Sulfur ylides generated from the reaction of adamantylidene and phenylcarbene with sulfur substrates

Article abstract of DOI:10.1016/S0040-4039(03)01589-2

Reaction of adamantylidene and phenylcarbene with ethylthiol, ethylene dithiol, allylethylsulfide, allylphenylsulfide, and trimethylenesulfide involves the formation of a sulfur ylide intermediate, followed by H-migration, 2,3-sigmatropic shift, or ring opening to give sulfides. The sulfur ylide formed in the reaction of phenylcarbene with trimethylenesulfide is directly observed by laser flash photolytic techniques.

Full text of DOI:10.1016/S0040-4039(03)01589-2

TETRAHEDRON
LETTERS
Pergamon
Tetrahedron Letters 44 (2003) 6519–6521
Sulfur ylides generated from the reaction of adamantylidene and
phenylcarbene with sulfur substrates
a
a,
b
Yuri N. Romashin, Michael T. H. Liu, * Brian T. Hill and Matthew S. Platz*
a
Department of Chemistry, University of Prince Edward Island, Charlottetown, PE, Canada C1A 4P3
Department of Chemistry, Ohio State University, 100 W. 18th Avenue, Columbus, OH 43210, USA
b
Received 17 April 2003; accepted 5 June 2003
Abstract—Reaction of adamantylidene and phenylcarbene with ethylthiol, ethylene dithiol, allylethylsulfide, allylphenylsulfide,
and trimethylenesulfide involves the formation of a sulfur ylide intermediate, followed by H-migration, 2,3-sigmatropic shift, or
ring opening to give sulfides. The sulfur ylide formed in the reaction of phenylcarbene with trimethylenesulfide is directly observed
by laser flash photolytic techniques.
©
2003 Elsevier Ltd. All rights reserved.
Sulfur ylides are increasingly useful intermediates in
synthetic organic chemistry. Their chemistry has been
thoroughly reviewed in a number of monographs and
mixture of two thioacetals via a sulfur ylide intermedi-
ate. Herein we report the photochemistry of 2-
2
adamantane-2,3%-[3H]-diazirine 1 and 3-phenyldiazirine
2 and the reactions of the photogenerated carbenes with
a number of sulfur containing organic compounds. In
addition, the intervention of a sulfur ylide in the reac-
tion of phenylcarbene with TMSF is demonstrated by
laser flash photolytic (LFP) techniques.
1
reviews. The generation of sulfur ylides from carbenes
and sulfur containing organic compounds is a useful
alternative to widely employed base-promoted method-
1
ology. Recently we reported the reaction of arylchloro-
carbene with trimethylenesulfide (TMSF) which gives a
Scheme 1.
Keywords: diazirine; carbene; adamantylidene; sulfur ylide; trimethylenesulfide; kinetics; laser flash photolysis.
*
Corresponding authors. Tel: +1-902-566-0565; fax: +1-902-566-0632 (M.T.H.L.); Tel: +1-614-292-0401; fax: +1-614-292-5151 (M.S.P.); e-mail: liu
upei.ca; platz.1@osu.edu, platz@chemistry.ohio-state.edu
@
0
040-4039/$ - see front matter © 2003 Elsevier Ltd. All rights reserved.
doi:10.1016/S0040-4039(03)01589-2

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Y. N. Romashin et al. / Tetrahedron Letters 44 (2003) 6519–6521
adamantylidene (Ad:) with thiols involves formation of
the sulfur ylide followed by H-migration to give sulfides
or 4 (Scheme 1).
3
Similarly, photolysis of diazirine 1 in i-octane in the
presence of ethyl- and phenylallylsulfides yielded
sulfides 5 (57% yield) and 6 (52% yield). The sulfide 6
could not be separated from allylphenylsulfide by
column chromatography, and the NMR spectrum of
the mixture was recorded. In this case, the formation of
sulfur ylide is followed by 2,3-sigmatropic shift to yield
the final product. Photolysis of diazirine 1 in the pres-
ence of TMSF leads to the formation of a sulfur ylide
followed by ring opening to yield sulfide 7 (46% yield).
Finally, irradiation of a solution of diazirine 2 and
TMSF in i-octane leads to allylbenzylsulfide 8 (10%
yield), similar to the product isolated from the reaction
Scheme 2.
2
of chlorocarbenes with TMSF (eluent hexane/ether=
9
5:5 was used). Selected physical data of sulfides 3–8
5
are provided.
LFP (308 nm, 17 ns) of phenyldiazomethane (PDM) in
1
Freon-113 produces singlet phenylcarbene ( PC) in
3
6
rapid equilibrium with the ground triplet state ( PC)
(
3
Scheme 2), which has no significant absorption above
00 nm. LFP in the presence of TMSF produces a
6,7
new transient signal with umax=340 nm (Fig. 1). The
transient is assigned to ylide 9, which has a lifetime
longer than 10 ms.
Figure 1. The transient absorption spectrum of the ylide 9
formed upon reaction of PC with TMSF.
1
3
We prepared diazirine 1 from 2-adamantanone and
Ylide 9 is formed after the laser pulse in an exponential
process (Fig. 2) which was analyzed to yield observed
rate constant kOBS. The value of kOBS is linearly depen-
dent on the concentration of TMSF. The slope of this
4
diazirine 2 from benzaldehyde. We photolyzed (350
nm) solutions of diazirine 1 (1 mmol) in the presence of
either ethylthiol or ethylene dithiol (10 mmol) in 10 mL
of i-octane at 25°C for 24 h. After the work-up, we
isolated sulfides 3 (85% yield) and 4 (65% yield) by
column chromatography on silica gel with eluent hex-
ane/ether=10:1. We suggest that the reaction of
7
−1 −1
plot (Fig. 3) is 4.2×10 M
s
which in the context of
K. Chlorophenylcarbene
Scheme 2 is equal to k
TMSF
1
( CPC) has a singlet ground state which reacts with
9
−1 −1 2
TMSF with rate constant 8.9×10 M s . Assuming
Figure 2. The formation of PhCH–TMSF ylide 9 (349 nm) following LFP of PDM in Freon-113 containing trimethylenesulfide.

Y. N. Romashin et al. / Tetrahedron Letters 44 (2003) 6519–6521
6521
Figure 3. The observed rate constant of formation of PhCH–TMSF ylide 9, as a function of TMSF concentration, monitored at
349 nm in Freon-113.
1
1
that singlet PC and CPC react with TMSF with
comparable rate constants leads to the deduction that
K=0.0048 and DG298°K=3.2 kcal/mol in favor of the
triplet state. This is consistent with previous
2. Romashin, Y. N.; Liu, M. T. H.; Bonneau, R. Tetrahedron
Lett. 2001, 42, 207–209.
3. Isaeu, S. D.; Yuchenko, A. G.; Stepanov, F. N.; Kolyada,
G. G.; Novikov, S.; Karpenko, N. F. J. Org. Chem. USSR
(Engl. Transl.) 1973, 9, 724.
6
,7
estimates.
4. Smith, R. A. G.; Knowles, J. R. J. Chem. Soc., Perkin
In summary, the photolysis of adamantylidene and
phenylcarbene in the presence of ethylthiol, ethylene
dithiol, allylethylsulfide, allylphenylsulfide, and TMSF
proceeds via the formation of a sulfur ylide as an
intermediate, followed by H-migration, 2,3-sigmatropic
shift, or ring opening to give sulfides. The existence of
the sulfur ylide in the reaction of phenylcarbene with
TMSF has also been demonstrated by laser flash pho-
tolytic techniques.
Trans. 2 1975, 686.
5. For 3: H NMR (300 MHz, CDCl ): l 1.27 (3H, t, J=7
1
3
Hz), 1.50–1.61 (2H, m), 1.71–2.01 (10H, m), 2.10–2.20
(2H, m), 2.55 (2H, t, J=7 Hz), 3.07 (1H, s). C NMR
13
(300 MHz, CDCl ): 15.496, 26.026, 27.842, 28.095, 32.401,
3
33.655, 38.157, 39.146, 53.084.
1
For 4: H NMR (300 MHz, CDCl ): l 1.37 (1H, t, J=8
3
Hz), 1.5–1.6 (2H, m), 1.7–2.0 (10H, m), 2.1–2.2 (2H, m),
2.63 (2H, t, J=7 Hz), 2.64 (2H, t, J=7 Hz), 3.035 (1H, s).
13
C NMR (300 MHz, CDCl ): 23.985, 27.804, 28.068,
3
3
0.462, 32.356, 33.671, 34.185, 38.114, 39.119, 53.582.
1
For 5: H NMR (300 MHz, CDCl ): l 1.22 (3H, t, J=7
3
Acknowledgements
Hz), 1.50–1.60 (2H, m), 1.61–1.91 (10H, m), 2.01–2.12
(
5
2H, m), 2.38 (2H, t, J=7 Hz), 2.51–2.63 (2H, m), 5.06–
.16 (2H, m), 5.97–6.13 (1H, m). C NMR (300 MHz,
13
M.T.H.L. and Y.N.R. wish to thank the NSERC of
Canada for its generous financial support. Support of
this work in Columbus, Ohio by The US National
Science Foundation is gratefully acknowledged. One of
us (B.T.H.) gratefully acknowledges support of an OSU
postdoctoral fellowship.
CDCl ): 14.488, 20.477, 27.906, 28.129, 33.291, 33.799,
3
3
4.730, 39.198, 39.830, 56.392, 116.673, 135.400.
1
For 6: H NMR (300 MHz, CDCl ): l 1.64–2.11 (12H, m),
3
2.40–2.46 (2H, m), 2.80–2.91 (2H, m), 5.08–5.22 (2H, m),
6
.23–6.41 (1H, m), 7.19–7.54 (5H, m).
1
For 7: H NMR (300 MHz, CDCl ): l 1.50–1.60 (2H, m),
3
1.70–1.98 (10H, m), 2.09–2.19 (2H, m), 3.02 (1H, s), 3.15
(
2H, d, J=7 Hz), 5.01–5.14 (2H, m), 5.72–5.89 (1H, m).
1
3
References
C NMR (300 MHz, CDCl
): 27.802, 27.807, 28.088,
3
32.595, 33.448, 34.864, 38.170, 39.061, 51.908, 116.698,
1
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