Olefination of N-Sulfinylimines under Mild Conditions

Article abstract of DOI:10.1002/ejoc.201601577

A very simple and efficient diastereoselective synthesis of 1,2-disubstituted alkenes has been achieved under mild conditions. Sulfoxide stabilised N-sulfinylimines reacted with in-situ-generated phosphonate carbanions to give 1,2-disubtituted alkenes in good to excellent yields. Different aryl phosphonates reacted with a range of electronically diverse N-sulfinylimines to give alkenes with >99:1 E selectivity. The most important feature of this protocol is that the reaction can be carried out at room temperature with inexpensive sodium hydride as the most effective base to generate the reactive phosphonate carbanions, and producing the alkenes with E selectivity in up to 85 % isolated yield.

Full text of DOI:10.1002/ejoc.201601577

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Accepted Article
Title: Olefination of N-Sulfinylimines under Mild Conditions
Authors: Shubhendu Dhara and Charles Diesendruck
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10.1002/ejoc.201601577
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Olefination of N-Sulfinylimines under Mild Conditions
Shubhendu Dhara [a] and Charles E. Diesendruck*[a]
is massive.[17] In contrast, the reaction of imines with
phosphonium ylides, while addressed, still requires further
investigation and optimization. Bestmann et al. first addressed
this reaction in 1963, but extremely high temperatures (in which
imines are probably not stable) were required to induce any
reactivity between imines and phosphonium ylides. Recently,
Tian et al. reported the stereoselective olefination of N-sulfonyl
imines with stabilised and unstabilised phosphonium ylides
under mild conditions.[18] His results inspired us to further
advance this reaction using the more useful, but less reactive,
N-sulfinyl imines with Wittig-Horner-Emmons reagents. To the
best for our knowledge, N-sulfinyl imines have not been tested
as ractants in the Wittig reaction and the stereoselectivity of this
reaction needs to be understood (Scheme 1), as the N-sulfinyl
imines can be converted to olefins after their use as directing
groups and/or chiral auxiliaries in different chemical reactions.
Abstract: A very simple and efficient diastereoselective synthesis of
1,2-disubstituted alkenes has been achieved under mild conditions.
The sulfoxide stabilised N-sulfinylimine reacted with in situ
generated phosphonate carbanion to give 1, 2-disubtituted alkenes
in good to excellent yields. Different aryl phosphonate reacted with a
range of electronically diverse N-sulfinylimine to afford in almost
greater than 99:1 E-selective alkenes. The most important feature of
this protocol is that the reaction can be performed at room
temperature using inexpensive sodium hydride as the most effective
base to generate the reactive phosphonate carbanion producing up
to 85 % isolated E-selective alkenes.
Introduction
Olefins are the ubiquitous building blocks in many naturally
occurring bioactive molecules and important reactive
intermediates in numerous organic transformations.[1]
A
Previous work:
mammoth of organic reactions including nucleophilic additions to
carbonyls (such as Wittig reaction,[2] Peterson olefination,[3] and
Julia olefination),[4] additions to alkynes,[5] alkenylations,[6]
eliminations,[7] alkyne reductions,[8] olefin metatheses[9] among
others[10] have been effectively devised for the stereoselective
synthesis of olefins. Importantly, new approaches for the
synthesis of olefins are still being investigated, as transformation
of different functional groups into olefins may be key in the total
synthesis of natural compounds, drugs etc.
Current work:
Electrophilic imines have been attracting much interest recently
owing to their simple preparation and usefulness as directing
group as well as inherent reactivity towards addition reactions in
organic chemistry.[11] Particularly, N-protected imines including
N-sulfinyl,[12] N-phosphonyl,[13] N-phosphoryl,[14] and N-
phosphinyl[15] have been used as chiral auxiliaries in nucleophilic
addition reactions. Given the importance of these electrophilic
imines in stereoselective synthesis as chiral auxiliaries,[16] it is
surprising that their reactions with phosphorous ylides have not
been studied, as their transformation into new useful functional
groups after exercising their role as directing group and/or chiral
auxiliary.
Scheme 1: Reaction of imines and phosphonium reagents
Results and Discussion
Initially, we tested the reaction between N-sulfinylimines with
Wittig reagents, but to our surprise, while good yields were
obtained under mild conditions, a ca. 1:1 mixture of E/Z isomers
(Scheme 2) was obtained. To improve selectivity, we decided to
test Wittig-Horner-Emmons stabilized carbanions, as these react
slower and provide enough time to direct the reaction to
thermodynamic product.[19] Indeed, when arylphosphonates
were reacted with N-sulfinylimines, E olefins were obtained
almost exclusively. These initial results first of all demonstrate
the high reactivity of N-sulfinylimine compared to regular imines,
as no heating is required. In addition, the high
diastereoselectivity shows the usefulness of this reaction in
converting these important directing groups and chiral
auxiliaries into olefins, which can be further functionalized in a
multi-step synthesis.
The Wittig reaction with stabilized and semi-stabilised
phosphoniumylides has been studied to a great extent and its
use in the synthesis of olefins (with or without stereoselectivity)
[a]
S. Dhara, C. E. Diesendruck
Schulich Faculty of Chemistry
Technion-Israel Institute of Technology
Haifa 3200003, Israel
E-mail: charles@tx.technion.ac.il
dharashubhendu@gmail.com
Supporting information for this article is given via a link at the end of
the document.((Please delete this text if not appropriate))
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10.1002/ejoc.201601577
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7
8
Naphthyl
4-pyridyl-
Butyl
5g
5h
5i
49
55
51
47
Wittig Reaction:
9
10
heptyl
5j
Wittig-Horner-Emmons:
[a] Reaction conditions: Sulfinamide 3 (1 mmol), aldehyde 4a-j (1.1 mmol),
anhy. CuSO4 (2 mmol), DCM (5 mL), rt, 12h-24h. [b] Isolated yield.
We started our study by optimizing reaction conditions. For that
goal, we chose N-benzylidenebutane-1-sulfinamide (5a) and
diethyl benzylphosphonate as the simplest model substrates.
We tested a range of bases that are typically used for the
preparation of carbanion (table 2). N-butyllithium and LDA in
THF at -78 ˚C induced the reaction, albeit in a non-selective
manner and leaving unconsumed sulfinylimine (which could be
reused later). DBU provided no product at all. Changing the
base to sodium hydride in 1,2-dimethoxyethane (DME) allowed
for complete conversion and higher yield, as well as
stereoselectivity of over 99% towards the E-alkene. The solvent
imparts great influence on yield and stereochemistry of the
reaction. In addition, sodium hydride presents the key advantage
of carrying out the reaction at room temperature. The reaction
required some excess of the base (2 equiv.) for complete
consumption of the starting N-sulfinylimine. In addition, a small
excess (1.2 mmol) of phosphonate was also used for complete
conversion.
Scheme
2:
Reaction
of
N-sufinylimines
with
semistabilized
triphenylphosphonium ylides and arylphosphonate carbanions
There are many approaches to the synthesis of N-sulfinylimines.
For this research, we decided to prepare butane-1-sulfinamide 3
and directly condense it with different aldehydes. Importanly, 3
may be prepared and attached as a single enantiomer[13] serving
as a chiral auxiliary; however, we decided to initially use the
racemic mixture, as to test the diastereoselectivity without the
advantage of the chiral auxiliary. Following a reported procedure
(Scheme 3),[20] we reacted 1-bromobutane and potassium
ethanethioate
ethanethioate
1
in refluxing THF, producing S-butyl
quantitatively. Amidation of S-butyl
2
ethanethioate to the corresponding S-butyl sulfinamide 3 was
accomplished in two steps in one pot: first, oxidation of
ethanethioate using acetic anhydride and sulfuryl chloride in 1,2-
dichloroethane (DCE) at -10 ˚C and subsequently, converted to
3 by treatment with ice cold aqueous ammonium solution. For
the preparation of N-sulfinylimines, various aldehydes (4a-j)
were employed. The imines (5a-j) are formed with the help of
the Lewis acidic dehydrated copper sulphate in refluxing DCM
(table 1).
The solvent influences the stereochemistry and yield of the
product in the reaction. Dimethoxyethane (DME) proved to
provide superior reaction yield and geometric control, leading to
complete conversion of the starting material and excellent
selectivity. Sodium hydride in DME at room temperature
overnight proved to be the optimal set of conditions for the
reaction of our model substrates giving 85 % isolated alkene.
Table 2. Optimization of reaction conditions[a]
Entry
Base
Solvent
Yield (%) [b]
E:Z ratio [c]
1[d]
2[e]
3
n-BuLi
LDA
NaH
DBU
DBU
NaH
NaH
NaH
THF
THF
THF
THF
DME
DME
ACN
DCE
40
53
50:50
56:44
90:4
--
Scheme 3: Synthesis of butylsufinylimines
Table 1. Synthesis of butylsufinylimines[a]
80
4
NR
NR
85
Entry
R
Product
Yields (%) [c]
5
--
1
2
3
4
5
6
Ph
5a
5b
5c
5d
5e
5f
64
65
76
57
50
48
6
>99:1
--
4-Cl-C6H4
7
trace
9
4-NO2-C6H4
3-OMe-C6H4
4-Me-C6H4
4-OMe-C6H4
8
--
[a] Reaction conditions: Sulfinylimine (1 mmol), phosphonate (1.2 mmol),
NaH (2 equiv.), solvent (2 mL), room temp., 12h.. [b] Isolated yields. [c] E:Z
ratio analysed form NMR spectrum. [d,e] -78 ˚C to rt, THF, 4h.
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With our ideal conditions found, (NaH in DME at room
temperature) we decided to test the scope of this reaction by
changing the electronic conditions in both reagents. First, we
looked at electronic effects in the N-sulfinylimines, maintaining
the same simple benzylphosphonate as a reactant (table 3). As
described above, phenylsulfinylimine provides exclusively E-
stilbene in 85 % isolated yield. The presence of substituents in
the phenyl ring of sulfinylimine does not affect the
diastereoselectivity of the obtained alkene but it affects reaction
yields. A methoxy substituent at the meta-position of the imine
reduced the isolated yield slightly to 75%. A 4-nitro group (table
3, entry 4) enhanced the reactivity of the imine to give trans-
alkene in excellent yield. The 4-chloro substituted aryl
sulfinylimine produced 1-chloro-4-styrylbenzene in 74 % yield
with greater than 99% E-geometry. On the other hand, electron-
donating effects, such as in the case of a methoxy in the para
position (table 3, entry 6) decreases the electrophilicity of the
imine, significantly reducing the yield of the reaction (30 %
isolated alkene). However, in the case of a methyl group at the
4-position the effect is reduced, and a good yield is obtained
(table 3, entry 5). Heteroaryl (e.g.; pyridyl) substituted
sulfinylimine also successfully reacted with phosphonate to
afford 60 % (E)-4-styrylpyridine as only steroisomeric product.
Our reaction also tolerated the bulky naphthylsulfinylimine giving
only (E)-1-styrylnaphthalene in excellent yield. Alkyl substituted
sulfinylimines react, albeit in poor yields to substituted styrenes
(table 3, entries 7, 8).
Next we tested the impact of an electron-donating substituents
in the phosphonate reactant. For this purpose, we prepared
diethyl 4-methoxybenzylphosphonate 6b from reacting 1-
(chloromethyl)-4-methoxybenzene with triehtylphosphite.[21]
A
broad range of electron rich and poor sulfinylimines were
reacted with 6b to provide the corresponding alkenes.
Importantly, the electron-donating group reduced the product
yields compared to phenylphosphonate 6a, as 4-OMe group in
6b decreases the basicity of the α-hydrogen to the phosphonate,
leading to an overall conversion of the starting material to the
carbanion, as evident by the NMR of the crude reaction mixture.
An additional methoxy substituent at 4 position in the imine
makes the imine even less reactive in the reaction, providing
only traces of the alkene, while methyl substitution afforded
moderate yield (table 4, entries 5, 6). Heteroaryl (e.g.; pyridyl)
substituted sulfinylimines were completely unreactive under
these reaction conditions, whereas electron withdrawing nitro
substituent enhanced the reaction yield to 74%. A bulky napthyl
group in the sulfinylimine is well tolerated in the reaction and
gave reasonable yield in excellent selectivity. Alkyl sulfinylimines
were almost unreactive in the reaction, providing trace amounts
of the substituted styrenes (table 4, entries 8, 9).
Table 4. Reaction of N-sulfinylimine with Electron Donating Wittig-Horner
reagent [a]
Table 3. Survey of stereoelectronic effects on the reaction of N-sulfinylimine
with Wittig-Horner reagent [a]
Entry
Ar
Product
Yield (%) [b]
E:Z ratio [c]
1
2
Ph
8a
8b
8c
8d
8e
8f
68
67
>99:1
4-Cl-C6H4
4-NO2-C6H4
3-OMe-C6H4
4-Me-C6H4
4-OMe-C6H4
Naphthyl
Butyl
>99:1
3
74
86:14
Entry
R
Product
Yield (%) [b]
E:Z ratio [c]
4
50
>99:1
1
2
Ph
7a
7b
7c
7d
7e
7f
85
74
>99:1
>99:1
97:3
5
49
>99:1
4-Cl-C6H4
4-NO2-C6H4
3-OMe-C6H4
4-Me-C6H4
4-OMe-C6H4
4-pyridyl-
Naphthyl
Butyl
6
trace
70
-
3
88
7
8g
8h
8i
>99:1
4
76
>99:1
>99:1
>99:1
>99:1
>99:1
-
8
trace
trace
0
-
-
-
5
84
9
Heptyl
6
30
10
4-pyridyl-
8j
7
7g
7h
7i
60
[a] Reaction conditions: Sulfinylimine (1 mmol), phosphonate (1.2 mmol),
NaH (2 equiv.), solvent (2 mL), rt, 12h. [b] Isolated yield. [c] E:Z ratio from
NMR.
8
85
9
trace
29
The effect of electron deficiency in Wittig-Horner reactants was
also tested. 6c containing an electron withdrawing nitro group at
the 4 position was prepared and used as a model compound. As
expected, the EWG group in 6c increased the reactivity and
therefore the isolated yields, while diastereoselectivity is
completely maintained, i.e., E alkenes were obtained exclusively.
The results in table 5 show good to excellent isolated yields
10
heptyl
7j
>99:1
[a] Reaction conditions: Sulfinylimine (1 mmol), benzyl phosphonate (1.2
mmol), NaH (2 equiv.), DME (2 mL), room temp., 12h. [b] Isolated yields. [c]
Stereoselective E:Z ratio was analyzed by NMR.
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10.1002/ejoc.201601577
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consistently with aromatic sulfinylimnes (table 5, entries 1-5).
Surprisingly, 4-nitro substituted sulfinylimine (table 4, entry 3)
was almost unreactive in this reaction, providing only traces of
the desired alkene. Electron donating substituents in the imine
still resulted in good amounts of the alkene (table 5, entries 5, 6).
Again, bulky naphthylsulfinylimine presented no significant
Conclusions
In summary, we have tested and optimized the Wittig-Horner-
Emmons reaction reaction of N-sulfoxide stabilised imines,
accomplishing the diastereoselective conversion of an important
chiral auxiliary into useful 1,2-disubstituted alkenes which can be
used to further functionalize the molecule. A broad range of
easily accessible aromatic and aliphatic N-sulfinylimines react
with electronically diverse arylphosphonates to give 1,2-
disubtituted alkenes in moderate to good yield and almost
complete E-selectivity. In contrast, alkylphosphonate was
problem, providing 9e in 84
Alkylsulfinylimines were again less reactive, but provided
moderate yields of 4-nitrostyrenes with excellent
diastereoselectivity (table 5, entries 7, 8).
% and 97:3 E/Z selectivity.
Table 5. Reaction of N-sulfinylimine with Electron Withdrawing Wittig-Horner
unsuccessful
in
these
reactions,
providing
N-
reagent [a]
sulfonamidophosphonates. Stereoselective addition of the
phosphonate to the N-sulfinylimine governs the geometric
outcome of the alkene, favouring E-selective alkenes.
Entry
R
Product
Yield (%) [b]
E:Z ratio [c]
1
2
3
4
5
6
7
8
9
Ph
9a
9b
9c
9d
9e
9f
73
81
>99:1
>99:1
-
4-Cl-C6H4
4-NO2-C6H4
3-OMe-C6H4
4-Me-C6H4
4-OMe-C6H4
Naphthyl
Butyl
trace
79
>99:1
>99:1
>99:1
93:7
66
75
9g
9h
9i
84
Scheme 4: Proposed Mechanism of the Olefination reaction
52
>99:1
>99:1
heptyl
39
Experimental Section
[a] Reaction conditions: Sulfinylimine (1 mmol), phosphonate (1.2 mmol),
NaH (2 equiv.), solvent (2 mL), room temp., 12h. [b] Isolated yield. [c] E:Z
ratio from NMR.
General Remarks All materials, unless otherwise stated, were
purchased from commercial sources and utilized without further
purification. Flash column chromatography was conducted with
silica gel 60 (230-400 mesh) from Merck. All 1H and 13C NMR
spectra were recorded using an AVANCE II 300 MHz and 400
MHz Bruker spectrometer at the Technion NMR facilities.
Chemical shifts (δ) are reported in ppm, relative to residual
CHCl3 as an internal reference (1H, 7.26 ppm; 13C, 77.16 ppm).
Coupling constants (J) are reported in hertz (Hz). Peak
multiplicity is indicated as follows: s (singlet), d (doublet), t
(triplet), q (quartet), and m (multiplet). High-resolution mass
Based on the results observed and the vast knowledge on the
Wittig-Horner reaction, we propose a similar mechanism for the
olefination of N-sulfinylimines.[15] After deprotonation, the
phosphonate carbanion adds in a reversible way to the imine,
with fast conversion between syn (A2) and anti (A1) intermediate.
Given the steric hindrance in A2, A1 exists in higher
concentrations. Ring closing to azaphosphatidin B then occurs
at the rate-determining step, followed by the irreversible ring
opening
(butylthio)oxyphosphoramidate
to
the
desired
alkenes
D
and
(Scheme
diethyl
4).
spectrometry was done in
Spectrometer, Waters ACQUITY UPLC System: ESI+, MeCN:
H2O (70:30) 0.25 mL/min.
a Waters LCT Premier Mass
Alkylphosphonates (e.g; diethyl butylphosphonate) provide low
conversions to the the desired styrene. The reason for that is
that A is more basic and the reaction is directed towards N-
sulfinamidophosphonate C by proton abstraction. Formation of C
is clearly seen by NMR analysis of crude reaction mixture.
General Procedure
Preparation of Sulfinamide:[22] In a 100 mL round bottom flask
1-bromobutane (2.534 g, 18.5 mmol) and potassium thioacetate
(4.05 g, 35.4 mmol) were refluxed in THF (50 mL) overnight.
Solvent was removed under reduced pressure and the
remaining dissolved in ethylacetate. The organic phase was
washed with saturated NaHCO3 solution (50 mL), and then the
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10.1002/ejoc.201601577
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aqueous phase was extracted with ethylacetate (3 x 50 mL). The
combined organic phase was evaporated to provide the pure
thioacetate 1 (2.44 g, quantitative) as a brown liquid. Compound
1 (2.44 g, 18 mmol) was dissolved in DCE (10 mL). Then, Ac2O
(1.92 mL, 20. 2 mmol) and SO2Cl2 (3.1 mL, 42.4 mmol) were
added at -10 ˚C and stirred for 30 min. The mixture was then
allowed to return to rt and the solvent was evaporated to a
brown oil. The oil was dissolved in CH2Cl2 and poured into ice
cold aqueous NH4OH solution (8 mL). The organic phase was
separated and the aqueous layer further extracted with CH2Cl2
(3 x 50 mL). The combined organic phase was evaporated to
provide pure sulfinamide 2 as an orange yellow liquid, 1.65 g,
72% yield. S-butyl ethanethioate (1): 1H NMR (300 MHz,
CDCl3) δ 2.75 (dd, J = 8.7, 5.7 Hz, 2H), 2.20 (d, J = 4.5 Hz, 3H),
1.42 (dd, J = 14.7, 7.5 Hz, 2H), 1.27 (dd, J = 14.2, 7.1 Hz, 2H),
0.79 (dd, J = 8.9, 5.4 Hz, 3H). 13C NMR (75 MHz, CDCl3) δ
195.5, 31.4, 30.3, 28.6, 21.7, 13.4; Butane-1-sulfinamide (2):
1H NMR (300 MHz, CDCl3) δ 3.03 – 2.78 (m, 1H), 2.41 (dd, J =
27.5, 14.7 Hz, 1H), 1.69 (dd, J = 30.9, 23.4 Hz, 2H), 1.51 – 1.21
(m, 2H), 0.92 (t, J = 7.2 Hz, 3H). 13C NMR (75 MHz, CDCl3) δ
56.3, 25.0, 21.5, 13.5.
(E)-N-(3-methoxybenzylidene)butane-1-sulfinamide
(5d):
1
Yellow liquid; 57% yield; H NMR (300 MHz, CDCl3) δ 8.50 (s,
1H), 7.38 – 7.25 (m, 3H), 7.06 – 6.92 (m, 1H), 3.77 (s, 3H), 2.89
(ddd, J = 13.1, 9.7, 6.1 Hz, 1H), 2.64 (ddd, J = 13.1, 9.6, 5.4 Hz,
1H), 1.71 (dd, J = 10.6, 4.3 Hz, 1H), 1.66 – 1.54 (m, 1H), 1.49 –
1.33 (m, 2H), 0.88 (t, J = 7.3 Hz, 3H). 13C NMR (75 MHz, CDCl3)
δ 161.6, 159.8, 135.0, 129.8, 122.5, 118.9, 112.7, 55.2, 55.1,
22.95, 21.8, 13.6; HRMS (ESI) m/z 240.1061, (calcd.
C12H18NO2S+, 240.1053).
(E)-N-(4-methylbenzylidene)butane-1-sulfinamide
(5e):
1
Yellow liquid; Yield 50%; H NMR (300 MHz, CDCl3) δ 8.55 (s,
1H), 7.72 (d, J = 8.1 Hz, 2H), 7.26 (d, J = 7.9 Hz, 2H), 2.94 (ddd,
J = 13.1, 9.7, 6.1 Hz, 1H), 2.69 (ddd, J = 13.1, 9.7, 5.4 Hz, 1H),
2.40 (s, 3H), 1.78 (tdd, J = 15.5, 9.5, 6.2 Hz, 1H), 1.69 – 1.59 (m,
1H), 1.47 (ddd, J = 10.4, 7.9, 2.9 Hz, 2H), 0.93 (t, J = 7.3 Hz,
3H). HRMS (ESI) m/z 240.1091; (calcd. C12H18NOS+, 224.1104).
(E)-N-(4-methoxybenzylidene)butane-1-sulfinamide
(5f):
1
Yellow liquid; Yield 48%; H NMR (300 MHz, CDCl3) δ 8.51 (s,
1H), 7.81 – 7.71 (m, 2H), 7.00 – 6.93 (m, 2H), 3.85 (s, 3H), 2.92
(ddd, J = 13.1, 9.7, 6.1 Hz, 1H), 2.67 (ddd, J = 13.1, 9.6, 5.5 Hz,
1H), 1.85 – 1.69 (m, 1H), 1.69 – 1.61 (m, 1H), 1.46 (ddd, J = 8.5,
7.1, 4.2 Hz, 2H), 0.93 (t, J = 7.3 Hz, 3H). 13C NMR (75 MHz,
CDCl3) δ 163.0, 160.8, 131.2 (2C), 127.0, 114.6, 114.2 (2C),
55.4, 23.0, 21.8, 13.6; HRMS (ESI) m/z 240.1091; (calcd.
C12H18NO2S+, 240.1053).
Preparation of N-Sulfinylimines 5:[23] In a 50 mL round bottom
flask, butylsulfinamide 2 (121 mg, 1 mmol) and aldehyde (1.2
mmol) were dissolved in CH2Cl2 (5 mL). Then, anhydrous
CuSO4 (351 mg, 2.2 mmol) was added and the mixture refluxed
for 12 h. The reaction mixture was then filtered and the solids
washed with CH2Cl2. The organic layer was dries over
anhydrous MgSO4. The solvent was evaporated and crude
product purified by column chromatography over silica gel.
(E)-N-(naphthalen-1-ylmethylene)butane-1-sulfinamide (5g):
1
Yellow liquid; 49% yield; H NMR (300 MHz, CDCl3): δ 9.17 (s,
1H), 8.98 (d, J = 8.3 Hz, 1H), 8.00 (dd, J = 12.5, 5.0 Hz, 2H),
7.88 (d, J = 7.9 Hz, 1H), 7.66 – 7.48 (m, 3H), 3.02 (ddd, J = 13.1,
9.8, 6.1 Hz, 1H), 2.89 – 2.69 (m, 1H), 1.85 – 1.68 (m, 2H), 1.52
– 1.38 (m, 2H), 0.99 – 0.89 (m, 3H). 13C NMR (75 MHz, CDCl3) δ
161.4, 133.8, 133.3, 131.7, 131.1, 129.1, 128.8, 127.9, 126.4,
125.1, 124.2, 55.5, 23.1, 21.9, 13.7; HRMS (ESI) m/z 260.1111,
(calcd. C15H18NOS+, 260.1104).
(E)-N-benzylidenebutane-1-sulfinamide (5a): Yellow liquid;
64% yield, 1H NMR (300 MHz, CDCl3) δ 8.58 (s, 1H), 7.85 – 7.75
(m, 2H), 7.55 – 7.38 (m, 3H), 2.94 (ddd, J = 13.1, 9.7, 6.1 Hz,
1H), 2.74 – 2.60 (m, 1H), 1.83 – 1.69 (m,1H), 1.69 – 1.59 (m,
1H), 1.44 (dtd, J = 15.4, 7.2, 3.2 Hz, 2H), 0.93 (d, J = 7.3 Hz,
3H); 13C NMR (75 MHz, CDCl3) δ 161.8, 133.8, 132.4, 129.3
(2C), 128.9 (2C), 55.2, 23.0, 21.8, 13.6; HRMS (ESI) m/z
210.0952, (calcd. C11H16NOS+, 210.0947).
(E)-N-(pyridin-4-ylmethylene)butane-1-sulfinamide
(5h):
Yellow liquid; 55% yield; 1H NMR (300 MHz, CDCl3) δ 8.73 (d, J
= 4.6 Hz, 2H), 8.55 (s, 1H), 7.74 – 7.56 (m, 2H), 2.94 (ddd, J =
13.1, 9.6, 6.1 Hz, 1H), 2.69 (ddd, J = 13.1, 9.7, 5.4 Hz, 1H), 1.85
– 1.67 (m, 1H), 1.67 – 1.53 (m, 1H), 1.53 – 1.34 (m, 2H), 0.89 (t,
J = 7.3 Hz, 3H). 13C NMR (75 MHz, CDCl3) δ 160.3, 150.7 (2C),
139.9, 122.4 (2C), 55.0, 23.0, 21.4, 13.6; HRMS (ESI) m/z
211.0901, (calcd. C10H15N2OS+, 211.0900).
(E)-N-(4-chlorobenzylidene)butane-1-sulfinamide
(5b):
1
Yellow liquid; 65% yield; H NMR (300 MHz, CDCl3): δ 8.54 (s,
1H), 7.79 – 7.69 (m, 2H), 7.42 (d, J = 8.5 Hz, 2H), 2.93 (ddd, J =
13.1, 9.6, 6.1 Hz, 1H), 2.68 (ddd, J = 13.1, 9.6, 5.4 Hz, 1H), 1.75
(ddd, J = 9.3, 6.9, 4.0 Hz, 1H), 1.70 – 1.60 (m, 1H), 1.48 – 1.39
(m, 2H), 0.94 – 0.87 (m, 3H). 13C NMR (75 MHz, CDCl3) δ 160.5,
138.6, 132.2, 130.4 (2C), 129.2(2C), 55.2, 23.0, 21.8, 13.6;
HRMS (ESI) m/z 244.0543, (calcd. C11H15ClNOS+, 244.0557).
(E)-N-butylidenebutane-1-sulfinamide (5i): Yellow liquid; 51%
yield; 1H NMR (200 MHz, CDCl3) d 8.08 (t, J = 4.8 Hz, 1H), 2.92
– 2.79 (m, 1H), 2.58 (dd, J = 6.6, 2.9 Hz, 1H), 2.47 (dt, J = 7.5,
3.6 Hz, 2H), 1.76 – 1.56 (m, 4H), 1.45 (dd, J = 7.1, 2.2 Hz, 2H),
0.96 (q, J = 7.3 Hz, 6H). 13C NMR (50 MHz, CDCl3) δ 168.5,
55.1, 37.9, 23.0, 21.9, 18.9, 13.7 (2C); HRMS (ESI) m/z
176.1004, (calcd. C8H18NOS+, 176.1104).
(E)-N-(4-nitrobenzylidene)butane-1-sulfinamide (5c): Light
1
Yellow Solid, 76% yield; H NMR (300 MHz, CDCl3): δ 8.66 (s,
1H), 8.30 (d, J = 8.8 Hz, 2H), 7.99 (d, J = 8.8 Hz, 2H), 2.98 (ddd,
J = 13.1, 9.7, 6.1 Hz, 1H), 2.73 (ddd, J = 13.1, 9.7, 5.4 Hz, 1H),
1.87 – 1.71 (m, 1H), 1.71 – 1.54 (m, 1H), 1.54 – 1.35 (m, 2H),
0.93 (t, J = 7.3 Hz, 3H). 13C NMR (75 MHz, CDCl3) δ 159.7,
149.7, 138.6, 130.0 (2C), 124.1 (2C), 55.1, 23.1, 21.8, 13.6;
HRMS (ESI) m/z 255.0803, (calcd. C11H15N2O3S+, 255.0798).
(E)-N-heptylidenebutane-1-sulfinamide (5j): Yellow liquid;
47% yield; 1H NMR (300 MHz, CDCl3) δ 7.98 (t, J = 4.8 Hz, 1H),
2.76 (ddd, J = 13.2, 9.6, 6.1 Hz, 1H), 2.53 – 2.46 (m, 1H), 2.44 –
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10.1002/ejoc.201601577
European Journal of Organic Chemistry
FULL PAPER
2.36 (m, 3H), 1.58 – 1.47 (m, 4H), 1.42 – 1.31 (m, 3H), 1.24 –
1.18 (m, 5H), 0.84 – 0.74 (m, 5H). 13C NMR (75 MHz, CDCl3) δ
168.4, 54.9, 35.8, 31.3, 28.6, 25.2, 22.8, 22.3, 21.7, 13.8, 13.5;
HRMS (ESI) m/z 218.1677, (calcd. C11H24NOS+, 218.1573).
(E)-1-styrylnaphthalene (7h): Yellow oil; Yield 85%; 1H NMR
(300 MHz, CDCl3) δ 8.22 (d, J = 8.9 Hz, 1H), 7.93 – 7.84 (m,
2H), 7.80 (d, J = 8.2 Hz, 1H), 7.75 (d, J = 7.2 Hz, 1H), 7.64 –
7.58 (m, 2H), 7.58 – 7.45 (m, 3H), 7.41 (dd, J = 10.1, 4.7 Hz,
2H), 7.28 (ddd, J = 11.4, 8.4, 1.6 Hz, 1H), 7.15 (d, J = 16.0 Hz,
1H). All the spectral data in accordance with literature report.[31]
General procedure for Olefination reaction with N-
Sulfinylimine: In a 25 mL round bottom flask NaH (20 mg of
NaH in 60% in oil, 2 mmol) was weighted and washed with
hexane. Then, arylphosphonate (1.2 mmol) was added
dissolved in dry DME (2 mL) and stirred for 30 min
(effervescence is observed). To this mixture, sulfinylimine (1
mmol) in DME (1 mL) was added and the reaction stirred at rt for
12 h. The reaction was then quenched with water and extracted
with CH2Cl2 (3 x 50 mL). The combined organic layer was dried
over anhydrous MgSO4 and filtered. The solvent was evaporated
under reduced pressure to get the product as a crude oil.
Purification was done by column chromatography over silica gel.
(E)-1-methoxy-4-styrylbenzene (8a): Yellow solid; Yield 68%;
1H NMR (300 MHz, CDCl3) δ 7.50 – 7.40 (m, 3H), 7.32 (t, J = 7.5
Hz, 1H), 7.22 (d, J = 8.8 Hz, 3H), 7.09 – 6.94 (m, 2H), 6.89 (dd,
J = 9.5, 7.4 Hz, 2H), 3.81 (s, 3H). All the spectral data in
accordance with literature report.[26]
(E)-1-chloro-4-(4-methoxystyryl)benzene (8b): Yellow liquid;
1
Yield 67%; H NMR (400 MHz, CDCl3) δ 7.35 (dd, J = 13.1, 8.6
Hz, 3H), 7.26 – 7.16 (m, 3H), 6.96 (d, J = 16.3 Hz, 1H), 6.88 –
6.78 (m, 3H), 3.76 (s, 3H). The 1H NMR spectrum, see below,
was compared with the previously reported spectrum.[32]
(E)-1,2-diphenylethene (7a): White solid; Yield 85%; 1H NMR
(300 MHz, CDCl3) δ 7.52 (d, J = 7.4 Hz, 4H), 7.36 (t, J = 7.4 Hz,
4H), 7.25 (dd, J = 9.7, 4.8 Hz, 2H), 7.11 (s, 2H); 13C NMR (75
(E)-1-methoxy-4-(4-nitrostyryl)benzene (8c): Yellow solid;
Yield 74%; 1H NMR (300 MHz, CDCl3) δ 8.18 (d, J = 8.9 Hz,
MHz, CDCl3) δ 137.2 (C), 128.6 (CH), 127.53 (CH), 126.41 (CH). 2H), 7.58 (d, J = 8.9 Hz, 2H), 7.48 (d, J = 8.8 Hz, 2H), 7.21 (d, J
All the spectral data in accordance with literature report.[24]
= 17.3 Hz, 1H), 6.99 (d, J = 16.3 Hz, 1H), 6.93 – 6.86 (m, 2H),
3.83 (s, 3H). All the spectral data in accordance with literature
report.[33] Z-isomer: 1H NMR (300 MHz, CDCl3) δ 8.06 (d, J =
8.8 Hz, 2H), 7.38 (d, J = 8.7 Hz, 2H), 7.12 (d, J = 8.6 Hz, 2H),
6.79 – 6.68 (m, 2H), 6.49 (d, J = 12.1 Hz, 2H), 3.77 (s, 2H).
(E)-1-chloro-4-styrylbenzene (7b): White solid; Yield 74%; 1H
NMR (300 MHz, CDCl3) δ 7.52 – 7.24 (m, 9H), 7.05 (s, 2H); 13C
NMR (75 MHz, CDCl3) δ 136.8, 135.7, 133.1, 129.2, 128.7,
128.6, 127.7, 127.6; 127.3, 126.4; All the spectral data in
accordance with literature report.[25]
(E)-1-methoxy-3-(4-methoxystyryl)benzene (8d): White solid;
Yield 50%; 1H NMR (300 MHz, CDCl3) δ 7.43 (d, J = 8.7 Hz,
2H), 7.24 (t, J = 7.9 Hz, 1H), 7.12 – 7.05 (m, 1H), 7.01 (s, 2H),
6.95 (s, 1H), 6.88 (d, J = 8.8 Hz, 2H), 6.78 (dd, J = 8.1, 2.5 Hz,
1H), 3.83 (s, 3H), 3.81 (s, 3H). All the spectral data in
accordance with literature report.[34]
(E)-1-nitro-4-styrylbenzene (7c): Yellow solid; Yield 88%; 1H
NMR (300 MHz, CDCl3) δ 8.21 (dd, J = 6.5, 4.7 Hz, 2H), 7.65 –
7.59 (m, 2H), 7.56 – 7.51 (m, 2H), 7.40 – 7.28 (m, 3H), 7.23 (d, J
= 2.8 Hz, 1H), 7.12 (d, J = 16.4 Hz, 1H). All the spectral data in
accordance with literature report.[26]
(E)-1-methoxy-4-(4-methylstyryl)benzene (8e): White solid;
Yield 49%; H NMR (300 MHz, CDCl3) δ 7.40 (dd, J = 16.0, 8.4
1
1
(E)-1-methoxy-3-styrylbenzene (7d): Yellow oil; Yield 76%; H
NMR (200 MHz, CDCl3) δ 7.54 (dd, J = 6.9, 1.3 Hz, 2H), 7.43 –
7.23 (m, 4H), 7.18 – 7.04 (m, 4H), 6.89 – 6.78 (m, 1H), 3.87 (s,
3H). All the spectral data in accordance with literature report. [27]
Hz, 4H), 7.14 (d, J = 7.9 Hz, 2H), 6.97 (d, J = 8.6 Hz, 4H), 6.88
(d, J = 8.8 Hz, 2H), 3.81 (s, 3H), 2.34 (s, 3H). All the spectral
data in accordance with literature report.[34]
(E)-1-methyl-4-styrylbenzene (7e): White solid; yield 84%; 1H
NMR (300 MHz, CDCl3) δ 7.51 (dd, J = 5.2, 3.3 Hz, 2H), 7.42 (d,
J = 8.1 Hz, 2H), 7.39 – 7.32 (m, 2H), 7.25 (dd, J = 7.5, 1.5 Hz,
1H), 7.17 (d, J = 7.9 Hz, 2H), 7.08 (d, J = 1.3 Hz, 2H), 2.36 (s,
3H). All the spectral data in accordance with literature report. [28]
(E)-1-(4-methoxystyryl)naphthalene (8g): Yellow liquid; Yield
70%; H NMR (300 MHz, CDCl3) δ 8.29 – 8.18 (m, 1H), 7.92 –
7.83 (m, 1H), 7.79 (d, J = 5.0 Hz, 1H), 7.75 – 7.69 (m, 2H), 7.59
– 7.44 (m, 5H), 7.11 (d, J = 16.0 Hz, 1H), 7.00 – 6.91 (m, 2H),
3.84 (s, 3H). All the spectral data in accordance with literature
report.[35]
1
(E)-1-methoxy-4-styrylbenzene (7f): White solid; Yield 30%; 1H
NMR (300 MHz, CDCl3) δ 7.51 – 7.38 (m, 4H), 7.33 (t, J = 7.5
Hz, 2H), 7.27 – 7.15 (m, 1H), 7.11 – 6.96 (m, 2H), 6.96 – 6.85
(m, 2H), 3.82 (s, 3H). All the spectral data in accordance with
literature report.[29]
(E)-1-nitro-4-styrylbenzene (9a): Yellow liquid; Yield 73%; 1H
NMR (300 MHz, CDCl3) δ 8.20 (d, J = 8.8 Hz, 2H), 7.62 (d, J =
8.8 Hz, 2H), 7.56 – 7.51 (m, 2H), 7.45 – 7.28 (m, 3H), 7.23 (d, J
= 2.5 Hz, 1H), 7.12 (d, J = 16.3 Hz, 1H). All the spectral data in
accordance with literature report.[26]
(E)-4-styrylpyridine (7g): Colourless oil; Yield 60%; 1H NMR
(300 MHz, CDCl3) δ 8.56 (s, 2H), 7.52 (dd, J = 8.3, 1.2 Hz, 2H),
7.36 – 7.23 (m, 6H), 7.00 (d, J = 16.3 Hz, 1H). All the spectral
data in accordance with literature report.[30]
(E)-1-chloro-4-(4-nitrostyryl)benzene (9b): Yellow Solid; Yield
81%; 1H NMR (300 MHz, CDCl3) δ 8.20 (d, J = 8.9 Hz, 2H), 7.60
(d, J = 8.8 Hz, 2H), 7.46 (d, J = 8.5 Hz, 2H), 7.34 (d, J = 8.6 Hz,
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10.1002/ejoc.201601577
European Journal of Organic Chemistry
FULL PAPER
2H), 7.27 – 7.13 (m, 1H), 7.09 (d, J = 16.4 Hz, 1H). All the
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(E)-1-methoxy-3-(4-nitrostyryl)benzene (9d): Yellow liquid;
Yield 79%; 1H NMR (300 MHz, CDCl3) δ 8.19 (d, J = 8.8 Hz,
2H), 7.60 (d, J = 8.8 Hz, 2H), 7.28 (dd, J = 15.9, 7.9 Hz, 1H),
7.19 (s, 1H), 7.12 (t, J = 3.7 Hz, 2H), 7.06 (dd, J = 4.9, 2.7 Hz,
1H), 6.94 – 6.81 (m, 1H), 3.84 (s, 3H). All the spectral data in
accordance with literature report.[37]
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(E)-1-methyl-4-(4-nitrostyryl)benzene (9e): Yellow solid; Yield
66%; 1H NMR (300 MHz, CDCl3) δ 8.19 (d, J = 8.8 Hz, 2H), 7.60
(d, J = 8.8 Hz, 2H), 7.43 (d, J = 8.1 Hz, 2H), 7.25 (d, J = 5.5 Hz,
1H), 7.19 (d, J = 8.4 Hz, 2H), 7.07 (d, J = 16.3 Hz, 1H), 2.36 (s,
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(E)-1-methoxy-4-(4-nitrostyryl)benzene (9f): Yellow solid;
Yield 75%; 1H NMR (300 MHz, CDCl3) δ 8.18 (d, J = 8.9 Hz,
2H), 7.57 (d, J = 8.8 Hz, 2H), 7.48 (d, J = 8.7 Hz, 2H), 7.28 –
7.14 (m, 1H), 6.98 (d, J = 16.3 Hz, 1H), 6.94 – 6.86 (m, 2H),
3.83 (s, 3H). All the spectral data in accordance with literature
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(E)-1-(4-nitrostyryl)naphthalene (9g): Yellow Solid; Yield 84%;
1H NMR (300 MHz, CDCl3) δ 8.24 (d, J = 8.8 Hz, 2H), 8.18 (d, J
= 7.9 Hz, 1H), 8.04 (d, J = 16.0 Hz, 1H), 7.87 (dd, J = 9.9, 8.1
Hz, 2H), 7.77 (d, J = 7.2 Hz, 2H), 7.69 (d, J = 8.8 Hz, 2H), 7.60 –
7.45 (m, 2H), 7.18 (d, J = 16.0 Hz, 1H); 13C NMR (75 MHz,
CDCl3) δ143.9, 133.7, 133.6, 131.2, 130.3, 129.5,129.2, 129.1,
128.7, 126.9 (2C), 126.4, 126.0, 125.5, 124.1 (2C), 124.0, 123.3.
All the spectral data in accordance with literature report.[39]
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(E)-1-nitro-4-(pent-1-en-1-yl)benzene (9h): Yellow Solid; Yield
52%; 1H NMR (300 MHz, CDCl3) δ 8.11 (d, J = 8.8 Hz, 2H), 7.42
(d, J = 8.8 Hz, 2H), 6.41 (t, J = 3.7 Hz, 2H), 2.21 (tdd, J = 7.5,
3.8, 1.4 Hz, 2H), 1.61 – 1.41 (m, 2H), 0.94 (t, J = 7.4 Hz, 3H). All
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(E)-1-nitro-4-(oct-1-en-1-yl)benzene (9i): Yellow Solid; Yield
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(d, J = 8.9 Hz, 2H), 6.41 (s, 2H), 2.33 – 2.12 (m, 2H), 1.45 (dd, J
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Acknowledgements
This work was supported by the Technion Start-up Grant. S.D. is
grateful to the Schulich Foundation for
fellowship. C.E.D. is grateful to the American Technion Society
for a Women’s Division Career Advancement Chair.
a post-doctoral
Keywords: diastereoselective • sulfinylimine • aryphosphonate •
olefination • Wittig-Horner-Emonns
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European Journal of Organic Chemistry
FULL PAPER
[16] a) G. Bernardinelli, S. Gillet, E. P. Kündig, R. Liu, A. Ripa, L.
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10.1002/ejoc.201601577
European Journal of Organic Chemistry
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Diastereoselective Olefination
Shubhendu Dhara[a] and Charles E.
Diesendruck *[a]
Page No. – Page No.
Olefination of N-Sulfinylimines under
Mild Conditions
Imines are highly useful directing groups, and coupled with a chiral auxiliary such
as sulfoxide group, a powerful tool in total synthesis. Here we show that these
groups can be converted in a very efficient diastereoselective route to 1,2-
disubstituted alkenes (>99:1 E isomer) under very mild conditions.
This article is protected by copyright. All rights reserved.