Ring closing metathesis and metal-catalyzed cyclopropanation for the preparation of sultone derivatives

Article abstract of DOI:10.24820/ark.5550190.p010.749

Ring closing metathesis (RCM) using Grubbs catalyst 2^nd generation as a catalyst was applied to prepare series of novel unsaturated sultones with high yields. Many attempts, were applied for the cyclopropanation of the allylic sultones by Simmon-smith cyclopropanation using diethyl zinc/diiodomethane or Zn-Cu/diiodomethane but in each case the corresponding cyclic adduct was not formed. A novel palladium or preferably rhodium-catalyzed cyclopropanation of unsaturated sultones with ethyl diazoacetate was achieved by the transition metal-catalyzed transfer of a CH-CO₂Et unit. The reaction was applied by a portion-wise addition of ethyl diazoacetate over 6h to a mixture of the sultones and palladium(II) acetate or rhodium(II) acetate dimer under low temperature (0-20 ^o C). The desired products of the cyclopropanation were achieved in each case, as a single diastereomer with 33- 37% yield in the allylic sultones and 10% for vinylic sultone.

Full text of DOI:10.24820/ark.5550190.p010.749

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Arkivoc 2018, part vii, 0-0
Ring closing metathesis and metal-catalyzed cyclopropanation for the
preparation of sultone derivatives
Korany A. Ali*a,b and Peter Metzc
a Applied Organic Chemistry Department, National Research Centre, 12622 Dokki, Giza, Egypt
bCenter of Excellence and advanced material- Nanotechnology Group, National Research Centre, 12622 Dokki,
Giza, Egypt
cOrganische Chemie I, Technische Universität Dresden, Bergstrasse 66, 01069 Dresden, Germany
Email: kornykhlil@gmail.com
Received 09-12-2018
Accepted 11-15-2018
Published on line 12-30-2018
Abstract
Ring closing metathesis (RCM) using Grubbs catalyst 2nd generation as a catalyst was applied to prepare series
of novel unsaturated sultones with high yields. Many attempts, were applied for the cyclopropanation of the
allylic sultones by Simmon-smith cyclopropanation using diethyl zinc/diiodomethane or Zn-Cu/diiodomethane
but in each case the corresponding cyclic adduct was not formed. A novel palladium or preferably rhodium-
catalyzed cyclopropanation of unsaturated sultones with ethyl diazoacetate was achieved by the transition
metal-catalyzed transfer of a CH-CO2Et unit. The reaction was applied by a portion-wise addition of ethyl
diazoacetate over 6h to a mixture of the sultones and palladium(II) acetate or rhodium(II) acetate dimer under
low temperature (0-20 o C). The desired products of the cyclopropanation were achieved in each case, as a
single diastereomer with 33- 37% yield in the allylic sultones and 10% for vinylic sultone.
H
EtO2C
step 1
O
R
( )
nS
O
H
HO
R
S
O
O
Cl
O
S
R
O
O
O
n=0,1
H
step 2-RCM
EtO2C
R
S
O
O
H
O
O
S
R
O
O
Keywords: Ring closing metathesis (RCM), carbenes generation; sultones, cyclopropanation
DOI: https://doi.org/10.24820/ark.5550190.p010.749
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Introduction
Sultones are important scaffolds in organic and bioorganic chemistry with good contribution in the synthesis
of different types of heterocycles.1-6 Additionally, Sultones act as sulfoalkylating agents in organic and natural
product synthesis7,8. Additionally, several publications have reported several biological activities of the
sultones that includes antitumor and antiviral (anti-HIV) activities.9-12
On the other hand, a great deal of interest has been focused on the cyclopropanes as they have a wide
contribution in the natural products and the biologically active synthetic compounds.13-16 Furthermore, the
ring strain of the ơ-bond in the cyclopropane ring make cyclopropane derivatives highly reactive in transition
metal catalyzed reactions.
The ring closing metathesis (RCM) and organometallic catalysis using Pd, Rh and Ru compounds are very
important tools for organic chemistry and pharmaceutical applications as they used for the preparation of
active ingredients in the field of organic chemistry and pharmaceutical industry.15-22
From these observations and in continuation of our interest of the chemistry of organo-sulfur heterocycles
and sultones chemistry, 22-26 we reported herein an interesting preparation of a series of unsaturated sultones
in addition to successful attempts of metal-catalyzed cyclopropanation on the sultone scaffold.
Results and Discussion
In this study, several allylic and vinylic sultones were prepared from the appropriate sulfonate and Subsequent
RCM. The unsaturated sulfonates (3) were prepared from the reaction of the primary or secondary alkenols
(2a,b) with allyl sulfonyl chloride (1), in the presence of TEA, under low temperature. We apply our modified
procedure to obtain high yields of the sulfonates (3) via completing the addition process of the reactant under
-20 o C and left the reaction under this temperature for 4 h (Scheme 1).
RCM was achieved by portion wise addition of Grubbs catalyst 2nd generation under reflux temperature on
a solution of the unsaturated sulfonate 3a or 3b to afford the corresponding sultone (4a,b). the structures of
the sultones (4a,b) were confirmed by the elemental analysis and spectral data. The 1H-NMR spectrum of the
4b revealed doublet signal at 1.35 ppm corresponding to CH3, multiplets near 5.63, 6.01 ppm for 2 allylic CH.
Since there was only a single publication on the intermolecular cyclopropanation of vinylic27 or allylic sultones
prior to our work we decided to investigate this transformation.
Many attempts, in this study, were applied for the cyclopropanation of the sultones 4a,b by Simmons-
Smith cyclopropanation using diethyl zinc/diiodomethane or Zn-Cu/diiodomethane, but in each case the
cyclopropanation for the corresponding cyclic adduct was not obtained (Scheme 1).
The successful attempts and the first investigation for the cyclopropanation of the sultones 4a,b with ethyl
diazoacetate to give the desired products as single diastereomers were achieved by palladium(II) acetate or
rhodium(II) acetate dimer as a catalyst. The cyclopropanation reaction was achieved via transition metal-
o
catalyzed transfer of a CH-CO2Et unit under low temperature 0-20 C. with continuous and slow addition of
ethyl diazoacetate over 6 h.
The yields of the cyclopropanation adducts 6a,b were 33 and 37 % in the case of rhodium (II) acetate
dimer that was higher than the using of palladium(II) acetate with yield 15 and 17%, respectively (Scheme 1).
The structure of the bicyclic compounds 6a,b were confirmed by the elemental analysis and spectral data. The
relative configuration of 6a,b was assigned by 2D NOESY analysis.The 1H-NMR spectrum of the 6a revealed
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signals at 1.25 (CH3), 1.52-1.62 (2CH), 1.90 (CH), 2.10-2.33 (2CH), 2,33 (CH), 3.01 (CH), 3.81 (CH), 4.10 (CH2),
and 4.95 (CH) ppm.
Scheme 1
To complete the overall picture for the preparation of novel sultones we have designed the synthetic
pathway to prepare new vinyl sultones as presented in scheme 2. Firstly, the secondary allylic alcohols were
prepared from the corresponding ketone using LiAlH4. Ethenesulfonyl chloride (10) was prepared in-situ from
the treatment of chloro ethyl sulfonyl chloride (9) with TEA under low temperature. The unsaturated sulfonate
derivatives (11) were readily prepared by esterification of the secondary alcohols (8) with the in-situ
generated ethenesulfonyl chloride (10) in the presence of TEA under low temperature (-40 o C). The structures
of the formed sulfonates were confirmed by elemental analysis and spectral data.
In this study, the second new series of sultones is the vinyl sultones (12) prepared by treatment of the
freshly prepared vinyl sulfonate (11) with Grubbs(II) catalyst that added portion wise under reflux temperature
(Scheme 2). The structures of the new vinyl sultones were confirmed by elemental analysis and spectral data.
(See the experimental part).
Several attempts were applied for the cyclopropanation of the vinyl sultones 12 using sulfur yields;
trimethylsulfonium bromide (CH3)3S+Br−, in the presence of potassium tert-butoxide in DMF but in each case
lead to decomposition of the sultones due to the base; potassium tert-butoxide.
Cyclopropanation of the vinyl sultones 12b, was achieved with very low yield (10%) by treatment with ethyl
o
diazoacetate in the presence of dirhodium(II) tetra acetate as a catalyst under low temperature 0-20 C. the
cyclopropanation was not achieved by palladium(II) acetate as catalyst (Scheme 2).
The constitution of the bicyclic sultone 14 was confirmed by the elemental analysis and spectral data, while
1
the relative configuration was tentatively assigned in analogy to sultones 6. The H-NMR spectrum of the
sultone 14 revealed presence of 3 characteristic bands multiplets near 0.97, 1.15 and 1.70 ppm corresponding
to the cyclopropane protons; 6-H, 4-H, and 5-H, respectivly. Two signals that are charactarestic for the ester
group were appeared as triplet and quartet at near 1.10 and 4.22 ppm, respectivly.
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Scheme 2
Scheme 3
New vinylic sultone constructed on benzene scaffold was obtained by RCM as presented in scheme 3. The
first step was the preparation of the unsaturated sulfonate 16 that was readily obtained by esterification of
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the 2-allylphenol (15) with ethenesulfonyl chloride (10), in the presence of TEA under low temperature (0-40).
The unsaturated sulfonate derivative (16) was formed with 78% yield and its structure was confirmed by
elemental analysis and spectral data. The vinyl sultone (17) was prepared with 90% yield by treatment the
sulfonate 16 with Grubbs catalyst 2nd generation under reflux temperature in DCM (Scheme 3).
The 1H-NMR spectrum of the sultone (17) revealed bands at 3.72 (m), 6.35 (m) and 6.48 (m) ppm
corresponding to CH2 and 2CH, respectivly. The aromatic protons apperd at 7.21-7.45 ppm.
The structure of the sultone (17) was fully confirmed by the X-ray single crystal analysis (Figure 1).
C3
C5
C4
C6
C2
C1
C7
C9
O3
C8
S1
O1
O2
Figure 1: X-ray crystal structure of compound 17
We have tried to apply the cyclopropanation reaction on the later sultone by different treatments with
ethyl diazoacetate in the presence of Pd(OAc)2 or Rh2(OAc)4 but in each case there was no reaction.
Conclusions
In this study, a novel palladium- or preferably rhodium-catalyzed cyclopropanation of unsaturated sultones
with ethyl diazoacetate to give the desired products as a single diastereomer have been achieved. These
densely functionalized heterocycles are surely highly interesting intermediates for the preparation of
pharmaceutically active compounds. The unsaturated sultones required for these investigations were readily
available by esterification of unsaturated alcohols with sulfonyl chlorides and subsequent ruthenium-catalyzed
ring-closing metathesis. With a range of novel sultones synthesized in this fashion, we first investigated
different conditions for cyclopropanation using the Simmons-Smith methodology and also sulfur ylide
chemistry to transfer an un-substituted methylene unit to the alkene moiety of the substrates. Whereas these
reactions did not work with the unsaturated sultones at hand, the transition metal-catalyzed transfer of a CH-
CO2Et unit finally succeeded as detailed above. Probably, the cyclopropanation of the vinylic sultones was
more difficult than the allylic sultones due to the high electron deficiency of the alkenes of the vinylic sultone.
But in case of the allylic sultones where the separation of the sulfonyl group and the olefin by CH2 group might
allow a [2+1] cycloaddition to give the desired cyclopropanes
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Experimental Section
General. Infrared spectra were recorded on a THERMONICOLET Avatar 360 instrument using ATR. NMR
1
1
spectra were recorded on a Bruker AC 300 P (300 MHz H, 75 MHz 13C), on a Bruker DRX 500 P (500 MHz H,
125 MHz C) or on a Bruker AC 600-P (600 MHz H, 151 MHz 13C) spectrometer. Chemical shifts () are
quoted in parts per million (ppm) downfield of tetramethylsilane, using residual proton-containing solvent as
internal standard (CDCl3 at 7.26 ppm). Abbreviations used in the description of resonances are: s (singlet), d
(doublet), t (triplet), q (quartet), br (broad). Coupling constants (J) are quoted to the nearest 0.1 Hz. Mass
spectra were recorded with an Agilent 5973N detector coupled with an Agilent 6890N GC (GC-MS, 70 eV) or
else with a Bruker Esquire-LC (direct injection as a methanolic NH4OAc solution, ESI). HRMS spectra were
recorded on a Bruker Daltonic "Impact II" (ESI-TOF). Elemental analysis was performed on a Hekatech EA 3000.
13
1
Preparation of prop-2-ene-1-sulfonyl chloride (1). Prop-2-ene-1-sulfonyl chloride (1) was prepared by our
modification on the reported method28 as in the following: To a stirred solution of allyl bromide (12.10 g,
0.1mol) in 100 mL distilled water was added Na2SO3 (15 g, 0.12mol). The reaction mixture was refluxed for 8h
then left to cool to room temperature. The reaction mixture was washed with Et2O several times and the
aqueous layer was evaporated under reduced pressure. The crude product was washed with methanol,
filtered off and left to dry to afford (10.2g, 0.07 mol, 71% yield) of sodium allysulfonate. The latter crude
product was stirred at zero temperature with 30 mL of POCl3 for 1/2 h then refluxed for 5 h and left to cool to
room temperature. 100 mL of THF was then added to the mixture then filtered off and washed several times
with dry THF. The filtrate was evaporated carefully on rotavapor and the residue was distilled under vacuum (5
mbar). Allylsulfonyl chloride was separated with boiling point range 37-43 oC as coreless oil (71%).
General procedure for the preparation of but-3-enyl prop-2-ene-1-sulfonate derivatives (3a,b). To a stirred
solution of the unsaturated alcohol (2a,b) (1.0 equiv.) and dry TEA (1.5 equiv.) in CH2Cl2 at low temperature (-
20 oC) was added ally sulfonyl chloride (1.2 equiv.) in CH2Cl2 drop by drop. The reaction mixture was left to stir
under this temperature for 4 h then left to stir for 0.5 h at room temperature. Pentane was then added and
the mixture was filtered through Celite. The filtrate was concentrated under reduced pressure and the crud
residue was purified by flash chromatography.
General procedure for the preparation of hex-5-en-2-yl ethane sulfonate derivatives (11a,b) and 2-
allylphenyl ethenesulfonate (16). A solution of the unsaturated alcohol (7a,b) (1.0 equiv.) and dry TEA (1.5
o
equiv.) in CH2Cl2 was stirred at low temperature (-40-0 C) under inert atmosphere in two necked flask. A
solution of 2-chloroethanesulfonyl chloride (1.3-1.5 equiv.) in CH2Cl2was then added drop by drop. The
reaction mixture left to stir under this temperature for 3-7 h. then diluted with pentane and filtered through
Celite. The filtrate was concentrated under reduced pressure and the crud residue was purified by flash
chromatography.
General procedure for the preparation of sultones 4a,b, 12a,b and 17. To a stirred solution of the sulfonates;
3a, 3b, 12a, 12b or 16 (1eq) in CH2Cl2, in three necked flask under argon atmosphere, was added Grubbs
catalyst 2nd generation (0.03-0.05 equiv.) in three portions. The reaction mixture was refluxed with stirring for
5-12 h. the solvent was evaporated under reduced pressure and the solid crude product was purified by
column chromatography (silica gel isohexane/ethyl acetate 9/1 or diethyl ether/pentane 1/1) to afford the
corresponding sultones 4a, 4b, 12a, 12b and 17, respectively.
General procedure for the rhodium catalyzed cyclopropanation using ethyl diazoacetate. To a stirred
solution of the sultone 4a, 4b, 12a, 12b and 17, respectively (1eq) and the appropriate catalyst; palladium
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diacetate or rhodium(II) acetate dimer )1-3 mol%) in CH2Cl2 under argon atmosphere, was added ethyl
diazoacetate (2-3 equiv.) in DCM over 6 h period using syringe pump. The solvent was evaporated under
reduced pressure and the solid crude product was purified by column chromatography (silica gel
isohexane/ethyl acetate 9/1) to afford the corresponding 3-oxa-2-thiabicyclo[5.1.0]octane 2,2-dioxide.
But-3-enyl prop-2-ene-1-sulfonate (3a). Compound 3a was prepared according the general procedure from
prop-2-ene-1-sulfonyl chloride (1) (2.1g, 15 mmol), but-3-en-1-ol (2a) (1g, 13.86 mmol) and TEA (2 mL).
Colorless oil Rf: 0.53 (Et2O/pentane; 1/1)29 ; Yield (2.44g, 90%). 1H NMR (CDCl3, 300 MHz): δH 2.32-2.48 (m, 2H,
CH2), 3.75 (d, J 7.2 Hz, 2 H, CH2), 4.33 (t, 2H, CH2), 5.05-5.15 (m, 2H, 2CH), 5.40-5.51 (m, 2H, 2CH), 5.71-5.95
(m, 2H, 2CH).
Pent-4-en-2-yl prop-2-ene-1-sulfonate (3b). Compound 3b was prepared according the general procedure
from prop-2-ene-1-sulfonyl chloride (1) (3 g, 21.4 mmol), pent-1-en-2-ol (2b) (1.5 g, 17.4 mmol) and TEA (3
mL). Colorless oil Rf: 0.65 (Et2O/pentane; 1/1); Yield (3.03 g, 92%). IR (KBr, vmax, cm-1): 3080, 2982, 2935,
1
1643,1424, 1336, 1258, 1162, 992, 904. H NMR (CDCl3, 300 MHz): δ (ppm)= 1.34 (d, J 6.2 Hz, 3 H, CH3), 2.28–
2.47 (m, 2 H, CH2), 3.73 (d, J 7.2 Hz, 2 H, CH2), 4.72–4.83 (m, 1 H, CH), 5.04–5.13 (m, 2 H, CH2), 5.33 – 5.43 (m, 2
H, CH2), 5.63 – 5.91 (m, 2 H, 2CH). 13C NMR (CDCl3, 75 MHz,) (δ ppm): 20.66 (q), 40.95 (t), 55.76 (t), 79.31 (d),
118.98 (t), 124.27 (d), 124.66 (d), 132.28 (d). GC-MS m/z(%):190 [M+] (2), 149 (73) [C5H9SO3+], 85 (16)
[C5H9O+], 69 (100) [C5H9+], 68 (37), 67 (37), 53 (11), 45 (7) [C2H5O+]. Anal. Calcd for C8H14O3S (190.26): C,
50.50; H, 7.42; S, 16.85. Found: C, 50.65; H, 7.68; S, 16.67.
6,7-Dihydro-3H-1,2-oxathiepine 2,2-dioxide (4a). Compound 4a was prepared according the general
procedure from but-3-enyl prop-2-ene-1-sulfonate (3a) (1.76 g, 10 mmol) and Grubbs catalyst 2nd generation
(0.26 g, 0.03 eq) as a colorless crystals (Et2O/Pentane:1/1); Yield (89%).28 1H NMR (CDCl3, 300 MHz): δH 2.55-
2.60 (m, 2H, CH2), 4.11-4.22 (m, 2H, CH2), 4.51-4.60 (d, 2H, CH2), 5.75-5.80 (m, 1H, CH), 6.23 (m, 1H, CH).
7-Methyl-6,7-dihydro-3H-1,2-oxathiepine 2,2-dioxide (4b). Compound 4b was prepared according the general
procedure from pent-4-en-2-yl prop-2-ene-1-sulfonate (3b) (0.95 g, 5 mmol) and Grubbs catalyst 2nd
generation (0.13 g, 0.03 eq) as a colorless crystals; yield (0.65 g, 80%); colorless crystals, Rf: 0.42
1
(Et2O/Pentane:1/1). IR (KBr, vmax, cm-1): 2981, 1453, 1349, 1326, 1154, 1038, 898, 755, 671. H NMR (300
MHz, CDCl3): δH 1.35 (d, J 6.4 Hz, 3 H, CH3), 2.25–2.37 (m, 1 H, CH), 2.57–2.71 (m, 1 H, CH), 2.73 – 3.83 (m, 1 H,
CH), 4.02 – 4.12 (m, 1 H, CH), 4.83 – 4.95 (m, 1 H, CH), 5.63 – 5.74 (m, 1 H, CH), 6.01 – 6.13 (m, 1 H, CH). 13C
NMR (75 MHz, CDCl3) (δ ppm): 21.91 (q), 35.84 (t), 50.72 (t), 82.08 (d), 119.73 (d), 133.84 (d). MS m/z(%):162
[M+] (2), 147 (3), 98 (8), 54 (100), 39 (50). Anal. Calcd for C6H10O3S (162.20):C, 44.43; H, 6.21 ; S, 19.77.
Found:C, 48.48; H, 6,24; S, 19,66.
Ethyl (1S,7S,8S)-4-oxa-3-thiabicyclo[5.1.0]octane-8-carboxylate 3,3-dioxide (6a). Compound 6a was prepared
as colorless low-melting crystals according the general procedure from 6,7-dihydro-3H-1,2-oxathiepine 2,2-
dioxide (4a) (0.148 g, 1 mmol), ethyl diazoacetate (9) (0.3 mL of ethyl diazoacetate in 5 mL DCM over 6 h) and
2 mol% of palladium diacetate (method A) (0.004 g) or Rhodium(II) acetate dimer (0.0044g, 1 mol%)(Method
B). Yield (A: 0.035 g, 15%, B: 0.077 g, 33%); colorless crystals; mp: 39-40 °C. IR (KBr, vmax, cm-1): 2996, 2981,
1
1712, 1397, 1345, 1151, 963, 891, 860, 729. H NMR (CDCl3, 500 MHz, COSY, NOSY): δH 1.25 (t, 3H, CH3), 1.52-
1.62 (m, 2H, 2CH), 1.90 (m, 1H, CH), 2.10-2.33 (m, 2H, 2CH), 2,33 (m, 1H, CH), 3.01 (m, 1H, CH), 3.81 (m, 1H,
CH), 4.10 (q, 2H, CH2), 4.95 (m, 1H, 1-H). 13C NMR (CDCl3, 125 MHz, HSQC, HMBC) δ (ppm): 14.09 (q), 15.89 (d),
23.15 (d), 23.51(d), 48.18 (t), 60.92 (t), 72.14 (t), 170.70 (s, C=O). MS m/z(%): 234 [M+] (8), 206 (13), 189 (58),
155 (20), 126 (75), 79 (81), 67 (100). Anal. Calcd for C9H14O5S (234.27): C, 46.14; H, 6.02; S, 13.69. Found: C,
46.21; H, 6.12; S, 13.60.
Ethyl (1S,5S,7S,8S)-5-methyl-4-oxa-3-thiabicyclo[5.1.0]octane-8-carboxylate 3,3-dioxide (6b). Compound 6b
was prepared as colorless low melting colorless crystals according the general procedure from 7-Methyl-6,7-
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dihydro-3H-1,2-oxathiepine 2,2-dioxide (4b) (0.162 g, 1 mmol), ethyl diazoacetate (9) (0.3 mL of ethyl
diazoacetate in 5 mL DCM over 6 h) and 2 mol% of palladium(II)acetate (method A) (0.004 g) or 1 mol% of
rhodium(II) acetate dimer (method B)(0.0044 g). Yield (A: 0.042 g, 17%, B: 0.092 g, 37%); colorless crystals;
mp: 42-43 °C. IR (KBr, vmax, cm-1): 2982, 1724, 1367, 1264, 1164, 1024, 919. 1H NMR (CDCl3, 500 MHz, COSY,
NOSY): δH 1.28 (t, 3H, CH3), 1.40 (d, 3H, CH3), 1.42-1.45 (m, 2H, 2CH), 1.75-1.90 (m, 2H, 2CH), 2,33 (m, 1H, CH),
3.01 (m, 1H, CH), 3.81 (m, 1H, CH), 4.20 (q, 2H, CH2), 4.95 (m, 1H, CH). 13C NMR (CDCl3, 125 MHz, HSQC, HMBC)
δ (ppm): 14.16 (q), 17.93 (d), 21.51 (q), 23.70 (d), 31.25 (d), , 37.38 (t) 53.14 (t), 61.16 (t), 81.84 (d), 171.08 (s,
C=O). MS m/z(%): 248 [M+] (10), 207 (33), 93 (48), 67 (100), 41 (50). Anal. Calcd for C10H16O5S (248.3): C, 48.37;
H, 6.50; S, 12.91. Found: C, 48.41; H, 6.42; S, 12.89.
Hex-5-en-2-yl ethenesulfonate (11a). Compound 11a was prepared as colorless oil according the general
procedure from hex-5-en-2-ol (8a) (1.25 g, 12.5 mmol), 2-chloroethanesulfonyl chloride (9) (2.14 g, 1.05
equiv.) and 3 mL TEA. Yield (0.148 g, 79%); Colorless oil; Rf: 0.73 (EtOAc: Isohexane, 1:4). IR (KBr, vmax, cm-1):
1
3074, 2981, 2938, 1357, 1169, 894, 724. H NMR (CDCl3, 300 MHz): δH1.48 (d, J 6.3 Hz, 3H, CH3), 1.52-1.78 (m,
2H, CH2), 2.12-2.21(m, 2H, CH2), 4.50-4.75 (m, 1H, CH), 4.48-5.15 (m, 2H, 2CH), 5.60-5.80 (m, 1H, CH), 6.0 (d, H,
13
J 7.3 Hz CH), 6.33 (d, H, J 7.3 Hz CH), 6.55 (m, 1H, CH). C NMR (CDCl3, 75 MHz) δ (ppm): 20.75, 29.19, 29.03,
35.68, 80.44, 115.57, 128.95, 133.75, 136.92. MS m/z(%):190 [M+] (5), 178 (100), 163 (25). Anal. Calcd for
C8H14O3S (190.26): C, 50.50; H, 7.42; S, 16.85. Found: C, C, 50.42; H, 7.50; S, 16.76.
Hept-6-en-3-yl ethenesulfonate (11b). Compound 11b was prepared according the general procedure from
hept-6-en-3-ol (8b) (1.14 g, 10 mmol), 2-chloroethanesulfonyl chloride (9) (2.5 g, 1.5 equiv.) and 4 mL TEA
Yield (0.137 g, 67%); Pale yellow oil; Rf: 0.58 (Et2O/Pentane: 1/1). IR (KBr, vmax, cm-1): 2968, 2938, 1357, 1162,
1
985, 755, 723. H NMR (CDCl3, 300 MHz): δH 0.89 (t, 3H, CH3), 1.60-1.81 (m, 4H, 2CH2), 2.10-2.38 (m, 2H, CH2),
4.50-4.61 (m, 1H, CH), 5.0-5.22 (m, 2H, 3CH), 5.6-5.75 (m, 2H, 2CH), 6.10 (d, J 7.8 HZ, 1H, CH),´6.31 (d, J 7.8 HZ,
H, CH), 6.51 5.0 (m, H, CH). 13C NMR (CDCl3, 75 MHz, δ ppm): 9.11(q), 27.22 (t), 29.03 (t), 34.06 (t), 85 (d),
+
115.34 (t), 128.71(t), 133.78 (d), 137.06 (d). MS m/z(%): 189 [M-CH3 ] (2), 175 (79; 149 (100);
+
+
91(90)[C2H3SO2 ]; 55 (95)[C4H7 ]. Anal. Calcd for C9H16O3S (204.28): C, 52.92; H, 7.89; S, 15.69. Found:C, 53.05;
H, 7.95; S, 15.72
7-Methyl-6,7-dihydro-5H-1,2-oxathiepine 2,2-dioxide (12a). Compound 12a was prepared according the
general procedure from hex-5-en-2-yl ethenesulfonate (11a) (0.88 g, 5 mmol), Grubbs catalyst 2nd generation
(0.13 g, 0.03 eq) as a colorless crystals; Yield (75%); Pale yellow oil. IR (KBr, vmax, cm-1): 3064, 1624, 1332, 1155,
1
1131, 890, 813, 782, 637. H NMR (CDCl3, 600 MHz): δH 1.37 (d, J 6.2 Hz, 3 H, CH3), 1.72-2.11 (m, 2H, 2CH-CH2),
2.32-2.51 (m, 2H, 2CH-CH2), 4.48 (m, 1H, CH), 6.43-6.51 (m, 2H, 2CH-vinyl). 13C NMR (CDCl3, 151 MHz): 20.89
(q), 25.12 (t), 29.95 (t), 80.70 (d), 129.44 (d), 140.57 (d). MS m/z(%):162 [M+] (6), 119 (100), 79 (9.6), 54 (82),
39 (90). Anal. Calcd for C6H10O3S (162.20): C, 44.43; H, 6.21 ; S, 19.77. Found: C, 44.48; H, 6,2; S, 19,66.
7-Ethyl-6,7-dihydro-5H-1,2-oxathiepine 2,2-dioxide (12b). Compound 12b was prepared according the
general procedure from hept-6-en-3-yl-ethenesulfonate (11b) (0.60 g, 2.94 mmol) and Grubbs catalyst 2nd
generation (0.078 g, 0.09 mmol, 0.03 equiv.) as a pale yellow oil. Yield (518 mg, 71%); Rf: 0.31 (Et2O/Pentane:
1
1/1); IR (KBr, vmax, cm-1): 2970, 2935, 1335, 1156, 891, 638. H NMR (CDCl3, 300 MHz): δH 0.91 (t, 3H, CH3),
1.50-1.62 (m, 1H, CH), 1.75-1.92 (m, 2H, 2CH), 2.10-2.20 (m, 1H, CH), 2.51-2.65 (m, 2H, 2CH), 4.52-4.61 (m, H,
CH), 6.33-6.51 (m, 2H, 2CH). 13C NMR (CDCl3, 75 MHz; δ ppm): 9.89 (q), 25.07 (t), 27.95 (t), 30.73 (t), 85.59 (d),
+
+
131.23 (d), 140.26 (d). MS m/z(%):176 [M+] (2), 147 (21) [M-C2H5 ], 119 (100), 83 (33), 54 (52) [C4H6 ]. Anal.
Calcd for C7H12O3S (176.23):C, 47.71; H, 6.86; S, 18.19. Found: C, 47.60; H, 6.57; S, 18.05.
Ethyl (1S,4S,7S,8R)-4-ethyl-3-oxa-2-thiabicyclo[5.1.0]octane-8-carboxylate 2,2-dioxide(14). Compound 14
was prepared as colorless low-melting crystals with low yield (10%) according the general procedure from 7-
ethyl-6,7-dihydro-5H-1,2-oxathiepine-2,2-dioxide (12b) (0.176 g, 1 mmol), ethyl diazoacetate (9) (0.3 mL of
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Ali, K. A. et al.
ethyl diazoacetate in 5 mL DCM over 6 h) and (0.0044 g, 1 mol%) rhodium(II) acetate dimer (method B). Yield
1
(A: 0%, B: .026 g, 10%); colorless crystals; mp: 45-47 °C. IR (KBr, vmax, cm-1): 2972, 1742, 1334, 1155, 890. H
NMR (CDCl3, 500 MHz): δH 0.97-1.10 (m, 3H, CH, CH3), 1.15-1.32 (m, 4H, 2CH2), 1.41 (t, 3H, CH3), 1.70-182 (m,
1H, CH), 2.05-2.21(m, 1H, CH), 2.51-2.62 (m, 2H, CH2), 4.20-4.29 (m, 2H, CH2), 4.22-4.32(m, 1H, CH), 4.85-4.98
(m, 1H, 1-H). 13C NMR (CDCl3, 125MHz; δ ppm): 11.22 (q), 14.17 (q), 17.8 (d), 20.90 (d), 25.12 (t), 28.2 (t), 32.59
(t), 61.05 (d), 62.1 (t), 68.20 (d), 189.70 (s). MS m/z(%):262 [M+] (2), 254 (33), 145 (48), 117 (100), 71 (50).
Anal. Calcd for C11H18O5S (262.32): C, 50.36; H, 6.92; S, 12.22. Found: C, 50.16; H, 6.78; S, 12.31.
2-Allylphenyl ethenesulfonate (16). Compound 16 was prepared according the general procedure from 2-
allylphenol (15) (1.34 g, 10 mmol), chloroethanesulfonyl chloride (9) (2.5 g, 1.5 equiv.) and 4 mL of TEA. Yield
(1.75 g, 78%); Pale yellow oil Rf: 0.55 (Et2O/Pentane: 1/1); IR (KBr, vmax, cm-1): 3069, 1486, 1368, 1179, 1149,
870, 775, 756. 1H NMR (300 MHz, CDCl3): δH 3.41-352 (m, 2H, CH2), 5.12-5.23 (m, 2H, =CH2), 5.92-6.12 (m, 1H,
CH), 6.22 (d, 1H, CH), 6.44 (d, 1H, CH), 6.75-6.90 (m, 1H, CH), 7.22-7.41 (m, 4H, 4CH-Ar). 13C NMR (75 MHz,
CDCl3; δ ppm): 34.11(CH2), 116.79 (CH2), 121.99 (CH), 127.16 (CH), 127.23 (CH), 127.52 (CH), 130.89 (CH),
131.23 (CH2), 132.58 (CH), 133.02 (CH), 135.42 (CH), 147.53 (CH). MS m/z (%): 224 [M+] (85), 133 (91), 105
(100), 77(51), 51 (20). Anal. Calcd for C11H12O3S(224.27):C, 58.91; H, 5.39; S, 14.30. Found:C, 58.82; H, 5.46; S,
14.32.
5H-Benzo[f][1,2]oxathiepine 2,2-dioxide (17). Compound 17 was prepared as colorless crystals according to
the general procedure from 2-allylphenyl ethenesulfonate (16) (0.60 g, 2.67 mmol) and Grubbs catalyst 2nd
generation (0.078 g, 0.09 mmol, 0.03 equiv. Yield (0.47 g, 90%); colorless crystals Et2O/Pentane: 1/1);. IR (KBr,
1
vmax, cm-1): 3054, 1613, 1351, 1168, 1147, 878, 767. H NMR (CDCl3, 300 MHz): δH 3.72-3.79 (m, 2H, CH2), 6.35
(m, 1H, CH), 6.48-6.52 (m, 1H, CH), 7.21-7.45 (m, 4H, 4CH-Ar). 13C NMR (CDCl3, δ ppm): 30.99, 123.51, 127.49,
127.64, 129.46, 129.70, 132.03, 137.52, 148.23. MS m/z(%):196 [M+] (26), 131 (100), 103 (26), 77 (22). Anal.
Calcd for C9H8O3S (196.22): C, 55.09; H, 4.11; S, 16.34. Found: C, 55.17; H, 3.95; S, 16.46.
Crystal data of compound 17: C9H8O3S M=196.22. a [Å]= 6.7227 (5), b [Å]= 7.2890 (5), c [Å]=9.6408 (7), 
[°]=84.431(2),  [°]=85.660(2), [°]=63.030 (2), V[Å3]=418.78 (5), T[K]= 100 (2). Figure 1 illustrates the structure
as determent. Full data can be obtained on requested from CCDC (CCDC 1867516)
Acknowledgements
The authors acknowledge the Science and Technology Development Fund (STDF), Egypt for financial support
of the research activities related to project; Project ID 25521.
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