 (100). Elemental analysis (%), calculated
for C H F O S : C 38.50, H 5.38. Found: C 38.50, H 5.12.
C H F O S
16 16 18 2 2
12
20
6
2 2
cis-2,3-Dipropyl-1,1-bis(trifluoromethanesulfonyl)cyclopropane
cis-(11c). Purification by preparative TLC (hexane−dichloromethane
cyclopropane trans-(11d). Purification by preparative TLC (hexane−
dichloromethane 9:1); a colorless oil (8 mg); IR (neat) ν = 2970,
2883, 1469, 1394, 1352, 1213, 1144, 1117, 1020, 912, 866, 727, 698,
9
1
:1); a colorless oil (22 mg); IR (neat) ν = 3057, 2966, 2933, 2877,
469, 1390, 1266, 1209, 1111, 741 cm ; H NMR (400 MHz,
−1
1
−
1
1
CDCl ) δ = 2.78−2.69 (m, 2H), 2.00−1.84 (m, 4H), 1.63−1.44 (m,
617 cm ; H NMR (400 MHz, CDCl ) δ = 2.79−2.67 (m, 2H),
3
3
13
4
H), 1.02 (t, J = 7.3 Hz, 6H); C NMR (75 MHz, CDCl ) δ = 119.8
2.02−1.66 (m, 4H), 1.51 (sext, J = 7.4 Hz, 4H), 1.01 (t, J = 7.4 Hz,
6H); C NMR (75 MHz, CDCl
F NMR (376 MHz, CDCl ) δ = −81.2 (t, J = 9.5 Hz, 6F), −102.6
3
1
1
13
28
(
1
3
q, J = 330.1 Hz), 119.4 (q, J = 330.3 Hz), 59.7, 37.6, 24.5, 22.3,
3
): δ = 67−63 (br), 29.0, 22.4, 13.7;
CF
CF
3.9; 1 F NMR (376 MHz, CDCl ) δ = −69.56 (s, 3F), −70.71 (s,
9
19
3
3
+
F); MS (EI) m/z (relative intensity) 390 (<1%, [M ]), 347 (8), 335
(br m, 2F), −104.3 (d, J = 249.2 Hz, 2F), −121.6 (m, 4F), −125.9 (m,
4F); MS (EI) m/z (relative intensity) 395 (19%), 123 (19), 87 (100),
81 (97), 69 (43), 67 (44), 55 (52); HRMS (ESI, negative) m/z calcd
(
6), 123 (9), 81 (100), 67 (50), 56 (31), 55 (36); HRMS (ESI,
+
positive) m/z calcd for C H F NaO S [(M + Na) ] 413.0292,
found 413.0307.
11
16
6
4 2
−
for C H F O S [(M − H) ] 689.0124, found 689.0103.
17
15 18
4 2
(1R*,2R*)-1-Propyl-2-(trifluoromethylthio)pentyl Trifluorometha-
(1R*,2S*)-1-Propyl-2-(nonafluorobutylthio)pentyl Nonafluorobu-
tanesulfinate anti-(12d) (A 1:1 Mixture of Diastereoisomers).
Purification by preparative TLC (hexane−dichloromethane 9:1); a
colorless oil (7 mg); IR (neat) ν = 2968, 2881, 1468, 1352, 1236,
nesulfinate syn-(12c). Purification by preparative TLC (hexane−
dichloromethane 9:1); a colorless oil (15 mg); IR (neat) ν = 2968,
−1 1
2
879, 1468, 1385, 1205, 1124, 920, 858, 791, 756, 698, 584 cm ; H
−1 1
NMR (400 MHz, CDCl ) δ = 4.68−4.59 (m, 1H for both isomers),
1138, 1001, 962, 864, 796, 746, 731, 692 cm ; H NMR (400 MHz,
3
3
1
0
1
.32 (ddd, J = 9.7, 4.6, 3.2 Hz, 1H) and 3.25 (ddd, J = 9.7, 4.6, 3.2 Hz,
H), 1.94−1.30 (m, 8H for both isomers), 0.98 (t, J = 7.5 Hz, 6H) and
CDCl ) δ = 4.68−4.61 (m, 1H for both isomers), 3.48 (dt, J = 7.9, 2.8
3
Hz, 1H) and 3.45 (dt, J = 7.9, 2.6 Hz, 1H), 1.94−1.29 (m, 8H for both
13
13
.96 (t, J = 7.5 Hz, 6H); C NMR (75 MHz, CDCl ) δ = 130.70 and
isomers), 1.01−0.94 (6H for both isomers); C NMR (75 MHz,
3
1
1
28
30.66 (q, J = 306.4 Hz each), 122.6 (q, J = 335.5 Hz for both
CDCl ): δ = 87.9 and 87.7, 48.2 (for both isomers), 35.4 and 34.9,
CF
CF
3
isomers), 85.5 and 85.2, 48.7 (for both isomers), 33.0 and 32.9, 32.5
and 32.3, 20.1 and 20.0, 18.8 (for both isomers), 13.5 and 13.3; 19
NMR (376 MHz, CDCl ) δ = −40.40 and −40.44 (s, 3F each),
31.4 and 30.1, 20.1 and 20.0, 18.8 and 18.6, 13.61 and 13.58, 13.44 and
19
F
13.40; F NMR (376 MHz, CDCl ) δ = −81.3 (t, J = 8.6 Hz, 3F for
3
both isomers), −81.5 (t, J = 8.6 Hz, 3F for both isomers), −85.3 and
−86.2 (AB type, J = 235.9 Hz, each 1F. Both signals appear as triplet, J
= 11.5 Hz), −85.6 and −86.2 (AB type, J = 235.9 Hz, each 1F. Both
signals appear as triplet, J = 11.5 Hz), −118.2 and −121.2 (AB type, J
= 248.6 Hz, each 1F. Both signals appear as triplet, J = 13.2 Hz),
−119.3 and −121.4 (AB type, J = 248.6 Hz, each 1F. Both signals
appear as triplet, J = 13.2 Hz), −120.9 (m, 1F for both isomers),
−121.1 (m, 1F for both isomers), −122.4 (m, 2F for both isomers),
−125.9 (m, 2F for both isomers), −126.6 (m, 2F for both isomers);
3
−
80.07 and −80.09 (s, 3F each); MS (EI) m/z (relative intensity) 213
+
(
(
[
16%, [(M − CF SO ) ]), 157 (9), 115 (17), 111 (14), 71 (15), 69
3
2
100), 55(98); HRMS (ESI, positive) m/z calcd for C H F NaO S
(M + Na) ] 369.0394, found 369.0386. Elemental analysis (%),
10
16
6
2 2
+
calculated for C H F O S ·1/2H O: C 33.80, H 4.82. Found: C
10
16
6
2
2
2
3
3.32, H 4.44; 4.46. The structure of syn-12c was determined by the
comparison of spectral data with those of an authentic sample,
prepared from cis-4-octene according to the reported procedure
21
+
(Scheme S2).
MS (EI) m/z (relative intensity) 363 (12%, [(M − C F SO ) ]), 307
4
9
2
cis-2,3-Dipropyl-1,1-bis(nonafluorobutanesulfonyl)cyclopropane
cis-(11d). Purification by preparative TLC (hexane−dichloromethane
(4), 265 (6), 111 (19), 69 (100), 55 (67); HRMS (ESI, positive) m/z
calcd for C H F NaO S [(M + Na) ] 669.0202, found 669.0182.
+
16
16 18
2 2
9
1
6
1
:1); a colorless oil (7 mg); IR (neat) ν = 2970, 2943, 2881, 1469,
Elemental analysis (%), calculated for C H F O S : C 29.73, H 2.49.
16 16 18 2 2
394, 1350, 1238, 1144, 1117, 1020, 1005, 943, 868, 779, 731, 698,
Found: C 29.97, H 2.78.
−
1 1
21 cm ; H NMR (400 MHz, CDCl ) δ = 2.83−2.67 (m, 2H), 2.0−
cis-2,3-Dibutyl-1,1-bis(trifluoromethanesulfonyl)cyclopropane
cis-(11e). Purification by preparative TLC (hexane−dichloromethane
9:1); a colorless oil (11 mg); IR (neat) ν = 2964, 2935, 2877, 1469,
3
13
.88 (m, 4H), 1.65−1.46 (m, 4H), 1.02 (t, J = 7.5 Hz, 6H); C NMR
28
19
(
125 MHz, CDCl ) δ = 62.5, 24.6, 22.3, 13.8; F NMR (376 MHz,
3
−
1 1
CDCl ) δ = −81.17 (t, J = 9.7 Hz, 3F), −81.18 (t, J = 9.7 Hz, 3F),
1392, 1203, 1109, 955, 856, 660, 636, 617 cm ; H NMR (400 MHz,
3
−
102.1 (t, J = 13.9 Hz, 2F), −103.4 (br s, 2F), −121.7 (s, 2F), −121.8
s, 2F), −125.9 (s, 4F); MS (EI) m/z (relative intensity) 241 (15%),
71 (6), 139 (6), 115 (5), 97 (26), 83 (65), 69 (100), 55 (58); HRMS
CDCl ) δ = 2.77−2.67 (m, 2H), 2.01−1.86 (m, 4H), 1.61−1.30 (m,
3
13
(
8H), 0.95 (t, J = 7.4 Hz, 6H); C NMR (100 MHz, CDCl ) δ = 119.6
3
1
19
1
(q, J = 272.5 Hz), 59.7, 37.8, 31.0, 22.4, 22.1, 13.8; F NMR (376
CF
G
DOI: 10.1021/acs.joc.6b00142
J. Org. Chem. XXXX, XXX, XXX−XXX

The Journal of Organic Chemistry
Article
MHz, CDCl ) δ = −69.5 (s, 3F), −70.7 (s, 3F); MS (EI) m/z (relative
79 (100), 69 (74), 55 (30); HRMS (ESI, positive) m/z calcd for
3
+
intensity) 241 (15%), 171 (6), 139 (6), 115 (5), 97 (26), 83 (65), 69
C H F NaO S [(M + Na) ] 396.9979, found 396.9972.
10
12
6
4 2
(
100), 55 (58); HRMS (ESI, positive) m/z calcd for C H F NaO S
trans-2-(Trifluoromethylthio)cycloheptyl Trifluoromethanesulfi-
13
20
6
4 2
+
[
(M + Na) ] 441.0605, found 441.0606.
1R*,2R*)-1-Butyl-2-(trifluoromethylthio)hexyl Trifluoromethane-
nate (12f) (A 1:1 Mixture of Diastereoisomers). Purification by
preparative TLC (hexane−dichloromethane 9:1); a colorless oil (14
mg); IR (neat) ν = 2939, 2866, 1460, 1201, 1124, 1011, 980, 960, 910,
(
sulfinate syn-(12e) (A 1:1 Mixture of Diastereoisomers). Purification
by preparative TLC (hexane−dichloromethane 9:1); a colorless oil (8
mg); IR (neat) ν = 2962, 2937, 2875, 1468, 1383, 1350, 1205, 1159,
−1 1
885, 849, 822, 804, 758 cm ; H NMR (400 MHz, CDCl ) δ = 4.79
3
(dt, J = 3.1, 5.8 Hz, 1H) and 4.67 (dt, J = 3.1, 6.5 Hz, 1H), 3.65 (ddd, J
= 7.8, 5.8, 3.1 Hz, 1H) and 3.48 (ddd, J = 8.6, 6.5, 3.1 Hz, 1H), 2.32−
−1
1
1
120, 943, 922, 868, 827, 758, 698 cm ; H NMR (400 MHz,
1
3
CDCl ) δ = 4.60−4.54 (m, 1H for both isomers), 3.30 (ddd, J = 9.5,
5
1.42 (m, 10H for both isomers); C NMR (100 MHz, CDCl ) δ =
3
3
1
1
.2, 2.6 Hz, 1H) and 3.23 (ddd, J = 9.5, 4.8, 3.3 Hz, 1H), 1.96−1.74
130.5 (q, J = 305.2 Hz for both isomers), 122.6 (q, J = 334.0 Hz
C
F
C
F
(
(
m, 3H for both isomers), 1.64−1.24 (m, 9H for both isomers), 0.934
t, J = 7.1 Hz, 6H) and 0.929 (t, J = 7.1 Hz, 6H); C NMR (100
for both isomers), 85.8 and 85.1, 50.7 and 49.7, 33.0 and 31.9, 31.1
13
19
and 29.9, 27.8 and 27.4, 25.2 and, 24.4, 21.4 and 20.7; F NMR (376
1
MHz, CDCl ) δ = 130.6 (q, J = 304.5 Hz for both isomers), 122.6
(
3
MHz, CDCl ) δ = −40.2 (s, 3F) and −40.3 (s, 3F), −80.0 (s, 3F) and
3
CF
3
1
q, J = 334.0 Hz for both isomers), 85.6 and 85.4, 49.03 and 48.97,
−80.5 (s, 3F); MS (EI) m/z (relative intensity) 197 (12%, [(M −
CF
+
0.7 (for both isomers), 30.20 and 30.07, 28.9 (for both isomers), 27.5
CF SO ) ]), 95 (100), 67 (33), 55 (18); HRMS (ESI, positive) m/z
3
2
+
and 27.4, 22.1 (for both isomers), 22.0 and 21.97, 13.7 (for both
calcd for C H F NaO S [(M + Na) ] 353.0081, found 353.0081.
9 12 6 2 2
isomers); 19F NMR (376 MHz, CDCl ) δ = −40.37 (s, 3F) and
Elemental analysis (%), calculated for C H F6O S : C 32.73, H 3.66.
3
9
12
2 2
−
(
1
40.42 (s, 3F), −80.03 (s, 3F) and −80.05 (s, 3F); MS (EI) m/z
Found: C 32.45, H 3.70. The structure of 12f was determined by the
comparison of spectral data with those of an authentic sample,
prepared from cycloheptene according to the reported procedure
+
relative intensity) 241 (25%, [(M − CF SO ) ]), 171 (5), 129 (5),
3
2
15 (9), 97 (33), 83 (85), 69 (100), 55(78); HRMS (ESI, positive)
+
21
m/z calcd for C H F NaO S [(M + Na) ] 397.0707, found
(Scheme S2).
12
20
6
2 2
3
3
97.0701. Elemental analysis (%), calculated for C H F O S : C
8.49, H 5.38. Found: C 38.19, H, 5.24. The structure of syn-12e was
9,9-Bis(trifluoromethanesulfonyl)bicyclo[6.1.0]nonane (11g). Pu-
rification by preparative TLC (hexane−dichloromethane 9:1); color-
less needles (recrystallized from pentane); mp 55−56 °C (6 mg); IR
(KBr) ν = 2922, 2864, 1475, 1446, 1394, 1369, 1209, 1111, 1005, 976,
12
20
6
2 2
determined by the comparison of spectral data with those of an
authentic sample, prepared from cis-5-decene according to the
reported procedure (Scheme S2).
21
−1 1
939, 856, 796, 750, 660, 634, 580 cm ; H NMR (400 MHz, CDCl )
3
trans-2,3-Dibutyl-1,1-bis(trifluoromethanesulfonyl)cyclopropane
trans-(11e). Purification by preparative TLC (hexane−dichloro-
methane 9:1); a colorless oil (16 mg); IR (neat) ν = 2962, 2933,
δ = 2.70−2.60 (m, 2H), 2.22−2.05 (m, 4H), 1.90−1.77 (m, 2H),
13
1
1.65−1.42 (m, 6H); C NMR (75 MHz, CDCl ) δ = 119.8 (q, J
=
F
3
CF
1
19
330.7 Hz), 119.3 (q, J = 330.1 Hz), 59.5, 37.7, 28.3, 25.6, 20.6;
CF
−1 1
2
877, 1468, 1390, 1203, 1109, 941, 785, 748, 665, 627 cm ; H NMR
NMR (376 MHz, CDCl ) δ = −68.7 (s, 3F), −70.5 (s, 3F); MS (EI)
3
+
(
1
400 MHz, CDCl ) δ = 2.73−2.64 (m, 2H), 2.01−1.89 (m, 2H),
m/z (relative intensity) 388 (<1%, [M ]), 319 (5), 255 (4, [(M −
CF SO ) ]), 185 (12), 121 (57), 93 (68), 79 (100), 67 (46), 55 (77);
HRMS (ESI, positive) m/z calcd for C H F NaO S [(M + Na) ]
3
13
+
.85−1.69 (m, 2H), 1.53−1.33 (m, 8H), 0.94 (t, J = 7.3 Hz, 6H);
C
3
2
1
+
NMR (75 MHz, CDCl ) δ = 119.5 (q, J = 330.1 Hz), 62.6, 40.6,
3
MS (EI) m/z (relative intensity) 241 (20%), 171 (7), 139 (5), 115
3
CF
11 14 6 4 2
1.0, 26.5, 22.3, 13.8; 19F NMR (376 MHz, CDCl ) δ = −70.4 (s, 6F);
3
411.0135, found 411.0135.
trans-2-(Trifluoromethylthio)cyclooctyl Trifluoromethanesulfi-
nate (12g) (A 1:1 Mixture of Diastereoisomers). Purification by
preparative TLC (hexane−dichloromethane 9:1); a colorless oil (9
mg); IR (neat) ν = 2931, 2864, 1469, 1448, 1201, 1119, 1026, 899,
(
7), 97 (38), 83 (84), 69 (100), 57 (33), 55 (81); HRMS (ESI,
+
positive) m/z calcd for C H F NaO S [(M + Na) ] 441.0605,
13
20
6
4 2
found 441.0581. Elemental analysis (%), calculated for C H F O S :
13
20
6
4 2
−1 1
C 37.32, H 4.82. Found: C 37.31, H 4.79.
839, 791, 758 cm ; H NMR (400 MHz, CDCl ) δ = 4.58 (dt, J = 8.8,
3
(
1R*,2S*)-1-Butyl-2-(trifluoromethylthio)hexyl Trifluoromethane-
4.3 Hz, 1H) and 4.52 (ddd, J = 9.2, 6.5, 2.3 Hz, 1H), 3.60 (ddd, J =
8.8, 7.3, 2.1 Hz, 1H) and 3.52 (ddd, J = 9.2, 7.2, 2.3 Hz, 1H), 2.36−
2.22 (m, 1H for both isomers), 2.20−1.20 (m, 11H for both isomers);
sulfinate anti-(12e) (A 1:1 Mixture of Diastereoisomers). Purification
by preparative TLC (hexane−dichloromethane 9:1); a colorless oil
13
1
(
8
(
12 mg); IR (neat) ν = 2962, 2935, 2875, 1468, 1383, 1201, 1120, 976,
C NMR (75 MHz, CDCl ) δ = 130.6 (q, J = 307.0 Hz), 122.7 (q,
3 CF
−1 1
1J = 336.3 Hz) and 117.3 (q, J = 336.9 Hz), 85.0 (both isomers),
1
81, 820, 758, 661 cm ; H NMR (400 MHz, CDCl ) δ = 4.66−4.57
m, 1H for both isomers), 3.27 (dt, J = 10.2, 3.1 Hz, 1H for both
isomers), 1.93−1.22 (m, 12H for both isomers), 0.934 and 0.930 (t, J
7.3 Hz, 3H each, both isomers); C NMR (125 MHz, CDCl ) δ =
3
30.7 (q, J = 306.3 Hz for both isomers), 122.73 (q, J = 335.0
Hz) and 122.70 (q, J = 333.8 Hz), 87.4 and 87.2, 49.8 (for both
3
CF CF
5
2
0.3 and 49.6, 32.2 and 30.9, 30.1 and 29.7, 25.6 (both isomers), 25.4,
5.2 (both isomers), 25.1, 24.4 and 23.5; F NMR (376 MHz,
19
13
=
1
CDCl ) δ = −40.1 (s, 3F) and −40.3 (s, 3F), −79.8 (s, 3F) and −80.5
3
1
1
+
CF
CF
(s, 3F); MS (EI) m/z (relative intensity) 279 (12%, [M − SO H] ),
167 (35), 149 (100), 112 (11), 83 (14), 71 (23), 70 (30), 57 (32), 55
2
1
CF
isomers), 32.7 and 32.4, 28.94 and 28.92, 27.8 and 27.3, 27.5 (for both
(
29); HRMS (ESI, positive) m/z calcd for C H F NaO S [(M +
10 14 6 2 2
isomers), 13.8 (for both isomers); 19F NMR (376 MHz, CDCl ) δ =
+
3
Na) ] 367.0237, found 367.0233. The structure of 12g was
determined by the comparison of spectral data with those of an
authentic sample, prepared from cyclooctene according to the
reported procedure (Scheme S2).
9,9-Bis(trifluoromethanesulfonyl)bicyclo[6.1.0]non-4-ene
(11h): Purification by preparative TLC (hexane−dichloromethane
9:1); a colorless solid (12 mg); IR (KBr) ν = 3018, 2966, 2933, 2902,
1657, 1493, 1450, 1392, 1365, 1201, 1136, 1115, 960, 877, 860, 710,
−
40.2 and −40.3 (s, 3F each), −79.5 and −80.2 (s, 3F each); MS (EI)
+
m/z (relative intensity) 241 (15%, [(M − CF SO ) ]), 171 (6), 129
3
2
2
1
(
3), 115 (5), 97 (36), 83 (77), 69 (100), 55 (70); HRMS (ESI,
+
positive) m/z calcd for C H F NaO S [(M + Na) ] 397.0707,
12
20
6
2 2
12
found 397.0708. The structure of anti-12e was determined by the
comparison of spectral data with those of an authentic sample,
prepared from trans-5-decene according to the reported procedure
Scheme S2).
8
fication by preparative TLC (hexane−dichloromethane 9:1); a
colorless oil (10 mg); IR (neat) ν = 2929, 2858, 1471, 1392, 1375,
201, 1157, 1105, 972, 916, 866, 837, 800, 750, 660, 634 cm ; H
21
−1 1
(
650, 613 cm ; H NMR (400 MHz, CDCl ) δ = 5.71−5.61 (m, 2H),
3
13
,8-Bis(trifluoromethanesulfonyl)bicyclo[5.1.0]octane (11f). Puri-
2.82−2.54 (m, 6 H), 2.28−2.11 (m, 4H); C NMR (125 MHz,
1
1
CDCl ) δ = 128.9, 119.4 (q, J = 330.3 Hz), 119.3 (q, J = 330.9
3 CF CF
Hz), 59.2, 36.5, 26.3, 26.0; MS (EI) m/z (relative intensity) 386 (8%,
−
1
1
+
1
[M ]), 183 (6), 119 (45), 91 (100), 81 (84), 67 (82), 54 (31).
NMR (400 MHz, CDCl ) δ = 2.86−2.74 (m, 2H), 2.36−2.11 (m,
trans-8-(Trifluoromethylthio)cyclooct-4-enyl Trifluoromethane-
sulfinate (12h) (A 1:1 Mixture of Diastereoisomers). Purification by
preparative TLC (hexane−dichloromethane 9:1); a colorless oil (8
mg); IR (neat) ν = 3026, 2943, 1655, 1487, 1471, 1435, 1203, 1119,
3
13
4
H), 2.07−1.91 (m, 3H), 1.46−1.28 (m, 3H); C NMR (75 MHz,
1
1
CDCl ) δ = 119.7 (q, J = 330.1 Hz), 119.3 (q, J = 330.1 Hz),
3
CF
CF
3
19
6
1.4 (sept, J = 2.6 Hz), 37.3, 31.2, 27.8, 22.7; F NMR (376 MHz,
CDCl ) δ = −69.4 (s, 3F), −71.3 (s, 3F); MS (EI) m/z (relative
intensity) 241 (4%, [(M − CF SO ) ]), 171 (22), 107 (41), 91 (48),
CF
−1 1
1016, 987, 937, 887, 804, 756, 735, 696, 663 cm ; H NMR (400
3
+
MHz, CDCl ) δ = 5.81−5.65 (m, 2 H for both isomers), 4.90 (ddd, J
3
2
3
H
DOI: 10.1021/acs.joc.6b00142
J. Org. Chem. XXXX, XXX, XXX−XXX

The Journal of Organic Chemistry
Article
=
8.4, 5.6, 2.7 Hz, 1H) and 4.84−4.73 (m, 1H), 3.80 (dt, J = 8.4, 5.6
temperature and stirred for 12 h. The reaction mixture was diluted
Hz, 1H) and 3.70 (dt, J = 4.3, 8.0 Hz, 1H), 2.63−2.01 (m, 8 H for
with Et O, and then washed with water and a saturated aqueous NaCl
2
both isomers); 13C NMR (100 MHz, CDCl ) δ = 130.5 (q, J
1
=
solution. The organic phase was dried over MgSO and evaporated in
3
CF
4
3
05.7 Hz for both isomers), 131.2 and 130.9, 130.1 and 128.9, 122.8
vacuo to give an oil, which was purified by column chromatography
1
(
q, J = 335.6 Hz for both isomers), 82.8 and 82.6, 47.0 and 45.7,
(hexane/dichloromethane 9:1) (R = 0.4) to afford ester syn-12c (68
CF
f
19
3
4.2, 33.1, 33.0, 32.9, 23.9 and 23.5, 22.0 and 21.0; F NMR (376
mg, 59%) as a 1:3 mixture of diastereoisomers.
MHz, CDCl ) δ = −41.7 (s, 3F) and −42.4 (s, 3F), −79.5 (s, 3F) and
The alcohol anti-28 was converted into corresponding tosylate 29
by using tosyl chloride in a typical tosylation conditions (Scheme S2).
(1R*,2S*)-1-Propyl-2-(trifluoromethylthio)-1-pentyl tosylate anti-
3
−
80.2 (s, 3F); MS (EI) m/z (relative intensity) 273 (57%, [(M −
+
CF ) ]), 209 (10), 139 (29), 107 (67), 91 (34), 79 (100), 67 (47), 53
3
21
1
(
26). Elemental analysis (%), calculated for C H F O S ·1/2H O: C
(29). A colorless oil; H NMR (400 MHz, CDCl ) δ = 7.81 (d, J =
3
10
12
6
2
2
2
3
4.19, H 3.73. Found: C 34.30, H 3.58. The structure of 12h was
8.2 Hz, 2H), 7.35 (d, J = 8.2 Hz, 2H), 4.06 (dt, J = 8.4, 3.0 Hz, 1H),
3.36−3.29 (m, 1H), 2.45 (s, 3H), 1.85−1.72 (m, 1H), 1.69−1.30 (m,
6H), 1.29−1.12 (m, 1H), 0.91 (t, J = 7.3 Hz, 3H), 0.87 (t, J = 7.3 Hz,
determined by the comparison of spectral data with those of an
authentic sample, prepared from cyclooctadiene according to the
21
19
1
19
reported procedure (Scheme S2).
-[2,2-Bis(trifluoromethanesulfonyl)ethyl]cyclopent-1-ene (13).
3H); F NMR (376 Hz, CDCl ) δ = −40.15 (s, 3F). H/ F NMR
3
1
chemical shifts of compound 29 were in good agreement with Billard’s
reported data.
Purification by acid base extraction with 1 N NaOH aq. and 1 N
HCl; a pale yellow oil (11 mg); IR (neat) ν = 3064, 2941, 2854, 1433,
In a similar manner, triflination of alcohol anti-28 produced ester
anti-12c (73%) as a 1:1 mixture of diastereoisomers. Authentic
samples of 12a, 12b, syn-12c, trans-12f, trans-12g, and trans-12h were
also prepared from olefins via Billard anti-1,2-S,O-addition and
triflination sequence (Scheme S2).
General Procedure for Thermal Decomposition of Bromo-
nium Ylide 1a in Aliphatic and Aromatic Hydrocarbons. A
Typical Example: Reaction with p-Xylene (Scheme 7). A
suspension of bromonium ylide 1a (41 mg, 0.082 mmol) in p-xylene
−
1 1
1
5
2
394, 1211, 1113, 779, 698 cm ; H NMR (400 MHz, CDCl ) δ =
3
.71 (s, 1H), 4.95 (t, J = 5.7 Hz, 1H), 3.28 (d, J = 5.7 Hz, 2H), 2.42−
13
.35 (m, 2H), 2.35−2.28 (m, 2H), 1.96 (quint, J = 7.2 Hz, 2H);
C
1
NMR (100 MHz, CDCl ) δ = 134.7, 131.4, 119.3 (q, J = 330.1 Hz),
3
CF
19
7
6
6.4, 34.3, 32.6, 26.4, 23.2; F NMR (376 MHz, CDCl ) δ = −73.3 (s,
F); MS (EI) m/z (relative intensity) 360 (7%, [M ]), 226 (23), 157
3
+
(
(
90), 93 (75), 91 (100), 79 (49), 77 (84), 67 (39), 53 (16); HRMS
−
ESI, negative) m/z calcd for C H F O S [(M − H) ] 358.9846,
9
9
6
4 2
(
8.2 mL) was heated in a sealed tube to 110 °C under argon and the
found 358.9855. Elemental analysis (%), calculated for C H F O S :
9
10
6
4 2
resulting clear colorless solution was stirred for 48 h. After cooling, the
yields of products were determined by H NMR (1,1,2,2-tetrachloro-
C 30.00, H 2.80. Found: C 29.96, H, 2.84.
1
General Procedure for Billard anti-1,2-S,O-Addition to
ethane as an internal standard). The reaction mixture was purified by
preparative TLC (ethyl acetate:hexane = 1:1) to yield pale yellow oil
contaminated with impurities. The oil was dissolved in dichloro-
methane and extracted with NaOH aqueous solution (1 M) two times,
the resulting aqueous phase was washed with dichloromethane several
times. After neutralization with HCl aqueous solution (1 M), the
aqueous phase was extracted with dichloromethane four times. The
dichloromethane phase was filtered and evaporated under an
aspiratory vacuum to give a 87:13 mixture of 2,5-dimethylphenylbis-
Olefins. A Typical Example: Synthesis of Authentic Sample
2
1
of β-Trifluoromethylthiosulfinate Ester 12.
To a stirred
solution of N-(trifluoromethylthio)aniline (292 mg, 1.5 mmol) in
dichloromethane (3.0 mL) was added trans-4-octene (237 mL, 1.5
mmol) and trifluoroacetic acid (281 mL, 3.8 mmol) under argon and
the mixture was stirred at 50 °C for 24 h. After cooling, the solvent was
removed under an aspiratory vacuum and then neutralized with excess
sodium carbonate in MeOH for 5 min. The mixture was poured into
5
% aqueous HCl and extracted with diethyl ether four times. The
(
trifluoromethanesulfonyl)methane (16) and 2-(4-methylphenyl)-1,1-
combined organic phases were dried over magnesium sulfate, filtered,
and evaporated an aspiratory vacuum to give an oil, which was purified
29
bis(trifluoromethanesulfonyl)ethane (17) (25.8 mg, 82%) as a
colorless oil. Authentic samples of o-14, m-14, p-14, and 16 were
prepared according to the Yamamoto’s method and compounds 17
and 19 were prepared according to the Yanai’s method.
,5-Dimethylphenylbis(trifluoromethanesulfonyl)methane (16).
Purified by preparative TLC (ethyl acetate:hexane:AcOH =
by column chromatography (dichloromethane−hexane 3:2) (R = 0.3)
f
2
2b
to give alcohol syn-28 (177 mg, 51%) as a pale yellow oil: IR (neat) ν
2
2c
−1 1
=
3377, 2962, 2877, 1466, 1383, 1120, 1018, 928, 845, 756 cm ; H
2
NMR (400 MHz, CDCl ) δ = 3.83−3.73 (m, 1H), 3.08 (ddd, J = 8.7,
3
5
.4, 3.4 Hz, 1H), 1.89−1.30 (m, 8H), 0.96 (t, J = 7.4 Hz, 3H), 0.95 (t,
1
3
1
1
1
00:100:1); a colorless oil (14 mg); IR (neat) ν = 2958, 1698,
457, 1391, 1210, 1111, 897, 784, 749, 703, 589, 490, 452 cm ; H
J = 7.4 Hz, 3H); C NMR (75 MHz, CDCl ) δ = 131.4 (q, J
3
=
CF
3
−1 1
19
05.6 Hz), 73.1, 52.5, 36.5, 35.2, 20.2, 19.1, 13.9, 13.7; F NMR (376
NMR (400 MHz, CD Cl ) δ = 7.79 (s, 1H), 7.36 (d, J = 7.7 Hz, 2H),
MHz, CDCl ) δ = −39.7 (s, 3F); MS (EI) m/z (relative intensity) 207
2
2
3
1
3
7
.29 (d, J = 7.7 Hz, 2H), 6.35 (s, 1H), 2.40 (s, 3H), 2.35 (s, 3H);
C
(
10%), 159 (9), 73 (80), 69 (20), 55 (100); HRMS (ESI, positive) m/
+
NMR (75 MHz, CDCl ) δ = 137.7, 136.2, 133.9, 131.8, 131.4, 119.4
z calcd for C H F NaO S [(M + Na + MeOH) ] 285.1112, found
3
10
21
3
2
1
(
q, J = 330.1 Hz), 76.3, 21.0, 18.6; HRMS (ESI, negative) m/z
2
85.1121.
1R*,2S*)-1-Propyl-2-(trifluoromethylthio)-1-pentanol anti-(28).
CF
−
calcd for C H F O S [(M − H) ] 382.9846, found 382.9830.
(
11
9
6
4 2
1
-[2,2-Bis(trifluoromethanesulfonyl)ethyl]-4-methylbenzene (17).
Purification by column chromatography (dichloromethane−hexane
Purified by preparative TLC (ethyl acetate:hexane:AcOH =
3
1
:2); pale yellow oil (155 mg); IR (neat) ν = 3377, 2962, 2875, 1468,
383, 1298, 1217, 1124, 1030, 849, 756 cm ; H NMR (400 MHz,
−1 1
1
1
7
2
1
00:100:1); a colorless oil (12 mg); IR (neat) ν = 2929, 1389,
−1 1
206, 1106, 687, 635, 586 cm ; H NMR (400 MHz, CDCl ) δ =
CDCl ) δ = 3.92−3.80 (m, 1H), 3.23 (dt, J = 9.9, 3.4 Hz, 1H), 1,98
3
3
.4−7.1 (m, 4H), 5.03 (t, J = 6.1 Hz, 1H), 3.76 (d, J = 6.1 Hz, 2 H),
(
br s, 1H, OH), 1.74−1.30 (m, 8H), 0.953 (t, J = 7.3 Hz, 3H), 0.95 (t,
1
3
1
3
1
.35 (s, 3H); C NMR (125 MHz, CDCl ) δ = 138.5, 130.0, 128.9,
J = 7.3 Hz, 3H); C NMR (75 MHz, CDCl ) δ = 131.2 (q, J
3
=
CF
3
3
1
19
19
19.3 (q, J = 327.5 Hz), 80.0, 30.2, 21.1; F NMR (376 MHz,
05.8 Hz), 73.7, 53.0, 35.7, 31.7, 20.4, 19.4, 13.9, 13.7; F NMR (376
CF
CDCl ) δ = −72.6 (s, 6F); HRMS (ESI, negative) m/z calcd for
MHz, CDCl ) δ = −39.8 (s, 3F); MS (EI) m/z (relative intensity) 207
3
3
−
C H F O S [(M − H) ] 382.9846, found 382.9823.
(
2%), 159 (4), 73 (58), 69 (8), 55 (100); HRMS (ESI, positive) m/z
11
2
9
6
4 2
+
-Methylphenylbis(trifluoromethanesulfonyl)methane o-(14).
calcd for C H F NaO S [(M + Na + MeOH) ] 285.1112, found
10
21
3
2
Purified by preparative TLC (ethyl acetate:hexane = 1:1); a colorless
oil (18 mg); IR (neat) ν = 2959, 1605, 1493, 1379, 1226, 1189, 1107,
2
85.1102.
Synthesis of syn- and anti-β-Thiosulfinate Esters 12c by
Triflination of Alcohols 28. A Typical Example: Synthesis of
−1 1
1058, 763, 458 cm ; H NMR (400 MHz, CDCl ) δ = 8.02 (d, J = 7.7
3
2
2
syn-12c. Sodium trifluoromethanesulfinate CF SO Na (83 mg, 0.53
Hz, 1H), 7.52 (t, J = 7.7 Hz, 1H), 7.43 (t, J = 7.7 Hz, 1H), 7.37 (d, J =
3
2
mmol) and mesitylenesulfonyl chloride (109 mg, 0.50 mmol) were
dissolved in MeCN (0.66 mL) at room temperature. After being
stirred for 1 h, the mixture was cooled to 0 °C and a solution of syn-28
7.7 Hz, 1H), 6.32 (s, 1H), 2.40 (s, 3H); 13C NMR (75 MHz, CDCl )
3
1
δ = 139.4, 132.9, 131.9, 131.2, 127.7, 117.6, 119.4 (q, J = 330.2 Hz),
CF
76.2, 19.1; 19F NMR (376 MHz, CDCl ) δ = −73.4 (s, 6F); HRMS
3
−
(
76 mg, 0.33 mmol) and pyridine (39 mg, 0.50 mmol) in MeCN (0.16
(ESI, negative) m/z calcd for C H F O S [(M − H) ] 368.9690,
10
7
6
4 2
mL) was added dropwise. This mixture was allowed to warm to room
found 368.9671.
I
DOI: 10.1021/acs.joc.6b00142
J. Org. Chem. XXXX, XXX, XXX−XXX

The Journal of Organic Chemistry
Article
3
-Methylphenylbis(trifluoromethanesulfonyl)methane m-(14).
reaction temperature was added 20−50 mL of the stock solution of
bromonium ylide 9 or chloronium ylide 10a from a microsyringe. The
absorbance change was fed to a computer through an interface and
processed by a pseudo-first-order kinetics program. The reaction
followed pseudo-first-order kinetics for at least 4 half-lives and the
pseudo-first-order rate constants kobs were calculated. The values for
triplicate runs were averaged.
Purified by preparative TLC (ethyl acetate:hexane = 1:1); a colorless
oil (13 mg); IR (neat) ν = 2948, 1605, 1490, 1386, 1215, 1105, 888,
−1 1
7
(
=
8
79, 734, 696, 592, 456 cm ; H NMR (400 MHz, CDCl ) δ = 7.45
3
br s, 4H), 5.87 (s, 1H), 2.44 (s, 3H); 13C NMR (75 MHz, CDCl ) δ
3
1
140.3, 133.8, 132.1, 129.8, 129.0, 119.7, 119.4 (q, JCF = 330.7 Hz),
0.8, 21.4; HRMS (ESI, negative) m/z calcd for C H F O S [(M −
10
7
6
4 2
−
H) ] 368.9690, found 382.9676.
-Methylphenylbis(trifluoromethanesulfonyl)methane p-(14).
2
9
4
ASSOCIATED CONTENT
■
Purified by preparative TLC (ethyl acetate:hexane = 1:1); a colorless
oil (12 mg); IR (neat) ν = 2933, 1610, 1512, 1391, 1380, 1218, 1187,
113, 1093, 838, 644, 510, 454 cm ; H NMR (400 MHz, CDCl ) δ
7.45 (br s, 2H), 7.36 (d, J = 8.1 Hz, 2H), 5.89 (s, 1H), 2.45 (s, 3H);
*
S
Supporting Information
−1 1
1
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acs.joc.6b00142.
3
=
1
3
1
C NMR (75 MHz, CDCl ) δ = 143.9, 131.7, 130.8, 119.4 (q, J
=
3
CF
UV spectra (Figure S1), Eyring plot (Figure S2), radical
trapping experiments (Scheme S1), synthesis of
authentic samples (Scheme S2), calculation results
19
3
(
30.7 Hz), 116.0, 80.7, 21.6; F NMR (376 MHz, CDCl ) δ = −72.4
3
s, 6F).
,4,6-Trimethylphenylbis(trifluoromethanesulfonyl)methane
2
22b
1
13
(
18). Purified by preparative TLC (ethyl acetate:hexane = 1:1); a
(Figure S3 and Table S1−S4). H/ C NMR spectra of
colorless oil (12 mg); IR (neat) ν = 2929, 1609, 1459, 1381, 1301,
184, 1113, 855, 787, 668, 623, 581 cm ; H NMR (400 MHz,
products. (PDF)
−1
1
1
CDCl ) δ = 7.08 (s, 1H), 7.00 (s, 1H), 6.48 (s, 1H), 2.61 (s, 3H), 2.35
3
13
AUTHOR INFORMATION
(
s, 3H), 2.32 (s, 3H); C NMR (75 MHz, CDCl ) δ = 142.7, 142.3,
■
*
*
3
1
1
39.7, 132.2, 130.5, 119.5 (q, JCF = 330.1 Hz), 77.8, 22.3, 21.1, 20.2.
-[2,2-Bis(trifluoromethanesulfonyl)ethyl]-3,5-dimethylbenzene
19). Purified by preparative TLC (ethyl acetate:hexane = 1:1); a
colorless oil (13 mg); IR (neat) ν = 2926, 2856, 1608, 1393, 1336,
Corresponding Authors
E-mail: kmiya@mol.f.u-tokyo.ac.jp.
E-mail: nakanishi@sys.wakayama-u.ac.jp.
*E-mail: uchiyama@mol.f.u-tokyo.ac.jp.
1
(
−1
1
1
212, 1113, 1038, 850, 768, 689, 581 cm ; H NMR (400 MHz,
CDCl ) δ = 6.96 (s, 1H), 6.89 (s, 2H), 5.05 (t, J = 6.2 Hz, 1H), 3.72
Notes
3
13
(
1
d, J = 6.2 Hz, 2 H), 2.31 (s, 6H); C NMR (125 MHz, CDCl ) δ =
The authors declare no competing financial interest.
3
1
39.1, 133.0, 130.2, 126.7, 119.4 (q, JCF = 328.8 Hz), 80.2, 30.4, 21.2;
−
HRMS (ESI, negative) m/z calcd for C H F O S [(M − H) ]
3
12
11
6
4 2
ACKNOWLEDGMENTS
■
97.0000, found 397.0008.
Cyclohexylbis(trifluoromethanesulfonyl)methane (23). Purifica-
This work was supported by a Grant-in-Aid for Scientific
Research (B, 23390006) and (C, 25460016) (JSPS). We thank
Central Glass Co., Ltd. (Japan) for a generous gift of BrF3.
tion by base acid extraction with 1 N NaOH aq. and 1 N HCl; a
colorless oil (12 mg); IR (neat) ν = 2935, 2862, 1454, 1392, 1209,
−1 1
1
113, 1055, 897, 796, 773, 714, 663, 617, 586, 573, 544, 501 cm ; H
NMR (400 MHz, CDCl ) δ = 4.77 (br s, 1H), 2.54 (br t, J = 11.8 Hz,
3
REFERENCES
■
1
6
H), 2.12−1.81 (m, 6H), 1.74 (d, J = 10.1 Hz, 1H), 1.39−1.16 (m,
H); 13C NMR (75 MHz, CDCl ) δ = 119.3 (q, J = 330.9 Hz), 80.6
1
(1) Buchner, E.; Feldmann, L. Ber. Dtsch. Chem. Ges. 1903, 36, 3509.
2) Reviews: (a) Hine, J. Divalent Carbon; Ronald Press: New York,
1964. (b) Kirmse, W. Carbene Chemistry; Academic Press: New York,
971. (c) Platz, M. S.; Moss, R. A.; Jones, M. Reviews of Reactive
Intermediate Chemistry; Wiley: Hoboken, NJ, 2007. (d) Moss, R. A.
Acc. Chem. Res. 1989, 22, 15.
(3) For seminal work on the reactions of electrophilic carbenes, see:
a) Webster, O. W. J. Polym. Sci., Part A: Polym. Chem. 2002, 40, 210.
(b) Sheppard, W. A.; Webster, O. W. J. Am. Chem. Soc. 1973, 95, 2675.
(c) Janulism, E. P., Jr.; Arduengo, A. J., III J. Am. Chem. Soc. 1983, 105,
3
CF
(
(
br s), 40.8, 29.5, 26.8, 25.0; HRMS (ESI, negative) m/z calcd for
−
C H F O S [(M − H) ] 361.0003, found 361.0008.
9
11
6
4 2
1
Cyclooctylbis(trifluoromethanesulfonyl)methane (24). Purifica-
tion by acid base extraction with 1 N NaOH aq. and 1 N HCl; a
colorless oil (11 mg); IR (neat) ν = 2927, 2860, 1417, 1450, 1392,
−1
1
1
211, 1113, 777, 704, 658, 609 cm ; H NMR (400 MHz, CDCl ) δ
3
(
=
4.79 (d, J = 1.5 Hz, 1H), 2.86 (br t, J = 9.1 Hz, 1H), 2.16−1.91 (m,
13
4
H), 1.91−1.75 (m,2H), 1.75−1.51 (m, 7H), 1.51−1.36 (m, 1H); C
1
NMR (75 MHz, CDCl ) δ = 119.2 (q, J = 330.7 Hz), 82.1 (br s),
3
CF
3
563. (d) Frey, H. M.; Stevens, D. R. J. Chem. Soc. 1965, 3101.
(4) (a) Hadjiarapoglou, L.; Spyroudis, S.; Varvoglis, A. J. Am. Chem.
3
9.1, 31.1, 26.6, 25.9, 25.5; HRMS (ESI, negative) m/z calcd for
−
C H F O S [(M − H) ] 389.0316, found 389.0316.
1
1
15
6
4 2
Soc. 1985, 107, 7178. (b) Zhu, S.-Z.; Chen, Q.-Y. J. Chem. Soc., Chem.
Commun. 1990, 1459. (c) Diekmann, J. J. Org. Chem. 1965, 30, 2272.
(d) Ortica, F.; Pohlers, G.; Coenjarts, C.; Bejan, E. V.; Cameron, J. F.;
Zampini, A.; Haigh, M.; Scaiano, J. C. Org. Lett. 2000, 2, 3591.
(e) Ochiai, M.; Okada, T.; Tada, N.; Yoshimura, A. Org. Lett. 2008, 10,
1425.
(5) (a) Hatjiarapoglou, L.; Varvoglis, A.; Alcock, N. W.; Pike, G. A. J.
Chem. Soc., Perkin Trans. 1 1988, 2839. (b) Adam, W.; Gogonas, E. P.;
Hadjiarapoglou, L. P. Synlett 2003, 1165.
1
,1-Bis(trifluoromethanesulfonyl)-3,3,5,5-tetramethylhexane
(25). Purification by base acid extraction with 1 N NaOH aq. and 1 N
HCl; a colorless oil (8 mg); IR (neat) ν = 2957, 2904, 1475, 1393,
−1 1
1
210, 1111, 890, 791, 709, 586, 544, 501, 436 cm ; H NMR (400
MHz, CDCl ) δ = 4.79 (t, J = 4.1 Hz, 1H), 2.47 (d, J = 4.1 Hz, 2 H),
3
13
1
.37 (s, 2H), 1.06 (s, 6H), 1.03 (s, 9H); C NMR (75 MHz, CDCl3)
δ = 120.5 (q, J = 329.7 Hz), 78.9, 55.5, 37.7, 36.8, 32.9, 32.3, 27.2;
HRMS (ESI, negative) m/z calcd for C H F O S [(M − H) ]
05.0634, found 405.0632.
1
CF
−
12
19
6
4 2
4
Kinetic Measurements (Table 1, Figure 1−3, Figure S1 and
(6) Hadjiarapoglou, L.; Varvoglis, A. Synthesis 1988, 1988, 913.
(7) (a) Hatjiarapoglou, L.; Varvoglis, A. J. Heterocycl. Chem. 1988, 25,
1599. (b) Batsila, C.; Gogonas, E. P.; Kostakis, G.; Hadjiarapoglou, L.
P. Org. Lett. 2003, 5, 1511.
(8) (a) Sander, W.; Strehl, A.; Winkler, M. Eur. J. Org. Chem. 2001,
2001, 3771. (b) Bucher, G.; Strehl, A.; Sander, W. Eur. J. Org. Chem.
2003, 2003, 2153. (c) Sander, W.; Kotting, C.; Hubert, R. J. Phys. Org.
Chem. 2000, 13, 561.
S2). Rates for thermal decomposition of bromonium ylide 9 and
chloronium ylide 10a were measured by monitoring the decrease in
absorbance at 275 nm at different temperatures in the range of 92−
1
08 °C on UV−vis spectrophotometer (Figure S1). The reaction
temperature was controlled by a temperature controller and accurate
to within ±0.1 °C. A stock solution of bromonium ylide 9 was
prepared by weighting and dissolving in dichloromethane (0.04 M) at
room temperature and stored in a refrigerator at −20 °C. To
perfluorodecalin (3.0 mL) in a quartz cuvette inserted in a cell
compartment of the spectrophotometer and equilibrated at the
(9) Loss of CO2 from dithiocarbonate 3b would give rise to
thiosulfonate 4b selectively. Both atoms of oxygen of CO probably
2
originate from the same sulfonyl group of 1b (ref 4a).
J
DOI: 10.1021/acs.joc.6b00142
J. Org. Chem. XXXX, XXX, XXX−XXX

The Journal of Organic Chemistry
Article
(
10) (a) Yang, Y.-D.; Azuma, A.; Tokunaga, E.; Yamasaki, M.; Shiro,
Zakrzewski, V. G.; Dapprich, S.; Daniels, A. D.; Strain, M. C.;
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J. B.; Ortiz, J. V.; Cui, Q.; Baboul, A. G.; Clifford, S.; Cioslowski, J.;
Stefanov, B. B.; Liu, G.; Liashenko, A.; Piskorz, P.; Komaromi, I.;
Martin, R. L.; Fox, D. J.; Keith, T.; Al-Laham, M. A.; Peng, C. Y.;
Nanayakkara, A.; Challacombe, M.; Gill, P. M. W.; Johnson, B.; Chen,
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D.02; Gaussian, Inc.: Wallingford, CT, 2004.
M.; Shibata, N. J. Am. Chem. Soc. 2013, 135, 8782. (b) Arimori, S.;
Takada, M.; Shibata, N. Org. Lett. 2015, 17, 1063. (c) Huang, Z.; Yang,
Y.-D.; Tokunaga, E.; Shibata, N. Org. Lett. 2015, 17, 1094.
(
11) (a) Bolton, E. E.; Schaefer, H. F., III J. Am. Chem. Soc. 1993,
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29, 5719. (c) O’Bannon, P. E.; Dailey, W. P. Tetrahedron Lett. 1988,
29, 987.
(
12) (a) Ochiai, M.; Tada, N.; Okada, T.; Sota, A.; Miyamoto, K. J.
(26) A smaller triplet/singlet gap (∼2 kcal) has been estimated for
Am. Chem. Soc. 2008, 130, 2118. (b) Ochiai, M.; Tada, N.; Murai, K.;
Goto, S.; Shiro, M. J. Am. Chem. Soc. 2006, 128, 9608. (c) Ochiai, M.;
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parent disulfonylcarbene 1a (ref 8a).
(27) For intramolecular thermal cyclopropanation of alkenes with
phenyliodonium ylides under metal-free conditions, see: (a) Moriarty,
R. M.; Tyagi, S.; Kinch, M. Tetrahedron 2010, 66, 5801. (b) Moriarty,
R. M.; Prakash, O.; Vaid, R. K.; Zhao, L. J. Am. Chem. Soc. 1989, 111,
6443. (c) Gallos, J. K.; Koftis, T. V.; Massen, Z. S.; Dellios, C. C.;
Mourtzinos, I. T.; Coutouli-Argyropoulou, E.; Koumbis, A. E.
Tetrahedron 2002, 58, 8043. See also ref 17.
(
13) Comparable values of 8−23 times were obtained from the
reported relative rate constants as substituent effects of the p-CF
group in the solvolysis of 1-cyclohexenyl(aryl) (tetrafluoroborato)-λ -
iodanes. See: (a) Okuyama, T.; Takino, T.; Sueda, T.; Ochiai, M. J.
Am. Chem. Soc. 1995, 117, 3360. (b) Ochiai, M.; Suefuji, T.;
Miyamoto, K.; Shiro, M. Org. Lett. 2005, 7, 2893. For solvolysis of 1-
3
3
(28) Chemical shifts of carbon atoms attached to fluorine atoms were
3
not determined.
cyclopentenyl(aryl) (tetrafluoroborato)-λ -bromanes, see: (c) Miyamo-
to, K.; Shiro, M.; Ochiai, M. Angew. Chem., Int. Ed. 2009, 48, 8931.
(29) Zhu, S.-Z.; Xu, B.; Zhang, J. Synthesis 1994, 1994, 261−263.
(
14) Hansch, C.; Leo, A.; Taft, R. W. Chem. Rev. 1991, 91, 165.
(
15) No cyclopropanation or 1,2-S,O-addition reaction was observed
in attempted thermal decomposition of iodonium ylide in an olefin
solvent under these conditions, and the iodonium ylide was recovered
unchanged.
(
16) For a preliminary study on relative leaving group abilities
3
3
between λ -iodanyl group and λ -bromanyl group, see: Miyamoto, K.
Yakugaku Zasshi 2014, 134, 1287.
(
17) The high degree of stereospecificity in thermal decomposition
+
−
of iodonium ylide PhI −C (CO Et) in (Z)- and (E)-3-heptene,
2
2
yielding cis- and trans-bis(ethoxycarbonyl) cyclopropane respectively,
suggests cyclopropanation by a singlet carbene. See: Camacho, M. B.;
Clark, A. E.; Liebrecht, T. A.; DeLuca, J. P. J. Am. Chem. Soc. 2000,
1
(
22, 5210.
18) Formation of S-trifluoromethyl thiosulfonate CF SO SCF 4a
3
2
3
19
(
ref 19) in 41% yield was detected by F NMR in solid-state
thermolysis (175 °C, 10 min) of bromonium ylide 9a in the absence of
olefin, although the reproducibility of the yield was poor.
(
(
19) De Marco, R. A.; Shreeve, J. M. Inorg. Chem. 1973, 12, 1896.
20) The structures of sulfinate esters 12c were confirmed by direct
comparison with authentic samples prepared independently. Billard
anti-1,2-oxy-trifluoromethylthiolation of olefins by using N-(trifluor-
omethanethio)aniline in the presence of CF CO H, followed by
3
2
alkaline hydrolysis, afforded syn- and anti-β-hydroxysulfide 28
stereoselectively (ref 21). Triflination of these alcohols 28 with
unstable CF SOCl, generated in situ from sodium trifluoromethane-
3
sulfinate and mesitylsulfonyl chloride, provided triflinates 12c in good
yields (ref 22).
(
21) Ferry, A.; Billard, T.; Langlois, B. R.; Bacque, E. Angew. Chem.,
Int. Ed. 2009, 48, 8551.
22) (a) Hendrickson, J. B.; Skipper, P. L. Tetrahedron 1976, 32,
627. (b) Hasegawa, A.; Ishikawa, T.; Ishihara, K.; Yamamoto, H. Bull.
(
1
Chem. Soc. Jpn. 2005, 78, 1401. (c) Yanai, H.; Egawa, S.; Taguchi, T.
Tetrahedron Lett. 2013, 54, 2160.
(
23) (a) Mbuvi, H. M.; Woo, L. K. Organometallics 2008, 27, 637.
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002, 67, 4165. (c) Ledon, H.; Linstrumelle, G.; Julia, S. Bull. Chim.
Soc. Fr. 1973, 6, 2065.
(
2
(
24) McNamara, O. A.; Maguire, A. R. Tetrahedron 2011, 67, 9.
(
25) Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.;
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K. N.; Burant, J. C.; Millam, J. M.; Iyengar, S. S.; Tomasi, J.; Barone,
V.; Mennucci, B.; Cossi, M.; Scalmani, G.; Rega, N.; Petersson, G. A.;
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M.; Li, X.; Knox, J. E.; Hratchian, H. P.; Cross, J. B.; Bakken, V.;
Adamo, C.; Jaramillo, J.; Gomperts, R.; Stratmann, R. E.; Yazyev, O.;
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Morokuma, K.; Voth, G. A.; Salvador, P.; Dannenberg, J. J.;
K
DOI: 10.1021/acs.joc.6b00142
J. Org. Chem. XXXX, XXX, XXX−XXX