Anti carbocyanative cyclization of enynes under nickel catalysis

Article abstract of DOI:10.1021/jo400342y

Anti carbocyanative cyclization using 1,6-enynes under nickel catalysis is described. This reaction is triggered by hydronickelation to alkenes followed by carbometalation. Steric repulsion caused by the bulky substituents on alkynes promotes isomerizatio

Full text of DOI:10.1021/jo400342y

Article
pubs.acs.org/joc
Anti Carbocyanative Cyclization of Enynes under Nickel Catalysis
Tomohiro Igarashi, Shigeru Arai,* and Atsushi Nishida
Graduate School of Pharmaceutical Sciences, Chiba University, 1-8-1 Inohana, Chuo-ku, Chiba 260-8675, Japan
S
* Supporting Information
ABSTRACT: Anti carbocyanative cyclization using 1,6-enynes under nickel
catalysis is described. This reaction is triggered by hydronickelation to
alkenes followed by carbometalation. Steric repulsion caused by the bulky
substituents on alkynes promotes isomerization of the carbon−carbon
double bond geometry in an organonickel intermediate to introduce both
alkyl and cyano groups in an anti fashion.
also occurred, but the resulting intermediate would be
INTRODUCTION
■
unsuitable for sequential carbometalative cyclization. This
cyclization reaction was not affected by an external ligand
(entry 2), and a higher loading of AC (20 equiv) improved the
yields of 2a (to 52%) and 3a (to 24%) (entry 3). These results
are summarized in Table 1.
To suppress the formation of simple hydrocyanation
products 4a and 5a, bulkier TIPS and TBDPS groups were
installed on C−C triple bonds (Table 2). As expected, their
bulkiness prevented alkyne hydrocyanation and exclusive
cyclization products were obtained with a remarkable improve-
ment of the 2/3 ratio when 1b was used (entry 1);however,
both the yield and ratio decreased with 1c (entry 2). These
results suggest that a bulkier silyl group is more favored to
reduce simple hydrocyanation that would give noncyclized
products. The structures of the 5-exo products Z-2b and E-2c
were confirmed by X-ray crystallographic analysis.11
The effect of the substituent at propargyl position was next
examined, and this was shown to significantly influence the
efficiency of cyclization. For example, 1d was transformed
exclusively to the corresponding 5-exo adduct 2d in 32% yield
(Table 3, entry 1). Its structure, including its stereochemistry,
was established to be E-form by X-ray crystallographic analysis.
This result indicates the C−C bonds that are newly created
through carbocyanation are oriented in an anti fashion. To the
best of our knowledge, this is the first example of anti
carbocyanation to nonactivated C−C triple bonds. Because the
addition of triphenylphosphite (1.2 equiv) slightly improved
the yield of E-2d (entry 2), the survey was continued under
these conditions. A reduced amount of AC (10 equiv) gave a
lower conversion to 2d and a significant amount of side
products 7 through C−N bond cleavage (entry 3). The
reaction was next investigated with a higher loading of AC (40
equiv), and E-2d was obtained in 65% yield as a sole product
(entry 4). A methyl group at the allylic position (1e) reduced
the efficiency of the cyclization, and E-2e was obtained in 37%
yield (entry 5).
A cyano group is a synthetic equivalent of carbonyl and related
functionalities, and its introduction into organic molecules,
particularly by transition metal catalysis, has been a major
challenge in synthetic organic chemistry. One of the most
fundamental protocols for its introduction has been catalytic
hydrocyanation to nonactivated carbon−carbon multiple
bonds1,2 using HCN with nickel catalysts3 (Chart 1, eq 1).
Since it was reported that C−CN bonds are easily cleaved4 and
suitable for cross coupling reactions,5 carbocyanation through
the cleavage of C−CN bonds by nickel complexes has been one
of the most powerful tools for the introduction of a cyano
functionality (eq 2).6 The hydro- and carbometalation occur via
migratory insertion so that the stereochemistry of the products
is always controlled to be syn (eq 1 and 2). Another
carbocyanation is Pd(II)-catalyzed 1,2-dicyanation through a
unique nucleophilic cyanation (cyanopalladation) (eq 3).7,8
This cyanation protocol has been quite useful for cyclization-
s8a,9 and [4+2] cycloaddition.10 Despite extensive investigations
to identify cyanation protocols under transition metal catalysis,
no examples that install both alkyl and cyano components in an
anti fashion such as eq 4 have been reported to date. In this
paper, we describe an alternative method for a regio- and
stereoselective hydro- and carbometalation sequence that
enables unprecedented anti carbocyanation through cyclization
(eq 5).
RESULTS AND DISCUSSION
■
Initially, we chose enyne 1a to study carbocyanative cyclization
using acetone cyanohydrin (AC) as an inexpensive and easy-to-
handle HCN source, in the presence of triphenylphosphite (1.2
equiv) and Ni[P(OPh3)]4 (10 mol %) at 150 °C (Table 1).
The reaction proceeded to give a mixture of 5- and 6-exo
products in respective yields of 32% and 3%. Careful
investigation revealed that the side products were 4a and 5a,
which could be obtained in 26% and 13% yields, respectively,
by hydrocyanation of a C−C triple bond of 1a (entry 1).
Products such as 6a were not observed at all. These results
indicate that cyclization could be triggered by the hydro-
nickelation of olefin, and its regioselectivity determines the ring
size of the products. Hydronickelation of a C−C triple bond
Received: February 20, 2013
Published: April 9, 2013
© 2013 American Chemical Society
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Chart 1
a
Table 1. Condition Survey Using 1a
a
Yields estimated by isolation of both stereoisomers.
Table 2. Substituent Effect
a
b
Both isomers are isolated. Inseparable stereoisomers.
To confirm the role of steric bulk around C−C triple bonds,
and stable functionality around the C−C triple bond is essential
for anti carbocyanation.
1f, which has a TMS group instead, was examined next
(Scheme 1). When the reaction was carried out for 15 h, major
products were assigned to be E- and Z-2f-H along with a small
amount of 2f. A shorter reaction time was effective for reducing
the above desilylated products to give an inseparable mixture of
E- and Z-2f in 34% yield. This result suggests that both a bulky
On the basis of these observations, a plausible catalytic
pathway that reasonably explains the regio- and stereochemistry
in the formation of 2 is shown in Scheme 2. The initial step is
the formation of Ni(II) from AC or HCN and Ni(0) followed
by regioselective hydronickelation to olefin. Bulky substituents
around the C−C triple bonds would be key functionalities for
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Table 3. Condition Survey Using TIPS Alkyne
a
Isolated yield.
Scheme 1. Reaction Using 1f
a
Determined by NMR analysis.
Scheme 2. Plausible Catalytic Pathway
fixing both multiple C−C bonds as a bidentate ligand to the Ni
center in A for smooth cyclization. This result suggests that the
intermediate A would be a key structure for cyclization.
Sequential 5-exo cyclization via carbometalation would give B,
which is then converted to syn-5-exo-2 through reductive
elimination from C. When significant steric repulsion between
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Table 4. Substrate Scope for Anti Carbocyanation
a
Isolated yield.
Scheme 3. Reaction of 1j
were recorded on a Fourier transform spectrophotometer. NMR
two substituents is observed in B, isomerization would be
promoted by the formation of a nickel−carbene intermediate12
D and the resulting C−C σ-bond rotation would convert the
double bond geometry to E-form, which gives anti-5-exo-2 as an
exclusive product. Isomerization of C−C double bonds in
alkenyl metal species (Pd,13a Ir13b) is also strongly influenced
by the steric bulk of the substituents.
The substrate scope is shown in Table 4. When 1g and 1h
were subjected to the optimized conditions, anti-5-exo-2g and
2h were obtained in respective yields of 29% and 31% without
any other cyclized products (entries 1 and 2). In the case of 1i,
a C−N bond cleavage mainly occurred to give 8 in 47% yield,
and 2i was obtained in only 7% yield (entry 3).
1
spectra were recorded at 400 and 600 MHz for H NMR and at 100
and 150 MHz for 13C NMR, with calibration using residual
undeuterated solvent as an internal reference. HRMS spectra were
obtained using an ESI mass spectrometer.
Typical Procedure for Representative Cyanative Cyclization
(synthesis of 2d). A solution of 1f (72.0 mg, 0.15 mmol), P(OPh)3
(55.4 mg, 0.18 mmol), Ni[P(OPh)3]4 (49.5 mg, 0.015 mmol, 10 mol
%), and acetone cyanohydrin (0.55 mL, 6.0 mmol) in toluene (0.3
mL) was heated for 24 h at 150 °C under an argon atmosphere. The
reaction was quenched by a mixture charged on a silica gel to be
purified by column chromatography (hexane:AcOEt = 5:1). 2d was
obtained as a colorless solid (48.1 mg, 0.096 mmol, 65%, mp 151−152
°C).
(Z)-2-(4-Methyl-1-tosylpyrrolidin-3-ylidene)-2-
(trimethylsilyl)acetonitrile (Z-2a). White solid (20.8 mg, 20%): 1H
NMR (CDCl3, 600 MHz) δ 7.70 (d, J = 8.4 Hz, 2H), 7.37 (d, J = 8.4
Hz, 2H), 4.12 (d, J = 16.8 Hz, 1H), 3.69 (d, J = 16.8 Hz, 1H), 3.23 (d,
J = 9.0 Hz, 1H), 3.19−3.12 (m, 2H), 2.45 (s, 3H), 1.28 (d, J = 7.2 Hz,
3H), 0.25 (s, 9H); 13C NMR (CDCl3, 150 MHz) δ 175.2, 144.4,
131.8, 130.0, 127.9, 118.2, 107.0, 53.9, 51.8, 41.7, 21.7, 19.0, −1.3; IR
(ATR) ν 2197, 1605, 1348, 1161 cm−1; HRMS (ESI) m/z calcd for
C17H24N2NaO2SSi [M + Na]+ 371.1225, found 371.1228; mp 125−
127 °C.
In the case of saccharin derivative such as 1j, the enyne
moiety was also suitable for cyanative cyclization to give 2j as a
diastereomixture (Scheme 3). The major product was assigned
to be trans on the basis of X-ray crystallography.
CONCLUSION
■
We have realized an unprecedented anti carbocyanation to
nonactivated C−C triple bonds under nickel catalysis. Bulky
substituents are essential for causing steric repulsion after
cyclization, and this effect would control the geometry of the
C−C double bond via a key nickel−carbene intermediate.
These new results may contribute to the development of
catalytic cyanation protocols, and their further application in
organic synthesis for the preparation of useful molecules is
currently underway.
(E)-2-(4-Methyl-1-tosylpyrrolidin-3-ylidene)-2-
1
(trimethylsilyl)acetonitrile (E-2a). Yellow oil (7.0 mg, 10%): H
NMR (CDCl3, 600 MHz) δ 7.72 (d, J = 7.8 Hz, 2H), 7.36 (d, J = 7.8
Hz, 2H), 4.35 (d, J = 17.4 Hz, 1H), 3.82 (d, J = 17.4 Hz, 1H), 3.40 (d,
J = 9.6 Hz, 1H), 3.10 (dd, J = 5.4, 9.6 Hz, 1H), 2.93 (quin, J = 5.4 Hz,
1H), 2.45 (s, 3H), 1.21 (d, J = 5.4 Hz, 3H), 0.26 (s, 9H); 13C NMR
(CDCl3, 150 MHz) δ 175.2, 144.2, 132.5, 130.0, 128.0, 118.2, 117.0,
55.1, 54.0, 38.3, 21.7, 20.8, −0.7; IR (ATR) ν 2962, 2159, 1452, 1348,
1160 cm−1; HRMS (ESI) m/z calcd for C17H24N2NaO2SSi [M + Na]+
371.1225, found 371.1228.
EXPERIMENTAL SECTION
■
General Remarks. All reactions were performed with dry solvents,
and reagents were purified by the usual methods. Reactions were
monitored by thin-layer chromatography carried out on 0.25 mm.
Column chromatography was performed with silica gel. IR spectra
(Z)-2-(1-Tosylpiperidin-3-ylidene)-2-(trimethylsilyl)-
1
acetonitrile (Z-3a). Yellow oil (10.3 mg, 12%): H NMR (CDCl3,
400 MHz) δ 7.63 (d, J = 8.4 Hz, 2H), 7.35 (d, J = 8.4 Hz, 2H), 3.68 (s,
2H), 3.10 (dd, J = 5.6, 5.6 Hz, 2H), 2.56 (dd, J = 6.0, 6.0 Hz, 2H), 2.45
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(s, 3H), 1.82 (tt, J = 5.6, 6.0 Hz, 2H), 0.36 (s, 9H); 13C NMR (CDCl3,
100 MHz) δ 165.3, 144.2, 132.6, 130.0, 128.0, 127.8, 119.0, 111.7,
50.5, 46.0, 34.0, 25.2, 21.6, −0.3; IR (ATR) ν 2957, 2181, 1598, 1443,
1348, 1161 cm−1; HRMS (ESI) m/z calcd for C17H24N2NaO2SSi [M +
Na]+ 371.1225, found 371.1227.
(E)-2-(1-Tosylpiperidin-3-ylidene)-2-(trimethylsilyl)-
acetonitrile (E-3a). White solid (6.1 mg, 7%): 1H NMR (CDCl3, 400
MHz) δ 7.71 (d, J = 8.4 Hz, 2H), 7.32 (d, J = 8.4 Hz, 2H), 3.97 (s,
2H), 3.26 (dd, J = 5.6, 6.0 Hz, 2H), 2.44 (s, 3H), 2.32 (dd, J = 6.4, 6.4
Hz, 2H), 1.75−1.69 (m, 2H), 0.23 (s, 9H); 13C NMR (CDCl3, 100
MHz) δ 165.1, 143.9, 134.0, 129.9, 127.9, 118.2, 110.8, 52.1, 45.7,
31.8, 24.8, 21.6, −0.5; IR (ATR) ν 2957, 2198, 1596, 1443, 1349, 1159
cm−1; HRMS (ESI) m/z calcd for C17H24N2NaO2SSi [M + Na]+
371.1225, found 371.1227; mp 87−93 °C.
(E)-N-Allyl-N-(2-cyano-3-(trimethylsilyl)allyl)-4-methylben-
zenesulfonamide (4a). Yellow oil (22.9 mg, 26%): 1H NMR
(CDCl3, 600 MHz) δ 7.76 (d, J = 8.4 Hz, 2H), 7.32 (d, J = 8.4 Hz,
2H), 6.66 (br, 1H), 5.78−5.72 (m, 1H), 5.23−5.20 (m, 2H), 4.04 (s,
2H), 3.90 (d, J = 7.2 Hz, 2H), 2.43 (s, 3H), 0.21 (s, 9H); 13C NMR
(CDCl3, 150 MHz) δ 151.6, 142.7, 135.3, 131.3, 128.5, 126.4, 124.7,
118.8, 117.0, 49.7, 46.2, 20.4, −1.9; IR (ATR) ν 2203, 1589, 1161
cm−1; HRMS (ESI) m/z calcd for C17H24N2NaO2SSi [M + Na]+
371.1225, found 371.1223.
(Z)-N-Allyl-N-(3-cyano-3-(trimethylsilyl)allyl)-4-methylben-
zenesulfonamide (5a). Brown oil (11.6 mg, 13%): 1H NMR
(CDCl3, 600 MHz) δ 7.66 (d, J = 8.4 Hz, 2H), 7.33 (d, J = 8.4 Hz,
2H), 6.76 (t, J = 6.6 Hz, 1H), 5.66 (ddt, J = 6.0, 10.8, 17.4 Hz, 1H),
5.21 (d, J = 10.8 Hz, 1H), 5.17 (d, J = 17.4 Hz, 1H), 4.01 (d, J = 6.0
Hz, 2H), 3.79 (d, J = 6.6 Hz, 2H), 2.44 (s, 3H), 0.28 (s, 9H); 13C
NMR (CDCl3, 150 MHz) δ 159.2, 150.5, 144.1, 136.8, 132.5, 127.2,
125.7, 119.9, 117.8, 50.7, 47.6, 21.7, −0.8; IR (ATR) ν 3065, 2203,
1488, 1161 cm−1; HRMS (ESI) m/z calcd for C17H24N2NaO2SSi [M +
Na]+ 371.1225, found 371.1228.
134.1, 130.0, 127.8, 119.0, 107.2, 52.3, 45.6, 32.7, 24.9, 21.6, 18.7, 12.7;
IR (ATR) ν 2238, 1461 cm−1; HRMS (ESI) m/z calcd for
C23H36N2NaO2SSi [M + Na]+ 455.2164, found 455.2170.
(Z)-2-(tert-Butyldiphenylsilyl)-2-(4-methyl-1-tosylpyrrolidin-
1
3-ylidene)acetonitrile (Z-2c). Yellow oil (30.0 mg, 20%): H NMR
(CDCl3, 600 MHz) δ 7.70−7.10 (m, 14H), 3.34−3.31 (m, 1H), 3.24
(d, J = 18 Hz, 1H), 3.17 (d, J = 9.6 Hz, 1H), 2.85 (dd, J = 9.6, 6.0 Hz,
1H), 2.68 (d, J = 18 Hz, 1H), 2.41 (s, 3H), 1.36 (d, J = 7.8 Hz, 3H),
1.13 (s, 9H); 13C NMR (CDCl3, 150 MHz) δ 182.0, 143.9, 135.89,
135.83, 131.3, 131.04, 130.97, 130.6, 130.4, 129.7, 128.6, 128.5, 127.9,
119.5, 101.6, 53.6, 52.6, 42.3, 28.2, 21.6, 19.2, 18.9; IR (ATR) ν 2923,
2853, 2200, 1669, 1577, 1464, 1351, 1161 cm−1; HRMS (ESI) m/z
calcd for C30H34N2NaO2SSi [M + Na]+ 537.2008, found 537.2027.
(E)-2-(tert-Butyldiphenylsilyl)-2-(4-methyl-1-tosylpyrrolidin-
3-ylidene)acetonitrile (E-2c). White solid (24.8 mg, 20%): 1H NMR
(CDCl3, 600 MHz) δ 7.76−7.24 (m, 14H), 4.41 (d, J = 17.4 Hz, 1H),
4.09 (d, J = 17.4 Hz, 1H), 3.05 (d, J = 9.6 Hz, 1H), 2.80 (dd, J = 5.4,
9.6 Hz, 1H), 2.46 (s, 3H), 2.12−2.10 (m, 1H), 1.11 (s, 9H), 0.37 (d, J
= 6.6 Hz, 3H); 13C NMR (CDCl3, 150 MHz) δ 181.1, 144.1, 135.8,
130.4, 130.0, 128.3, 128.3, 127.9, 119.6, 102.1, 55.0, 54.2, 38.4, 27.6,
27.0, 26.3, 21.7, 18.8; IR (ATR) ν 3047, 2240, 1541 cm−1; HRMS
(ESI) m/z calcd for C30H34N2NaO2SSi [M + Na]+ 537.2008, found
537.1997; mp 213−215 °C. CCDC no. 858856.
(Z)-2-(tert-Butyldiphenylsilyl)-2-(1-tosylpiperidin-3-ylidene)-
1
acetonitrile (Z-3c). Yellow oil (6.5 mg, 6%): H NMR (CDCl3, 600
MHz) δ 7.72 (d, J = 7.8 Hz, 2H), 7.54−7.32 (m, 8H), 7.10 (d, J = 8.4
Hz, 2H), 6.98 (d, J = 8.4 Hz, 2H), 2.97 (s, 2H), 2.87 (dd, J = 5.4, 5.4
Hz, 2H), 2.69 (dd, J = 6.0, 6.6 Hz, 2H), 2.36 (s, 3H), 1.85 (dddd, J =
5.4, 5.4, 6.0, 6.6 Hz, 2H), 1.20 (s, 9H); 13C NMR (CDCl3, 150 MHz)
δ 170.2, 143.7, 135.9, 135.5, 132.2, 130.0, 129.4, 128.3, 127.8, 120.1,
106.5, 52.2, 45.6, 33.7, 27.4, 24.6, 21.6, 19.0; IR (ATR) ν 2857, 2197,
1684, 1558, 1507, 1458, 1353, 1166 cm−1; HRMS (ESI) m/z calcd for
C30H34N2NaO2SSi [M + Na]+ 537.2008, found 537.2008.
(E)-2-(tert-Butyldiphenylsilyl)-2-(1-tosylpiperidin-3-ylidene)-
(Z)-2-(4-Methyl-1-tosylpyrrolidin-3-ylidene)-2-
(triisopropylsilyl)acetonitrile (Z-2b). White solid (40.8 mg, 40%):
1H NMR (CDCl3, 600 MHz) δ 7.68 (d, J = 7.8 Hz, 2H), 7.34 (d, J =
1
acetonitrile (E-3c). Yellow solid (3.6 mg, 3%): H NMR (CDCl3,
600 MHz) δ 7.75 (d, J = 8.4 Hz, 2H), 7.62−7.38 (m, 4H), 7.40−7.34
(m, 6H), 4.14 (s, 2H), 3.10 (dd, J = 5.4, 6.0 Hz, 2H), 2.44 (s, 3H),
1.76 (dd, J = 6.0, 6.6 Hz, 2H), 1.13−1.10 (m, 11H); 13C NMR
(CDCl3, 150 MHz) δ 170.8, 143.9, 135.8, 135.5, 132.3, 130.02, 129.96,
128.6, 128.5, 128.2, 128.0, 127.9, 119.4, 105.6, 52.0, 45.5, 33.2, 27.4,
26.9, 23.8, 21.7, 18.7; IR (ATR) ν 2931, 2859, 2202, 1577, 1428, 1352,
1165 cm−1; HRMS (ESI) m/z calcd for C30H34N2NaO2SSi [M + Na]+
537.2008, found 537.1997; mp 95−101 °C.
7.8 Hz, 2H), 4.18 (dd, J = 0.8, 16.8 Hz, 1H), 3.70 (d, J = 16.8 Hz, 1H),
3.31−3.26 (m, 2H), 3.05 (dd, J = 7.2, 9.6 Hz, 1H), 2.43 (s, 3H), 1.30
(tt, J = 7.2, 7.8 Hz, 3H), 1.29 (d, J = 6.6 Hz, 3H), 1.08 (d, J = 7.8 Hz,
9H), 1.05 (d, J = 7.2 Hz, 9H); 13C NMR (CDCl3, 150 MHz) δ 177.6,
144.4, 142.7, 129.9, 128.0, 119.2, 104.0, 53.7, 52.1, 42.5, 21.7, 19.5,
18.48, 18.42. 12.0; IR (ATR) ν 2213, 1647, 1597, 1349, 1160 cm−1;
HRMS (ESI) m/z calcd for C23H37N2O2SSi [M + H]+ 433.2345,
found 433.2353; mp 136−137 °C. CCDC no. 857691.
(E)-2-(3-Methyl-1-tosyl-1-azaspiro[4.5]decan-4-ylidene)-2-
(triisopropylsilyl)acetonitrile (E-2d). White solid (48.1 mg, 65%):
1H NMR (CDCl3, 600 MHz) δ 7.75 (d, J = 7.8 Hz, 2H), 7.28 (d, J =
(E)-2-(4-Methyl-1-tosylpyrrolidin-3-ylidene)-2-
(triisopropylsilyl)acetonitrile (E-2b). White solid (20.4 mg, 20%):
1H NMR (CDCl3, 600 MHz) δ 7.73 (d, J = 8.4 Hz, 2H), 7.34 (d, J =
7.8 Hz, 2H), 3.47 (d, J = 10.2 Hz, 1H), 3.32 (d, J = 4.8, 10.2 Hz, 1H),
2.79−2.75 (m, 1H), 2.65−2.59 (m, 1H), 2.41 (s, 3H), 2.38−2.20 (m,
2H), 1.90 (d, J = 14.4 Hz, 1H), 1.71−1.56 (m, 6H), 1.41−1.35 (m,
3H), 1.12 (d, J = 3.6 Hz, 9H), 1.11 (d, J = 3.6 Hz, 9H), 0.98 (d, J = 6.6
Hz, 3H); 13C NMR (CDCl3, 150 MHz) δ 190.5, 143.2, 139.2, 129.6,
127.2, 119.1, 100.8, 74.7, 53.8, 38.9, 34.7, 33.8, 22.4, 22.0, 21.7, 21.6,
20.2, 18.9, 12.7; IR (ATR) ν 2945, 2868, 2189, 1597, 1570, 1464,
1340, 1159 cm−1; HRMS (ESI) m/z calcd for C28H45N2O2SSi [M +
H]+ 501.2790, found 501.2963; mp 151−152 °C. CCDC no. 862635.
(E)-2-((2R,3S)-2,3-Dimethyl-1-tosyl-1-azaspiro[4.5]decan-4-
ylidene)-2-(triisopropylsilyl)acetonitrile (E-2e). Brown oil (9.4
8.4 Hz, 2H), 4.38 (d, J = 16.2 Hz, 1H), 3.98 (d, J = 16.2 Hz, 1H), 3.45
(d, J = 10.2 Hz, 1H), 3.08 (dd, J = 6.6, 10.2 Hz, 1H), 2.88 (dd, J = 6.6,
6.6 Hz, 1H), 2.43 (s, 3H), 1.29 (q, J = 7.2 Hz, 3H), 1.18 (q, J = 6.6 Hz,
3H), 1.07 (d, J = 7.2 Hz, 18H); 13C NMR (CDCl3, 150 MHz) δ 176.6,
144.1, 132.9, 130.0, 128.0, 119.3, 103.7, 55.3, 53.7, 39.0, 21.7, 20.5,
18.7, 12.2; IR (ATR) ν 2188, 1636, 1558, 1339 cm−1; HRMS (ESI)
m/z calcd for C23H36N2NaO2SSi [M + Na]+ 455.2164, found
455.2179; mp 84−91 °C.
(Z)-2-(1-Tosylpiperidin-3-ylidene)-2-(triisopropylsilyl)-
1
1
acetonitrile (Z-3b). Colorless oil (7.8 mg, 9%): H NMR (CDCl3,
mg, 39%): H NMR (CDCl3, 600 MHz) δ 7.79 (d, J = 8.4 Hz, 2H),
400 MHz) δ 7.60 (d, J = 8.4 Hz, 2H), 7.35 (d, J = 8.4 Hz, 2H), 3.58 (s,
2H), 3.04 (dd, J = 5.6, 5.6 Hz, 1H), 2.63 (dd, J = 6.4, 6,4 Hz, 2H), 2.44
(s, 3H), 1.84 (tt, J = 5.6, 6.4 Hz, 2H), 1.46 (q, J = 7.2 Hz, 3H), 1.14 (d,
J = 7.2 Hz, 18H); 13C NMR (CDCl3, 100 MHz) δ 166.8, 144.3, 131.8,
130.0, 128.1, 119.9, 108.3, 51.5, 46.3, 34.3, 25.2, 21.7, 18.7, 12.7; IR
(ATR) ν 1647, 1457, 1166 cm−1; HRMS (ESI) m/z calcd for
C23H36N2NaO2SSi [M + Na]+ 455.2164, found 455.2168.
7.27 (d, J = 8.4 Hz, 2H), 3.84 (q, J = 7.2 Hz, 1H), 2.75 (dt, J = 4.8,
13.8 Hz, 1H), 2.58 (q, J = 7.2 Hz, 1H), 2.48−2.23 (m, 4H), 2.41 (s,
3H), 2.04−2.01 (m, 2H), 1.74−1.55 (m, 3H), 1.38 (tt, J = 7.2, 7.8 Hz,
3H), 1.28 (d, J = 7.2 Hz, 3H), 1.14 (d, J = 7.8 Hz, 9H), 1.12 (d, J = 7.2
Hz, 9H), 0.73 (d, J = 7.2 Hz, 3H); 13C NMR (CDCl3, 150 MHz) δ
190.8, 139.7, 129.6, 127.2, 120.8, 119.2, 102.6, 74.1, 63.6, 45.5, 39.7,
34.5, 23.0, 22.2, 22.0, 21.6, 21.5, 20.9, 19.02, 18.98, 12.6; IR (ATR) ν
2933, 2188, 1464, 1342, 1163 cm−1; HRMS (ESI) m/z calcd for
C29H46N2NaO2SSi [M + Na]+ 537.2946, found 537.2943.
(E)-2-(1-Tosylpiperidin-3-ylidene)-2-(triisopropylsilyl)-
1
acetonitrile (E-3b). Brown oil (2.7 mg, 3%): H NMR (CDCl3, 600
MHz) δ 7.72 (d, J = 8.4 Hz, 2H), 7.31 (d, J = 8.4 Hz, 2H), 4.07 (s,
2H), 3.28 (dd, J = 6.0, 6.0 Hz, 1H), 2.41 (s, 3H), 2.33 (dd, J = 6.0, 6.0
Hz, 2H), 1.73 (tt, J = 6.0, 6.0 Hz, 2H), 1.34 (q, J = 7.2 Hz, 3H), 1.06
(d, J = 7.2 Hz, 18H); 13C NMR (CDCl3, 150 MHz) δ 166.9, 143.9,
2-(3-Methyl-1-tosyl-1-azaspiro[4.5]decan-4-ylidene)-2-
(trimethylsilyl)acetonitrile (inseparable mixture of E- and Z-
1
2f). White powder (22.2 mg, 1.8:1, 34%): H NMR (CDCl3, 600
MHz) δ 7.74 (d, J = 7.2 Hz, 2H), 7.67 (d, J = 7.8 Hz, 2 × 0.69H),
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7.28−7.25 (m, 2 + 2 × 0.69H), 3.95 (dd, J = 9.0, 13.8 Hz, 1 × 0.69H),
3.45 (dd, J = 5.4, 10.8 Hz, 1H), 3.39 (d, J = 10.8 Hz, 1H), 3.17 (d, J =
7.8, 13.8 Hz, 1 × 0.69H), 2.75−2.73 (m, 1H), 2.62−2.56 (m, 1 ×
0.69H), 2.42 (s, 3 × 0.69H), 2.41 (s, 3H), 2.49−2.34 (m, 3H), 2.30−
1.57 (m, 10H), 1.42−1.36 (m, 0.3H), 1.29−1.20 (m, 3.8H), 1.18 (d, J
= 6.6 Hz, 3 × 0.69H), 0.97 (d, J = 7.2 Hz, 3H), 0.38 (s, 9 × 0.69H),
0.27 (s, 9H); 13C NMR (CDCl3, 150 MHz) δ 187.3, 186.4, 150.5,
144.2, 143.3, 138.9, 137.0, 129.9, 129.7, 129.6, 127.6, 127.4, 125.7,
120.2, 119.8, 118.1, 105.5, 104.0, 74.4, 73.8, 53.4, 52.5, 41.7, 41.2, 37.9,
34.8, 34.7, 34.24, 34.22, 33.2, 31.0, 29.7, 25.3, 25.0, 24.5, 23.2, 22.7,
22.5, 21.9, 21.8, 21.63, 21.57, 21.2, 20.8, 19.2, 2.2, −0.2; IR (ATR) ν
2931, 2189, 1453, 1340 cm−1; HRMS (ESI) m/z calcd for
C22H32N2NaO2SSi [M + Na]+ 439.1851, found 439.1856; mp 112−
116 °C.
cm−1; HRMS (ESI) m/z calcd for C35H45N2O2SSi [M + H]+
585.2971, found 585.2976.
(E)-2-((2S,9bS)-9b-Isopropyl-2-methyl-5,5-dioxido-2,3-
dihydrobenzo[d]pyrrolo[1,2-b]isothiazol-1(9bH)-ylidene)-2-
(triisopropylsilyl)acetonitrile (trans-2j). White solid (18.7 mg,
1
21%): H NMR (CDCl3, 600 MHz) δ 8.31 (d, J = 8.4 Hz, 1H), 7.75
(d, J = 7.8 Hz, 1H), 7.57−7.54 (m, 2H), 4.04 (d, J = 12 Hz, 1H),
3.73−3.68 (m, 1H), 3.37 (dd, J = 12, 4.8 Hz, 1H), 3.00−2.95 (m, 1H),
1.47 (m, 3H), 1.19 (d, J = 7.2 Hz, 9H), 1.16 (d, J = 7.2 Hz, 9H), 0.85
(d, J = 7.2 Hz, 3H), 0.75 (d, J = 6.6 Hz, 3H); 13C NMR (CDCl3, 150
MHz) δ 181.8, 142.5, 135.0, 134.1, 130.0, 123.8, 121.9, 121.5, 104.8,
84.3, 52.8, 42.3, 35.9, 21.7, 19.1, 19.0, 17.5, 12.8; IR (ATR) ν 2947,
2869, 2190, 1573, 1466, 1387, 1169 cm−1; HRMS (ESI) m/z calcd for
C25H38N2NaO2SSi [M + Na]+ 481.2321, found 481.2314; mp 168−
172 °C. CCDC no. 905347.
(Z)-2-(3-Methyl-1-tosyl-1-azaspiro[4.5]decan-4-ylidene)-
acetonitrile (Z-2f-H). White solid (8.4 mg, 10%): 1H NMR (CDCl3,
600 MHz) δ 7.73 (d, J = 8.4 Hz, 2H), 7.28 (d, J = 8.4 Hz, 2H), 5.13
(d, J = 2.4 Hz, 1H), 3.79 (dd, J = 8.4, 12 Hz, 1H), 2.98 (dd, J = 9.6, 12
Hz, 1H), 2.72−2.66 (m, 1H), 2.42 (s, 3H), 2.35−2.26 (m, 2H), 2.14−
2.05 (m, 2H), 1.86−1.80 (m, 2H), 1.72−1.65 (m, 3H), 1.53−1.46 (m,
1H), 1.03 (d, J = 6.6 Hz, 3H); 13C NMR (CDCl3, 150 MHz) δ 178.5,
143.6, 138.7, 129.8, 127.2, 115.7, 89.9, 73.4, 53.3, 39.0, 35.3, 33.1, 24.1,
22.1, 21.8, 21.6, 16.8; IR (ATR) ν 2924, 2854, 2217, 1451, 1325, 1156,
929 cm−1; HRMS (ESI) m/z calcd for C19H24N2NaO2S [M + Na]+
367.1456, found 367.1453; mp 140−145 °C. CCDC no. 911816.
(E)-2-(3-Methyl-1-tosyl-1-azaspiro[4.5]decan-4-ylidene)-
acetonitrile (E-2f-H). Colorless oil (18.7 mg, 20%): 1H NMR
(CDCl3, 600 MHz) δ 7.72 (d, J = 8.4 Hz, 2H), 7.28 (d, J = 8.4 Hz,
2H), 5.62 (d, J = 1.8 Hz, 1H), 3.51 (dd, J = 7.2, 10.2 Hz, 1H), 3.13−
3.09 (m, 2H), 2.77 (dt, J = 4.2, 13.2 Hz, 1H), 2.48 (dt, J = 4.8, 13.2
Hz, 1H), 2.41 (s, 3H), 1.83−1.69 (m, 6H), 1.52−1.38 (m, 2H), 1.19
(d, J = 6.6 Hz, 3H); 13C NMR (CDCl3, 150 MHz) δ 177.6, 143.5,
138.1, 129.7, 127.4, 116.0, 92.7, 70.7, 52.5, 38.3, 34.8, 33.7, 23.9, 22.3,
22.2, 21.6, 19.7; IR (ATR) ν 2930, 2874, 2219, 1455, 1330, 1155, 816
cm−1; HRMS (ESI) m/z calcd for C19H24N2NaO2S [M + Na]+
367.1456, found 367.1451.
(E)-2-((9bS)-9b-Isopropyl-2-methyl-5,5-dioxido-2,3-
dihydrobenzo[d]pyrrolo[1,2-b]isothiazol-1(9bH)-ylidene)-2-
(triisopropylsilyl)acetonitrile (inseparable mixture of trans-
1
and cis-2j, its ratio = 1/0.71): H NMR (CDCl3, 600 MHz) δ 8.50
(d, J = 7.8 Hz, 1 × 0.71H), 8.31 (d, J = 8.4 Hz, 1H), 7.75 (d, J = 7.8
Hz, 1H), 7.73 (d, J = 7.8 Hz, 1 × 0.71H), 7.67−7.64 (m, 2 × 0.71H),
7.57−7.54 (m, 2H), 4.19 (dd, J = 9.6, 13.2 Hz, 1H), 4.04 (d, J = 12 Hz,
1H), 3.70 (tt, J = 6.0, 6.6 Hz, 1H), 3.44 (tt, J = 6.6, 6.6 Hz, 1H), 3.37
(dd, J = 12, 4.8 Hz, 1H), 3.26−3.21 (m, 1 × 0.71H), 3.00−2.93 (m, 1
+ 1 × 0.71H), 1.49−1.40 (m, 3 + 3 × 0.71H), 1.29 (d, J = 6.6 Hz, 3 ×
0.71H), 1.19 (d, J = 7.2 Hz, 9H), 1.16 (d, J = 7.2 Hz, 9H), 1.12 (d, J =
6.6 Hz, 3 + 3 × 0.71H), 1.08 (d, J = 7.8 Hz, 9 × 0.71H), 1.05 (d, J =
7.8 Hz, 9 × 0.71H), 0.90 (d, J = 6.6 Hz, 3 × 0.71H), 0.85 (d, J = 7.2
Hz, 3H), 0.75 (d, J = 6.6 Hz, 3H); 13C NMR (CDCl3, 150 MHz) δ
182.9, 181.9, 142.5, 139.5, 134.8, 134.2, 133.8, 133.7, 130.3, 130.1,
126.7, 123.7, 121.9, 121.8, 121.5, 121.4, 107.6, 104.7, 86.9, 84.3, 52.8,
51.6, 42.3, 40.7, 35.9, 35.3, 21.9, 21.5, 19.6, 19.3, 19.11, 19.06, 19.0,
18.9, 18.6, 17.6, 17.5; IR (ATR) ν 2946, 2868, 2191, 1582, 1312, 1178
cm−1; HRMS (ESI) m/z calcd for C25H38N2NaO2SSi [M + Na]+
481.2321, found 481.2314.
N-Allyl-N-(3-(tert-butyldiphenylsilyl)prop-2-yn-1-yl)-4-meth-
ylbenzenesulfonamide (1c). Yellow oil: 1H NMR (CDCl3, 600
MHz) δ 7.71−7.67 (m, 3H), 7.57−7.55 (m, 3H), 7.42−7.36 (m, 3H),
7.34−7.32 (m, 3H), 6.96 (d, J = 8.4 Hz, 2H), 5.79 (ddt, J = 6.6, 10.8,
17.4 Hz, 1H), 5.28 (dd, J = 1.2, 17.4 Hz, 1H), 5.25 (dd, J = 1.2, 10.8
Hz, 1H), 4.32 (s, 2H), 3.90 (d, J = 6.6 Hz, 2H), 2.10 (s, 3H), 0.94 (s,
9H); 13C NMR (CDCl3, 150 MHz) δ 143.6, 135.5, 134.9, 133.6,
132.9, 132.1, 129.8, 129.7, 127.8, 120.2, 102.2, 86.5, 49.1, 37.0, 27.0,
21.4, 18.4; IR (ATR) ν 2931, 2185, 1507, 1473, 1429, 1351, 1164
cm−1; HRMS (ESI) m/z calcd for C29H33NNaO2SSi [M + Na]+
510.1899, found 510.1887.
N-Allyl-4-methyl-N-(1-((triisopropylsilyl)ethynyl)cyclohexyl)-
benzenesulfonamide (1d). Yellow oil: 1H NMR (CDCl3, 600
MHz) δ 7.71 (d, J = 8.4 Hz, 2H), 7.22 (d, J = 8.4 Hz, 6.05 (ddt, J =
6.0, 10.2, 17.4 Hz, 1H), 5.25 (d, J = 17.4 Hz, 1H), 5.12 (dt, J = 1.2,
10.2 Hz, 1H), 4.22 (dd, J = 1.2, 6.0 Hz, 2H), 2.38 (s, 3H), 2.04−1.95
(m, 4H), 1.64−1.55 (m, 5H), 1.04−0.90 (m, 21H); 13C NMR
(CDCl3, 150 MHz) δ 142.7, 140.1, 137.6, 129.5, 127.3, 116.5, 107.2,
88.2, 63.6, 50.9, 37.9, 24.9, 23.8, 21.5, 18.7, 11.3; IR (ATR) ν 2933,
2860, 2170, 1445, 1330, 1157, 863 cm−1; HRMS (ESI) m/z calcd for
C27H43NNaO2SSi [M + Na]+ 496.2682, found 496.2669.
N-(But-3-en-2-yl)-4-methyl-N-(1-((triisopropylsilyl)ethynyl)-
cyclohexyl)benzenesulfonamide (1e). Colorless oil: 1H NMR
(CDCl3, 400 MHz) δ 7.76 (d, J = 8.4 Hz, 2H), 7.21 (d, J = 8.4 Hz,
2H), 6.44 (ddd, J = 6.8, 10.8, 17.6 Hz, 1H), 5.17 (d, J = 17.6 Hz, 1H),
5.10 (d, J = 10.8 Hz, 1H), 4.75 (dq, J = 6.8, 6.8 Hz, 1H), 2.39 (s, 3H),
2.12−1.95 (m, 4H), 1.73 (d, J = 6.8 Hz, 3H), 1.62−1.55 (m, 4H), 1.07
(br, 21H); IR (ATR) ν 2938, 2863, 2170, 1599, 1462, 1326, 1154
cm−1; HRMS (ESI) m/z calcd for C28H45NNaO2SSi [M + Na]+
510.2838, found 510.2831.
(E)-2-(Triisopropylsilyl)-2-(2,2,4-trimethyl-1-tosylpyrrolidin-
1
3-ylidene)acetonitrile (2g). White solid (27.9 mg, 29%): H NMR
(CDCl3, 600 MHz) δ 7.74 (d, J = 8.4 Hz, 2H), 7.28 (d, J = 8.4 Hz,
2H), 3.21−3.20 (m, 2H), 2.88−2.84 (m, 1H), 2.41 (s, 3H), 2.01 (m,
3H), 1.75 (m, 3H), 1.41−1.34 (m, 3H), 1.12−1.09 (m, 21H); 13C
NMR (CDCl3, 150 MHz) δ 187.1, 143.4, 137.8, 129.7, 127.5, 119.1,
101.1, 70.6, 52.4, 38.9, 27.1, 24.0, 21.6, 21.4, 18.88, 18.85, 12.6; IR
(ATR) ν 2948, 2868, 2192, 1580, 1463, 1333, 1158 cm−1; HRMS
(ESI) m/z calcd for C25H40N2NaO2SSi [M + Na]+ 483.2477, found
483.2466; mp 139−143 °C. CCDC no. 877975.
(E)-2-(2,2-Diethyl-4-methyl-1-tosylpyrrolidin-3-ylidene)-2-
(triisopropylsilyl)acetonitrile (2h). White solid (30.5 mg, 31%): 1H
NMR (CDCl3, 600 MHz) δ 7.76 (d, J = 8.4 Hz, 2H), 7.30 (d, J = 8.4
Hz, 2H), 3.39 (dd, J = 9.6, 6.0 Hz, 1H), 3.27 (d, J = 9.6 Hz, 1H),
2.93−2.88 (m, 1H), 2.93−2.88 (m, 1H), 2.60−2.47 (m, 2H), 2.41 (s,
3H), 2.36−2.27 (m, 2H), 1.47−1.39 (m, 3H), 1.16 (d, J = 7.8 Hz,
9H), 1.14 (d, J = 7.2 Hz, 9H), 0.63 (t, J = 7.8 Hz, 3H), 0.62 (t, J = 6.6
Hz, 3H); 13C NMR (CDCl3, 150 MHz) δ 184.1, 143.4, 137.8, 129.7,
127.2, 118.9, 102.8, 80.9, 55.1, 37.6, 32.9, 30.7, 22.6, 21.6, 19.0, 18.7,
12.5, 10.6, 9.9; IR (ATR) ν 2944, 2868, 2189, 1597, 1462, 1335, 1160
cm−1; HRMS (ESI) m/z calcd for C27H44N2NaO2SSi [M + Na]+
511.2790, found 511.2789; mp 196−197 °C. CCDC no. 877574.
(E)-2-(4-Methyl-2,2-diphenyl-1-tosylpyrrolidin-3-ylidene)-2-
(triisopropylsilyl)acetonitrile (2i) (obtained at 90% purity).
1
Yellow oil (9.7 mg, 7%): H NMR (CDCl3, 600 MHz) δ 7.49−7.06
(m, 14H), 4.13 (dd, J = 7.8, 9.0 Hz, 1H), 3.84 (d, J = 9.0 Hz, 1H),
3.17−3.15 (m, 1H), 2.36 (s, 3H), 1.32−0.91 (m, 24H); 13C NMR
(CDCl3, 150 MHz) δ 169.3, 155.7, 147.3, 143.3, 141.8, 136.6, 134.2,
133.6, 131.2, 130.5, 130.0, 129.7, 129.4, 129.2, 129.1, 129.0, 128.7,
128.4, 128.20, 128.18, 127.9, 127.7, 127.5, 127.4, 127.3, 127.1, 127.0,
126.8, 126.7, 121.6, 120.8, 120.2, 118.1, 115.5, 115.4, 114.9, 114.7,
56.6, 23.9, 21.7, 19.1, 18.9, 18.8, 18.7, 17.8, 12.7, 12.4, 11.8, 11.5, 11.4;
IR (ATR) ν 2942, 2890, 2865, 2172, 1597, 1491, 1447, 1343, 1160
N-Allyl-4-methyl-N-(1-((trimethylsilyl)ethynyl)cyclohexyl)-
benzenesulfonamide (1f). Colorless oil: 1H NMR (CDCl3, 600
MHz) δ 7.72 (d, J = 8.4 Hz, 2H), 7.24 (d, J = 8.4 Hz, 2H), 6.02 (ddt, J
= 4.8, 10.8, 17.4 Hz, 1H), 5.26 (dd, J = 1.2, 17.4 Hz, 1H), 5.14 (dd, J =
1.2, 10.8 Hz, 1H), 4.15 (d, J = 4.8 Hz, 2H), 2.39 (s, 3H), 2.03−1.92
(m, 4H), 1.64−1.50 (m, 5H), 1.14−1.10 (m, 1H), 0.07 (s, 9H); 13C
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NMR (CDCl3, 150 MHz) δ 142.8, 139.8, 137.4, 129.4, 127.5, 116.6,
105.3, 91.8, 63.1, 50.6, 37.8, 37.8, 24.9, 23.8, 21.6, −0.1; IR (ATR) ν
2933, 2860, 1599, 1445, 1330, 1157, 863 cm−1; HRMS (ESI) m/z
calcd for C21H31NNaO2SSi [M + Na]+ 412.1742, found 412.1737.
N-Allyl-4-methyl-N-(2-methyl-4-(triisopropylsilyl)but-3-yn-
2-yl)benzenesulfonamide (1g). Orange oil: 1H NMR (CDCl3, 400
MHz) δ 7.73 (d, J = 8.4 Hz, 2H), 7.25 (d, J = 8.4 Hz, 2H), 6.09−6.02
(m, 1H), 5.27 (dd, J = 1.6, 17.2 Hz, 1H), 5.15 (dd, J = 1.6, 10 Hz, 1H),
4.22 (d, J = 5.6 Hz, 2H), 2.40 (s, 3H), 1.69 (s, 6H), 1.06−0.96 (m,
21H); 13C NMR (CDCl3, 100 MHz) δ 142.8, 139.9, 129.5, 127.2,
116.9, 110.1, 84.5, 57.6, 51.2, 31.1, 21.5, 18.6, 11.2; IR (ATR) ν 2942,
2891, 2864, 2164, 1599, 1462, 1384, 1332, 1153, 880 cm−1; HRMS
(ESI) m/z calcd for C24H39NNaO2SSi [M + Na]+ 456.2369, found
456.2380.
(21590003), helpful discussion in “Workshop on Chirality in
Chiba University (WCCU)”, and kind support for X-ray
crystallographic analysis by Mr. Masaki Hoshi (Chiba
University).
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■
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N-Allyl-N-(3-ethyl-1-(triisopropylsilyl)pent-1-yn-3-yl)-4-
methylbenzenesulfonamide (1h). Yellow solid: 1H NMR (CDCl3,
600 MHz) δ 7.76 (d, J = 8.4 Hz, 2H), 7.25 (d, J = 8.4 Hz, 2H), 5.94−
5.84 (m, 1H), 5.05 (d, J = 17.4 Hz, 1H), 4.99 (d, J = 10.2 Hz, 1H),
4.18 (d, J = 6.0 Hz, 2H), 2.41 (s, 3H), 2.31−2.74 (m, 2H), 1.95−1.92
(m, 2H), 1.09−1.04 (m, 21H), 1.00 (t, J = 7.2 Hz, 6H); 13C NMR
(CDCl3, 150 MHz) δ 147.8, 139.4, 129.2, 127.7, 116.4, 107.3, 83.8,
69.3, 67.3, 51.7, 33.6, 21.4, 18.6, 11.2, 9.8; IR (ATR) ν 2941, 2865,
2174, 1599, 1461, 1350, 1159, 883 cm−1; HRMS (ESI) m/z calcd for
C26H43NNaO2SSi [M + Na]+ 484.2682, found 484.2688; mp 47−50
°C.
N-Allyl-N-(1,1-diphenyl-3-(triisopropylsilyl)prop-2-yn-1-yl)-
1
4-methylbenzenesulfonamide (1i). Yellow oil: H NMR (CDCl3,
600 MHz) δ 7.52−7.49 (m, 4H), 7.24−7.22 (m, 2H), 7.18−7.15 (m,
6H), 7.05−7.03 (m, 2H), 6.15−6.09 (m, 1H), 5.12−5.07 (m, 1H),
4.24 (d, J = 5.4 Hz, 2H), 2.36 (s, 3H), 1.10−1.06 (m, 21H); 13C NMR
(CDCl3, 150 MHz) δ 143.3, 141.0, 139.7, 135.8, 129.7, 128.9, 127.7,
127.5, 127.4, 117.9, 108.7, 90.0, 71.7, 52.7, 21.5, 18.7, 11.5; IR (ATR)
ν 2890, 2160, 1598, 1491, 1448, 1338, 1158, 882 cm−1; HRMS (ESI)
m/z calcd for C34H43NNaO2SSi [M + Na]+ 580.2681, found 580.2668.
2-Allyl-3-isopropyl-3-((triisopropylsilyl)ethynyl)-2,3-
1
dihydrobenzo[d]isothiazole 1,1-dioxide (1j): H NMR (CDCl3,
400 MHz) δ 7.78 (d, J = 7.6 Hz, 1H), 7.63−7.59 (m, 1H), 7.55−7.50
(m, 2H), 6.12−6.03 (m, 1H), 5.44 (d, J = 17.2 Hz, 1H), 5.26 (d, J = 10
Hz, 1H), 4.21 (dd, J = 6.4, 16.4 Hz, 1H), 4.04 (dd, J = 6.4, 16.4 Hz,
1H), 2.35 (tt, J = 6.8, 6.8 Hz, 1H), 1.04−1.02 (m, 21H), 0.99 (d, J =
6.8 Hz, 6H); 13C NMR (CDCl3, 100 MHz) δ 138.4, 134.2, 134.1,
132.9, 129.7, 124.5, 121.4, 118.5, 103.7, 90.6, 69.4, 46.1, 39.6, 18.8,
17.5, 17.4, 11.2; IR (ATR) ν 2943, 2864, 1463, 1387, 1160, 998, 930
cm−1; HRMS (ESI) m/z calcd for C24H37NNaO2SSi [M + Na]+
454.2212, found 454.2206; mp 68−71 °C.
(7) Arai, S.; Nishida, A. Synlett 2012, 23, 2880.
(8) (a) Arai, S.; Sato, T.; Koike, Y.; Hayashi, M.; Nishida, A. Angew.
Chem., Int. Ed. 2009, 48, 4528. (b) Arai, S.; Sato, T.; Nishida, A. Adv.
Synth. Catal. 2009, 351, 1897.
(9) Arai, S.; Koike, Y.; Nishida, A. Adv. Synth. Catal. 2010, 352, 893.
(10) (a) Arai, S.; Koike, Y.; Hada, H.; Nishida, A. J. Am. Chem. Soc.
2010, 132, 4522. (b) Arai, S.; Koike, Y.; Hada, H.; Nishida, A. J. Org.
Chem. 2010, 75, 7573.
(11) For Z-2b (CCDC no. 857691), E-2c (858856), E-2d (862635),
E-2f-H (911816), 2g (877975), 2h (877574), and trans-2j (905347),
these data can be obtained free of charge from The Cambridge
Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_request/
cif.
(12) For Ni catalysis, see: (a) Huggins, J. M.; Bergman, R. G. J. Am.
Chem. Soc. 1981, 103, 3002. (b) Yamamoto, Y.; Suginome, M. J. Am.
Chem. Soc. 2005, 127, 15706.
(Cyclohex-1-en-1-ylethynyl)triisopropylsilane (7). Colorless
1
oil: H NMR (CDCl3, 600 MHz) δ 6.15 (m, 1H), 2.14−2.07 (m,
4H), 1.63−1.55 (m, 4H), 1.08−1.04 (m, 21H); 13C NMR (CDCl3,
150 MHz) δ 135.5, 121.2, 109.4, 87.0, 29.8, 25.7, 22.3, 21.6, 18.7, 11.4;
IR (ATR) ν 2144, 1677, 1462 cm−1; LRMS (EI) m/z 226 (M+), 233
(M+ − Me2 − H), 219 (M+ − iPr), 191, 88, 70, 61; HRMS (ESI) m/z
calcd for C17H30NaSi [M + Na]+ 285.2015, found 285.2017.
ASSOCIATED CONTENT
■
(13) (a) Murakami, M.; Yoshida, T.; Kawanami, S.; Ito, Y. J. Am.
Chem. Soc. 1995, 117, 6408. (b) Kezuka, S.; Okado, T.; Niou, E.;
Takeuchi, R. Org. Lett. 2005, 7, 1711.
S
* Supporting Information
1
Copies of H and 13C NMR spectra for all new compounds.
This material is available free of charge via the Internet at
http://pubs.acs.org.
AUTHOR INFORMATION
Corresponding Author
*Fax, (+81)-43-226-2942; e-mail, arai@p.chiba-u.ac.jp.
■
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
We gratefully acknowledge financial support from a Grant-in-
Aid for Scientific Research(C) from JSPS KAKEHNHI
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dx.doi.org/10.1021/jo400342y | J. Org. Chem. 2013, 78, 4366−4372