New [2,3]-sigmatropic rearrangement of allylsulfinylcarbanions

Full text of DOI:10.1023/A:1016310915283

Russian Journal of Organic Chemistry, Vol. 38, No. 3, 2002, pp. 450 451. Translated from Zhurnal Organicheskoi Khimii, Vol. 38, No. 3, 2002,
pp. 471 472.
Original Russian Text Copyright
2002 by Kirii, Yurchenko, Fokin.
SHORT
COMMUNICATIONS
New [2,3]-Sigmatropic Rearrangement
of Allylsulfinylcarbanions
A. V. Kirii, A. G. Yurchenko, and A. A. Fokin
Kievskii politekhnicheskii institut National Technical University, pr. Pobedy 37, Kiev, 03056 Ukraine
Received October 17, 2001
[2,3]-Sigmatropic rearrangements of unsaturated
sulfoxides, in particular of aryl- or tert-butyl allyl
sulfoxides [1], involve the oxygen atom and lead to
formation of allyl alcohols. The activation barriers
to such transformations are usually high [2], and the
rearrangements require severe temperature conditions
and removal of intermediate unsaturated alkanesul-
fenates from the reaction zone. Carbanionic rearrange-
ments of alkyl allyl sulfoxides have not been studied
previously.
cyclohexyl sulfoxides to give -hydroxy sulfoxides
II. Treatment of the latter with chlorotrimethylsilane
yields trimethylsilyl derivatives III whose reaction
with dimethyl sulfoxide sodium salt under severe
conditions (130 C, DMSO) involves new carbanionic
[2,3]-sigmatropic rearrangement of allyl sulfoxides
IV into sulfenates V and leads to formation of highly
substituted previously inaccessible thiols VI [3]
(Scheme 1).
[2,3]-Sigmatropic rearrangement of carbanion A
[R1 = R2 = R4 = H, R3R5 = (CH2)4] derived from
sulfoxide IVd occurs under mild conditions ( 78 C,
We have found that carbonyl compounds I react
with lithium derivatives of methyl butyl and methyl
Scheme 1.
R1 = R5 = H, R2 = Pr, R3 = R4 = Me (a); R1 = R4 = H, R2 = Pr, R3R5 = (CH2)4 (b); R1R2 = (CH2)5, R3 = R4 = Me, R5 = H (c);
R1 = R2 = R4 = H, R3R5 = (CH2)4 (d).
1070-4280/02/3803-0450$27.00 2002 MAIK Nauka/Interperiodica

NEW [2,3]-SIGMATROPIC REARRANGEMENT OF ALLYLSULFINYLCARBANIONS
451
butyllithium, THF/HMPA) and yields, after alkylation
with methyl iodide, the corresponding -unsaturated
sulfoxide VII.
(2H), 2.8 2.2 m (3H), 2.1 0.9 m (15H). 13C NMR
spectrum (CDCl3), C, ppm: 150.3, 108.6, 54.4, 50.8,
38.8, 33.5, 29.2, 28.4, 22.3, 20.1, 13.7.
Thiols VIa VIc and sulfoxide VII. -Hydroxy
sulfoxides IIa IId and their trimethylsilyl derivatives
IIIa IIId were synthesized by the procedure reported
in [1]. Compounds IIIa IIIc were brought into sub-
sequent transformations without preliminary purifica-
tion. A mixture of 24 mmol of NaH and 20 ml of
anhydrous DMF was stirred for 5 min at 130 C, and
a solution of 8 mmol of compound IIIa IIIc in 5 ml
of DMSO was added. The mixture was kept for
20 min, cooled, diluted with 50 ml water, and treated
with methylene chloride. The extract was evaporated,
and the residue was purified by column chromatog-
raphy on silica gel using pentane as eluent.
A solution of sulfoxide IVd [4] in 8 ml of THF
was cooled to 70 C, and a 1 N solution of butyl-
lithium (3 mmol) in hexane was added. The mixture
was kept for 1 h at room temperature, and 9 mmol
of methyl iodide was added. The mixture was diluted
with 5 ml of water and extracted with carbon tetra-
chloride. The extract was evaporated, and the residue
was purified by column chromatography on silica gel
using chloroform as eluent.
1-(1,1-Dimethyl-2-propenyl)cyclohexane-1-thiol
(VIc). Yield 61%. H NMR spectrum, , ppm: 5.7 m
(1H), 5.2 4.7 m (2H), 2.4 s (1H), 2.1 1.2 m (10H),
1.12 s (6H). 13C NMR spectrum, C, ppm: 144.5,
113.2, 57.0, 44.5, 33.4, 25.9, 22.4, 22.3.
1
1-Methylsulfinylmethyl-2-methylenecyclohexane
(VII) (a mixture of diastereoisomers, 62:38, GLC).
Yield 97%. 1H NMR spectrum, , ppm: 4.81 s, 4.77 s,
4.68 s, 4.64 s, 3.1 2.9 m, 2.8 2.6 m, 2.62 s, 2.60 s,
2.3 1.9 m, 1.8 1.3 m. 13C NMR spectrum, , ppm:
150.6, 149.1, 107.7, 106.3, 58.6, 39.3, 39.0, 37.8,
37.3, 35.3, 34.4, 34.3, 32.9, 28.3, 28.2, 24.5, 24.1.
1
The H and 13C NMR spectra were measured on
a Varian VXR-300 spectrometer at 300 and 75 MHz,
respectively; TMS was used as internal reference.
REFERENCES
1. Hoffman, R.W., Angew. Chem., 1979, vol. 91,
pp. 625 634.
2. Jones-Hertzog, D.K. and Jorgenson, W.L., J. Org.
Chem., 1995, vol. 60, pp. 6682 6683.
3,3-Dimethyl-1-heptene-4-thiol (VIa). Yield 58%.
1H NMR spectrum, , ppm: 5.8 m (1H), 5.0 m (2H),
2.6 m (1H), 2.4 s (1H), 1.8 1.6 m (2H), 1.25 s (6H),
1.2 0.8 m (5H). 13C NMR spectrum, C, ppm: 146.3,
113.2, 67.2, 53.6, 35.3, 24.4, 21.5, 13.7.
3. Kushko, A.O., Yurchenko, A.G., Kirii, A.B., Likho-
tvorik, I.P., and Fokin, A.A., Russ. J. Org. Chem.,
1998, vol. 34, no. 5, pp. 733 734.
4. Trofimov, B.A., Mikhaleva, A.I., Petrova, O.V., and
Sigalov, M.V., Zh. Org. Khim., 1988, vol. 24, no. 10,
pp. 2095 2101.
1-(2-Methylenecyclohexyl)butane-1-thiol (VIb).
1
Yield 65%. H NMR spectrum, , ppm: 4.8 4.5 m
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 38 No. 3 2002