"Instant methylide" modification of the Corey-Chaykovsky epoxide synthesis

Article abstract of DOI:10.1081/SCC-120021041

We report that Me₃S(O)⁺I^- (1) and Me₃S⁺I^- (2) form stable, dry mixtures with KOt-Bu and NaH, respectively, which remain stable upon prolonged storage (> 1 year). The corresponding methylides (Me₂SO=CH₂ and Me₂S=CH₂) are generated upon addition of DMSO or DMSO/THF solutions of carbonyl compounds, cleanly affording epoxides via the Corey-Chaykovsky reaction in good yields and short reaction times (as short as 20 min when 1-2 mmol of various ketones and aldehydes were treated with a mixture of 1 and KOt-Bu at 50-60°C).

Full text of DOI:10.1081/SCC-120021041

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“Instant Methylide” Modification of the
Corey–Chaykovsky Epoxide Synthesis
James A. Ciaccio a , Antoinette L. Drahus a , Regina M. Meis a , Carice T. Tingle a , Michael
Smrtka a & Richard Geneste a
a Department of Chemistry, Fordham University, Bronx, New York, USA
Version of record first published: 17 Aug 2006.
To cite this article: James A. Ciaccio , Antoinette L. Drahus , Regina M. Meis , Carice T. Tingle , Michael Smrtka & Richard
Geneste (2003): “Instant Methylide” Modification of the Corey–Chaykovsky Epoxide Synthesis, Synthetic Communications: An
International Journal for Rapid Communication of Synthetic Organic Chemistry, 33:12, 2135-2143
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SYNTHETIC COMMUNICATIONSÕ
Vol. 33, No. 12, pp. 2135–2143, 2003
‘‘Instant Methylide’’ Modification of the
Corey–Chaykovsky Epoxide Synthesis
#
James A. Ciaccio, Antoinette L. Drahus, Regina M. Meis,
Carice T. Tingle,Michael Smrtka,and Richard Geneste
*
Department of Chemistry, Fordham University, Bronx,
New York, USA
ABSTRACT
We report that Me3S(O)þIÀ (1) and Me3SþIÀ (2) formstable, dry
mixtures with KOt-Bu and NaH, respectively, which remain stable
upon prolonged storage (>1 year). The corresponding methylides
(Me2SO¼CH2 and Me2S¼CH2) are generated upon addition of
DMSO or DMSO/THF solutions of carbonyl compounds, cleanly
affording epoxides via the Corey–Chaykovsky reaction in good yields
and short reaction times (as short as 20 min when 1–2 mmol of
various ketones and aldehydes were treated with a mixture of 1
and KOt-Bu at 50–60ꢀC).
*Correspondence: James A. Ciaccio, Department of Chemistry, Fordham
University, Bronx, NY 10458, USA; E-mail: ciaccio@fordham.edu.
#FordhamUniversity Clare Boothe Luce Scholar.
2135
DOI: 10.1081/SCC-120021041
Copyright & 2003 by Marcel Dekker, Inc.
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2136
Ciaccio et al.
Key Words: Epoxide synthesis; Corey–Chaykovsky reaction; Sul-
furylide.
The Corey–Chaykovsky reaction is the standard method for prepar-
ing monosubstituted and 2,2-disubstituted epoxides from aldehydes and
ketones, respectively. In the original report,[1] the methylene transfer
agents, dimethylsulfoxonium methylide (DMSY)[2] and dimethylsulfo-
niummethylide, were formed by treating Me 3S(O)þIÀ (1) and Me3SþIÀ
(2) with NaH in anhyd. DMSO or DMSO/THF. Subsequent condensa-
tions with aldehydes and ketones were performed at 50ꢀC for 1–2 h using
DMSY and at 0–25ꢀC for 0.5–1 h using dimethylsulfonium methylide,
affording the corresponding epoxides in 56–97% yields.
Modifications of the reaction have been reported in which methylides
were obtained by deprotonation of either sulfonium[3] or sulfoxonium[4]
salts in nonaqueous media using various bases (including KOt-Bu),[4]
by phase-transfer catalysis in heterogeneous alkaline media,[5] using
basic microcrystalline solids in slightly hydrated solid–liquid media,[6]
using solvent free conditions,[7] and by fluorodesilylation of dialkyl[(tri-
methylsilyl)methyl]sulfonium salts in nonbasic media.[8] A method
for generation of Me3SþHSO4À and reaction in situ with ketones and
benzaldehyde has also been described.[9] Much recent attention
has focused on asymmetric variations of the reaction using chiral sulfur
benzylides that are formed under a variety of conditions.[10]
Reminiscent of Schlosser–Schaub alkyltriphenylphosphonium salt-
base mixtures (‘‘instant ylides’’ for Wittig olefination of carbonyl com-
pounds),[11] we have found that 1 and 2 formstable, dry mixtures with
KOt-Bu and NaH, respectively, which remain stable upon prolonged
storage (>1 year). The corresponding methylides are generated upon
addition of DMSO or DMSO/THF solutions of carbonyl compounds
to the salt-base mixture, affording the corresponding epoxides in yields
of 55–98% after stirring either at roomtemperature or below (when using
equimolar mixtures of 1 and KOt-Bu, or 2 and NaH), or briefly heating
to 50–60ꢀC (when using an equimolar mixture of 1 and KOt-Bu) (Sch. 1).
As shown in Table 1, condensation of a number of enolizable and
nonenolizable ketones (3a–g) and an aldehyde (4a) with DMSY occurred
at room temperature in DMSO upon treatment with two molar
equivalents of an equimolar mixture of 1 and KOt-Bu. The correspond-
ing epoxides (5a–h) were cleanly afforded in yields of 73–92% and
reactions were complete within 2 h when performed on 1–2 mmol of car-
bonyl compound; similar yields were obtained by stirring the reaction
mixtures overnight. By heating the mixtures to 50–60ꢀC, epoxides were

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Corey-Chaykovsky Epoxide
2137
Scheme 1.
Table 1. Reaction conditions for epoxide synthesis using ‘‘instant methylide’’
salt-base mixtures.
Me3SOI/KOt-Bu Me3SOI/KOt-Bu Me3SI/NaH
roomtemp
yield (%)
(time, h)
50–60ꢀC
yield (%)
(time, h)
0–25ꢀC
yield (%)
(time, h)
Carbonyl
substrate
Prod.
no.a
3a
3b
3c
5a
5b
5c
86 (0.50)
80 (16)
87 (0.67)
89 (0.33)
92 (0.33)
81 (2.0)
98 (16)
86 (0.67)
87 (16)
84 (1.5)
89 (16)
86 (0.40)
82 (16)
96 (4.9)
3d
3e
3f
5d
5e
5f
87 (0.5)
90 (16)
80 (0.33)
84 (0.33)
81 (0.33)
72 (6.0)
79 (16)
70 (2.0)b
55 (16)
82 (0.42)
92 (16)
80 (0.50)
3g
5g
73 (1.0)
80 (0.75)
73 (1.0)c
4a C11H23 À CHO
4b
5h
5i
78 (1.2)
—
94 (0.25)
—
76 (16)
80 (6.0)
aYields are for isolated products using 1–2 mmol carbonyl substrate as starting
material.
bObtained as a 1:1.4 mixture of diastereomers, as determined by 1H NMR
integration.
cUsing 6.4 mmol of 3g.

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2138
Ciaccio et al.
obtained in yields of 73–94% and most reaction times were shortened to
20 min.
Condensations with dimethylsulfonium methylide were carried out
at ice bath temperature by adding DMSO/THF solutions of carbonyl
compounds to an equimolar mixture of 2 and NaH, followed by slow
warming to room temperature. Reactions were complete within 6 h, or
could be stirred at roomtemperature overnight, and cleanly afforded
epoxides in yields of 55–98%; although yields of epoxides fromseveral
enolizable substrates (3d–g, 4a) were slightly lower than those obtained
when using 1 and KOt-Bu.
This ‘‘instant methylide’’ modification of the Corey–Chaykovsky
reaction offers a quick, convenient, and experimentally simple prepara-
tion of monosubstituted and 2,2-disubstituted epoxides, with advan-
tages over conventional procedures: ease of handling (the mixture of
sulfoxoniumor sulfoniumsalt and base can be stored indefinitely
under anhydrous conditions without significant loss of activity);
methylides are generated in the presence of the carbonyl substrate;
and reaction times are relatively short (as short as 20 min when treat-
ing 1–2 mmol of carbonyl substrate with a mixture of 1 and KOt-Bu at
50–60ꢀC).
Cyclopropanation of conjugated carbonyl compounds and in
situ reactions of epoxides prepared by this method are currently being
examined.
EXPERIMENTAL
Reactions were performed under a dry nitrogen atmosphere using
glassware that was oven-dried at 120ꢀC. All solvents, reagents, and
carbonyl substrates are commercially available. Tetrahydrofuran
(THF) was freshly distilled under nitrogen fromdark blue or purple
solutions of sodiumand benzophenone; all other solvents and reagents
were used without purification. Analytical TLC was performed using
Hard Layer Silica Gel GHLF UNIPLATES with inorganic binder
(Analtech, Inc.) and Riedel-deHaen TLC plates, silica gel (60 F
254), 0.2 mm thickness on aluminum (available from Aldrich Chem.
Co.). Plates were visualized by UV, I2, and/or 10% phosphomolybdic
acid in absolute ethanol. 1H spectra were recorded at 300 MHz and
13C spectra were recorded at 75 MHz on a Bruker AvanceTM DPX300
spectrometer with the use of CDCl3 as solvent. Chemical shifts were
measured relative to internal TMS. After an aqueous work-up, epox-
ides were afforded in good yield (avg. yield in Table 1 is 83%) from

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Corey-Chaykovsky Epoxide
2139
either ketones or aldehydes (including enolizable substrates), and the
crude products generally were obtained pure enough to be used directly
for further reactions, as determined by TLC, 13C and 1H NMR
analyses. Epoxides 5a–i (Table 1) have been reported previously, and
our NMR data are in agreement with the published data.
Preparation of the Sulfoxonium/Sulfonium Salt and
Base Mixtures
Appropriate amounts (see below) of the powdered salt and base were
thoroughly mixed, placed in glass, screw cap bottles, and then stored in
desiccators with no significant loss in activity for samples stored >1 year:
Me3SI (4.29 g; 21.0 mmol) þ NaH (dry; 0.500 g; 20.8 mmol)
¼ 4.3 mmol methylide/g
Me3SOI (5.90 g; 26.8 mmol) þ KOt-Bu (3.00 g; 26.7 mmol)
¼ 3.0 mmol methylide/g
General Procedure Using an Equimolar Mixture of
Me3SOI (1) and KOt-Bu
An anhyd. DMSO (8 mL) solution of the carbonyl compound
(1–2 mmol) was added all at once to a dry mixture (1.5 to 2 molar equiva-
lents) of 1 and KOt-Bu in a small round-bottomed flask at room
temperature. The resulting clear solution was stirred for either
20–45 min while the flask was immersed in an oil bath heated to
50–60ꢀC, or overnight at roomtemperature (or until TLC analysis
revealed the absence of carbonyl compound). The mixture was then
treated with water (50 mL) and extracted with diethyl ether (3 ꢁ 20 mL).
The combined organic extracts were washed either with water or brine
(3 ꢁ 50 mL), dried over anhyd. MgSO4, filtered, and evaporated in vacuo
to afford the corresponding epoxide.
General Procedure Using an Equimolar Mixture of
Me3SI (2) and NaH
A solution of the carbonyl compound (1–2 mmol) in anhyd. DMSO
(6 mL) and THF (1–3 mL) was added in small portions over 5–10 min to

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2140
Ciaccio et al.
a mixture (3 molar equivalents) of 2 and NaH in anhyd. THF (1–2 mL)
that was stirring in a small round-bottomed flask immersed in an ice
water bath. The mixture was slowly warmed to room temperature and
the resulting clear solution was stirred either overnight or until TLC
analysis revealed the absence of carbonyl compound. The mixture was
then treated with water (50 mL) and extracted with diethyl ether
(3 ꢁ 20 mL). The combined organic extracts were washed either with
water or brine (3 ꢁ 50 mL), dried over anhyd. MgSO4, filtered, and
evaporated in vacuo to afford the corresponding epoxide.
2,2-Diphenyloxirane (5a)[1c]: M.p. 54–55ꢀC (lit. 55–56ꢀC). 1H NMR ꢀ
7.20 (m, 10H), 3.10 (s, 2H). 13C NMR ꢀ 140.03, 128.71, 128.39, 127.92,
62.26, 57.29.
1
2-Methyl-2-phenyloxirane (5b)[12]: H NMR ꢀ 7.35 (m, 5H), 2.95 (d,
1H, J ¼ 5 Hz), 2.78 (d, 1H, J ¼ 5 Hz), 1.71 (s, 3H). 13C NMR ꢀ 141.60,
128.73, 121.85, 125.71, 57.40, 57.14, 22.21.
1
2-Methyl-2-(4-methylphenyl)oxirane (5c)[13]: H NMR ꢀ 7.20 (d, 2H),
7.10 (d, 2H), 2.90 (d 1H), 2.80 (d, 1H), 2.30 (s, 3H), 1.65 (s, 3H).
13C NMR ꢀ 138.57, 137.54, 129.42, 125.64, 57.47, 57.09, 22.28, 21.48.
1
2-Hexyl-2-methyloxirane (5d)[4a]: H NMR ꢀ 2.54 (d, 1H), 2.49 (d,
1H), 1.59–1.10 (m, 13H), 1.20 (s), 0.80 (t, 3H). 13C NMR ꢀ 57.07,
53.86, 36.64, 31.67, 29.22, 25.11, 22.46, 20.76, 13.95.
1-Oxaspiro[2.6]nonane (5e)[1c]: 1H NMR ꢀ 2.60 (s, 2H), 1.75–1.50 (m,
12H). 13C NMR ꢀ 60.58, 55.70, 35.84, 28.86, 24.54.
6-t-Butyl-1-oxaspiro[2.5]octane (5f )[1c,6a]: (Single diastereomer), pre-
1
pared using 1 and KOt-Bu. H NMR ꢀ 2.64 (s, 2H), 1.94–1.68 (m, 4H),
1.44–1.24 (m, 4H), 1.12–1.00 (m, 1H), 0.89 (s, 9H). 13C NMR ꢀ 58.37,
53.82, 47.14, 33.37, 32.48, 27.58, 24.82.
1,7,10-Trioxadispiro[2.2.4.2]dodecane (5g)[14]: 1H NMR ꢀ 4.00 (s, 4H),
2.70 (s, 2H), 2.00–1.30 (m, 8H). 13C NMR ꢀ 108.00, 64.30, 57.68, 53.88,
32.75, 30.37.
1
2-Undecyloxirane (5h)[15]: H NMR ꢀ 2.90 (m, 1H), 2.74 (dd, 1H),
2.45 (dd, 1H), 1.6–1.2 (m, 20H), 0.88 (t, 3H). 13C NMR ꢀ 52.33, 47.01,
32.43, 31.86, 29.58, 29.50, 29.40, 29.29, 25.92, 22.63, 14.03.
1
2-Styryloxirane (5i)[5b,5f,6a]: H NMR ꢀ 7.42–7.15 (m, 5H), 6.78 (d,
1H), 5.85 (dd, 1H), 3.50 (m, 1H), 3.00 (dd, 1H), 2.75 (dd, 1H). 13C NMR
ꢀ 135.93, 134.40, 128.48, 127.91, 126.81, 126.28, 52.47, 49.05.
ACKNOWLEDGMENTS
We are grateful for the generous financial support provided by: the
FordhamUniversity Clare Boothe Luce Scholars Program(support for

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Corey-Chaykovsky Epoxide
2141
ALD); Mr. Stephen Bepler and Mr. Jack Walton, Members of the
FordhamCollege at Rose Hill Board of Visitors (support for MS); the
FordhamUniversity Collegiate Science and Technology Entry Program
(CSTEP) (support for CTT and RG); Research Corporation Cottrell
College Science Award No. C-3698; and the National Science
Foundation’s Division of Undergraduate Education through grant
DUE #9650684.
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Received in the USA October 17, 2002

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