Domino Michael-seleno Pummerer type reaction (additive seleno Pummerer reaction)

Article abstract of DOI:10.1039/b004912n

Domino Michael-seleno Pummerer type reaction (additive seleno Pummerer type rearrangement) has been realised by the reaction of 1,3-dicarbonyl compounds with vinyl selenoxides in the presence of amine and chlorosilane. The Royal Society of Chemistry 2000.

Full text of DOI:10.1039/b004912n

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Domino Michael–seleno Pummerer type reaction (additive seleno
Pummerer reaction)
Hisahiro Hagiwara,*a Koji Kafuku,a Hitoshi Sakai,a Miki Kirita,b Takashi Hoshi,a
Toshio Suzukia and Masayoshi Andob
1
a Graduate School of Science and Technology and b Faculty of Engineering, Niigata University,
8050, 2-nocho, Ikarashi, Niigata 950-2181 Japan
Received (in Cambridge, UK) 20th June 2000, Accepted 30th June 2000
Published on the Web 17th July 2000
Table 1 Domino Michael–seleno Pummerer reaction
Domino Michael–seleno Pummerer type reaction (additive
seleno Pummerer type rearrangement) has been realised by
the reaction of 1,3-dicarbonyl compounds with vinyl
selenoxides in the presence of amine and chlorosilane.
Entry
Reagentsa
Product
Yield (%)
1
2b
3
4
5
6
7
8
9
(TMS)2NH–TMSCl
(TMS)2NH–TMSCl
(TMS)2NH–TBDMSCl
(TMS)2NH–DMPSCl
(TMS)2NH
(C6H11)2NH–DMPSCl
(C6H11)2NH–TESClc
(C6H11)2NH–TBDPSClc
(C6H11)2NH–(CF3CO)2O
6
6
52
70
38
39
25
27
36
43
18
Pummerer rearrangement of sulfoxide is a versatile reaction
which transfers the oxidation state of sulfoxide onto a carbon
at the α-position through acylation of sulfoxide to give
α-acyloxysulfide.1 The synthetic utility of α-acyloxysulfide has
been exemplified by the formation of aldehydes by hydrolysis2
or vinyl sulfide by elimination of carboxylic acid.3 Intermediary
thionium ions have also been utilised as initiators for cationic
cyclisation4 or asymmetric induction.5 In addition, various
additive Pummerer reactions involving domino Michael–
Pummerer type reactions6 have also been reported as useful
synthetic transformations. However, in spite of the abundance
of sulfoxide Pummerer reactions, the reaction of selenoxide has
not been common because facile elimination of the selenenic
acid residue from selenoxide occurs soon after oxidation of
selenide even at low temperature. Thus, limited and specific
examples have been reported so far,7,8 in which there were no
β-hydrogens to the selenoxide in most cases.8 To the best of
our knowledge, there is only one example of additive seleno
Pummer reaction, which involves the reaction of vinyl
selenoxide with ketene via a 3,3-sigmatropic rearrangement of
oxyselenonium enolate.9
6
6
6
7
8
9
10
a Reaction was carried out at ice bath temperature for 2–3 h. b Vinyl
selenoxide 1 was added 2 h after stirring indanedione 2, (TMS)2NH and
TMSCl. c TESCl = chlorotriethylsilane; TBDPSCl = chloro(tert-butyl)-
diphenylsilane.
We herein show our first observation of a domino Michael–
seleno Pummerer type reaction (additive seleno Pummerer type
rearrangement) by the reaction of 1,3-dicarbonyl compounds
with vinyl selenoxides in the presence of amine and chlorosilane
in the course of our investigation on reactivity of vinyl selen-
oxide as a partner for domino Michael–Michael-substitution
reaction (bicycloannulation).10
As a representative example, reaction of 2-phenylindane-1,3-
dione 2 with phenyl vinyl selenoxide 111 in the presence of
hexamethyldisilazane [(TMS)2NH] and chlorotrimethylsilane
(TMSCl) in dichloromethane provided trimethylsiloxyselenide
6 in 52% yield. Some results are shown in Table 1 and Scheme 1.
The yield was improved when a solution of the indanedione 2,
(TMS)2NH and TMSCl in dichloromethane was stirred for 2 h
prior to addition of the vinyl selenoxide 1 (Table 1, entry 2).
The reaction also proceeded without TMSCl albeit in lower
yield (Table 1, entry 5). Without amine, the starting indanedione
2 was recovered completely. (TMS)2NH gave the best result
among other amines tested (diethylamine, triethylamine, diethyl-
aminotrimethylsilane, DBU or dicyclohexylamine). TMSCl was
the best among other chlorosilanes due to higher reactivity and
diminished steric bulkiness towards O-silylation as well as
nucleophilic attack on the selenonium ion (Scheme 1). Actually,
in Table 1, entry 3 or 4, the TMS group of (TMS)2NH was
introduced selectively even in the presence of chloro(tert-
butyl)dimethylsilane (TBDMSCl) or chlorodimethylphenyl-
silane (DMPSCl) while in entry 6 in the absence of (TMS)2NH
bulkier DMPS group was introduced. These observations
indicate that the yields of the products do not depend on the
Scheme 1 Reagents: i, Chlorosilane or (CF3CO)2O; ii, MCPBA–
CH2Cl2 or PTSA–H2O–THF; iii, allyl bromide–NaH–THF; iv, O3–
CH2Cl2–Me2S.
stability of products 6–10. More reactive silylating reagent such
as trimethylsilyl iodide or trimethylsilyl trifluoromethane-
sulfonate provided complex mixtures.
DOI: 10.1039/b004912n
J. Chem. Soc., Perkin Trans. 1, 2000, 2577–2578
This journal is © The Royal Society of Chemistry 2000
2577

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proceeds via domino silyl transfer (Mukaiyama) type Michael
addition followed by seleno Pummerer type reaction as shown
in Scheme 1.
In summary, among many possible combinations of domino
process,12 the present reaction offers the first example of
domino Michael–seleno Pummerer type reaction (additive
Pummerer reaction) and a new alternative procedure to intro-
duce a formylmethyl unit to 1,3-dicarbonyl compounds.
Experimental
Phenyl vinyl selenoxide 1 was prepared according to the known
procedure.11
To a stirred solution of 2-phenylindane-1,3-dione 2 (221 mg,
0.99 mmol) in dichloromethane (2 ml) was added (TMS)2NH
(254 µl, 1.2 mmol) at 0 ЊC under a nitrogen atmosphere. After
being stirred for 10 min, TMSCl (152 µl, 1.2 mmol) was added
and the solution was stirred for a further 2 h at 0 ЊC. A solution
of phenyl vinyl selenoxide (245 mg, 1.23 mmol) in dichlo-
romethane (2 ml) was added and stirring was continued at room
temperature for 30 min. Evaporation of the solvent in vacuo
followed by medium pressure liquid chromatography (eluent:
ethyl acetate–n-hexane = 1:3) provided the domino product 6
(343 mg, 70%); needles, mp 96–98 ЊC; IR (CCl4) νmax/cmϪ1 3061,
2957, 1747, 1712, 1601, 1479, 1253, 1111; 1H-NMR (200 MHz,
CDCl3) δ (ppm) Ϫ0.30 (s, 9H), 2.77 (dd, 1H, J 14.3, 3.61 Hz),
3.34 (dd, 1H, J 14.3, 10.8 Hz), 5.49 (dd, 1H, J 10.8, 3.61 Hz),
and 7.18–8.01 (m, 14H Ph); 13C-NMR (125 MHz, CDCl3)
δ (ppm) Ϫ0.7 (q) × 3, 46.6 (t), 61.6 (s), 75.0 (d), 123.2 (d), 124.0
(d), 126.7 (d) × 2, 127.4 (d), 127.6 (d), 128.8 (d) × 2, 129.1
(d) × 2, 129.1 (s), 134.0 (d) × 2, 135.2 (d), 135.6 (d), 137.0 (s),
141.7 (s), 142.0 (s), 198.9 (s), and 200.7 (s).
Notes and references
1 R. Pummerer, Ber. Dtsch. Chem. Ges., 1910, 43, 1401.
2 H. Sugihara, R. Tanikaga and A. Kaji, Synthesis, 1978, 881.
3 H. Hagiwara, K. Nakayama and H. Uda, Bull. Chem. Soc. Jpn.,
1975, 48, 3769.
4 H. Ishibashi and M. Ikeda, Yuki Gosei Kagaku Kyokaishi, 1989, 47,
330.
Fig. 1
5 Y. Kita and T. Shibata, Yuki Gosei Kagaku Kyokaishi, 1994, 52, 746.
6 Y. Kita, O. Tamura, F. Itoh, H. Yasuda, T. Maki and Y. Tamura,
Chem. Pharm. Bull., 1987, 35, 562.
The structure of the selenide 6 was determined by spectro-
scopic and synthetic means. m-Chloroperbenzoic acid oxid-
ation or acid catalyzed hydrolysis of 6 provided aldehyde 11
which was identical with authentic 11 independently prepared
by allylation of the indanedione 2 followed by ozonolysis
(Scheme 1).
Based on the results cited above, generality of the present
reaction was further investigated and some representative
examples are compiled in Fig. 1. Not only phenyl vinyl selen-
oxide 1 but also p-chlorophenyl vinyl selenoxide or isopropenyl
phenyl selenoxide provided domino products 18–21, though
elimination of trimethylsilanol occurred in the reaction of iso-
propenyl phenyl selenoxide to afford vinyl selenides 20 and 21.
Under prolonged reaction time, the latter reaction led to the
formation of 22 or the aldehyde 11. Some of the diastereomeric
mixtures were separable by medium pressure liquid chromato-
graphy. These diastereomers were stable enough to recover
intact after reflux in dichloromethane.
7 J. A. Marshall and R. D. Royce Jr., J. Org. Chem., 1982, 47, 693;
K. Surowiec and T. Fuchigami, J. Org. Chem., 1992, 57, 5781;
T. Kataoka, Y. Ohe, A. Umeda, T. Iwamura, M. Yoshimatsu and
H. Shimizu, Chem. Pharm. Bull., 1994, 42, 811; A. M. Morella and
A. D. Ward, Aust. J. Chem., 1995, 48, 445; F. Emery and P. Vogel,
Synlett, 1995, 420; S. V. Pitre, M. V. C. Reddy, Y. D. Vankar and
K. P. Madhusudanan, Synth. Commun., 1997, 27, 267.
8 N. Miyoshi, S. Murai and N. Sonoda, Tetrahedron Lett., 1977, 18,
851; G. Galambos and V. Simonidesz, Tetrahedron Lett., 1982, 23,
4371; H. Fujihara, R. Saito, M. Yabe and N. Furukawa, Chem.
Lett., 1992, 1437; K. Uneyama, Y. Tokunaga and K. Maeda,
Tetrahedron Lett., 1993, 34, 1311; T. Kataoka, Y. Ohe, A. Umeda,
T. Iwamura, M. Yamashita and H. Shimizu, J. Chem. Soc., Chem.
Commun., 1993, 577; W. Lowe and T. Rutjes, J. Heterocyc. Chem.,
1995, 32, 43; T. Yokomatsu, Y. Shioya, H. Iwasawa and S. Shibuya,
Heterocycles, 1997, 46, 463.
9 J. P. Marino and M. W. Kim, Tetrahedron Lett., 1987, 28, 4925.
10 H. Hagiwara, H. Sakai, M. Kirita, T. Hoshi, T. Suzuki and
M. Ando, Tetrahedron, 2000, 56, 1445.
11 M. Shimizu and I. Kuwajima, J. Org. Chem., 1980, 45, 2921.
12 L. F. Tietze and U. Beifuss, Angew. Chem., Int. Ed. Engl., 1993, 32,
131.
Reaction of trimethylsilylenol ether 3 (R = TMS) of the
indanedione 2 with the vinyl selenoxide 1 provided the selenide 6
in 67% yield. This result along with the results in Table 1,
Entries 1–4 supports the theory that the present reaction
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J. Chem. Soc., Perkin Trans. 1, 2000, 2577–2578