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1724 J . Org. Chem. 1998, 63, 1724-1726
A New Syn th esis of Selen ol Ester s via
Ca r bop h ilic Ad d ition of Or ga n ocop p er
Rea gen ts to Ca r bon yl Selen id e
Shin-ichi Fujiwara,* Akira Asai,† Tsutomu Shin-ike,
Nobuaki Kambe,† and Noboru Sonoda*,†,‡
It is reported, for example, that PhLi attacks only at
the selenium atom of 1,1,3,3-tetramethylindane-2-selone18a
and 2,6-xylyl isoselenocyanate21 even though the corre-
sponding thio analogues predominantly or exclusively
give carbophilic products. This is also the case for SeCO,
i.e., the simple carbophilic addition of organometallic
reagents (RM) to SeCO expressed by eq 1 hardly proceeds
when organolithiums or Grignard reagents are used.
Indeed, the reaction of SeCO with an equimolar
amount of PhLi at -78 °C resulted in selenophilic attack
with concomitant elimination of CO giving rise to PhSeBn
Department of Chemistry, Osaka Dental University,
Hirakata, Osaka 573-1121, J apan, and Department of
Applied Chemistry, Faculty of Engineering, Osaka
University, Suita, Osaka 565-0871, J apan
Received September 15, 1997
Carbonyl sulfide (SCO) reacts with Grignard reagents
exclusively at the carbonyl carbon1 and has been used
for introduction of a thiocarboxyl unit into organic
molecules.2,3 Although carbonyl selenide (SeCO)4 has
potential synthetic utility as the most straightforward
selenocarboxylation reagent, practical use of SeCO has
been limited only to the synthesis of ureas and carbam-
ates by the reaction with amines and amino alcohols,
respectively.5 This is mostly because, in contrast to the
thiocarbonyl compounds,6-16 selenocarbonyl compounds
are prone to undergo selenophilic addition when treated
with organolithiums or Grignard reagents.17-23 Here we
report the selenocarboxylation with SeCO via carbophilic
addition of organocopper reagents (eq 1).
(10) (a) Beak, P.; Yamamoto, J .; Upton, C. J . J . Org. Chem. 1975,
40, 305. (b) Walter, W.; Lu¨ke, H.-W. Angew. Chem., Int. Ed. Engl. 1977,
16, 535. (c) Karakasa, T.; Hanzawa, T.; Motoki, S. Bull. Chem. Soc.
J pn. 1979, 52, 3469. (d) Tominaga, Y.; Kohra, S.; Hosomi, A. Tetra-
hedron Lett. 1987, 28, 1529.
(11) (a) Walter, W.; Bode, K.-D. Angew. Chem., Int. Ed. Engl. 1966,
5, 447. (b) Entenmann, G. Chem. -Ztg. 1977, 101, 508. (c) Gosselin, P.;
Masson, S.; Thuillier, A. Tetrahedron Lett. 1978, 2715. (d) Ito, Y.;
Kobayashi, K.; Saegusa, T. Tetrahedron Lett. 1979, 1039. (e) Krapcho,
A. P.; Stephens, W. P. J . Org. Chem. 1980, 45, 1106. (f) Kelly, T. R.;
Echavarren, A.; Chandrakumar, N. S.; Ko¨ksal, Y. Tetrahedron Lett.
1984, 25, 2127. (g) Seyferth, D.; Hui, R. C. Tetrahedron Lett. 1984,
25, 5251. (h) Ares, J . J . Synth. Commun. 1991, 21, 625.
(12) (a) J ensen, K. A.; Henriksen, L. Acta Chem. Scand. 1968, 22,
1107. (b) Meijer, J .; Ruitenberg, K.; Westmijze, H.; Vermeer, P.
Synthesis 1981, 551. (c) Seyferth, D.; Hui, R. C. Tetrahedron Lett. 1984,
25, 2623. (d) Verkruijsse, H. D.; Brandsma, L. J . Organomet. Chem.
1987, 332, 95. (e) Ali, S. M.; Tanimoto, S. J . Org. Chem. 1989, 54, 5603.
Only one example of thiophilic attack: (f) Okazaki, R.; Fujii, T.;
Inamoto, N. J . Chem. Soc., Chem. Commun. 1984, 1010.
(13) (a) Narasimhan, L.; Sanitra, R.; Swenton, J . S. J . Chem. Soc.,
Chem. Commun. 1978, 719. (b) Nicolaou, K. C.; McGarry, D. G.;
Somers, P. K.; Veale, C. A.; Furst, G. T. J . Am. Chem. Soc. 1987, 109,
2504.
† Osaka University.
‡ Current address: Department of Applied Chemistry, Faculty of
Engineering, Kansai University, Suita, Osaka 564-8680, J apan.
(1) Weigert, F. Chem. Ber. 1903, 36, 1007.
(2) Thiocarboxylation towards carbon nucleophiles such as enolates
(a, b), phosphorous ylides (c), and an acyllithium (d). (a) Demuynck,
C.; Thullier, A. Bull. Soc. Chim. Fr. 1969, 2434. (b) Vedejs, E.; Nader,
B. J . Org. Chem. 1982, 47, 3193. (c) Bestmann, H. J .; Saalbaum, H.
Bull. Soc. Chim. Belg. 1979, 88, 951. (d) Seyferth, D.; Hui, R. C.
Tetrahedron Lett. 1984, 25, 2623.
(3) Thiocarboxylation towards heteroatom nucleophiles such as
alcoholates (a), phenolates (b), and amines (a). (a) Ferm, R. J . Chem.
Rev. 1957, 57, 621. (b) Chanyshev, N. T.; Kalaschnikov, S. M.;
Kuramshin, E. M.; Naimushin, A. I.; Imashev, U. B. Zh. Obshch. Khim.
1990, 60, 2568; Chem. Abstr. 1991, 115, 28833r.
(14) (a) Seebach, D. Chem. Ber. 1972, 105, 487. (b) Nilsson, N. H.;
Senning, A. Chem. Ber. 1974, 107, 2345. (c) Saquet, M. C. R. Acad.
Sci., Ser. C 1976, 283, 641.
(15) Schaumann, E.; Walter, W. Chem. Ber. 1974, 107, 3562.
(16) (a) Barbaro, G.; Battaglia, A.; Giorgianni, P.; Maccagnani, G.;
Macciantelli, D. J . Chem. Soc., Perkin Trans. 1 1986, 381. (b) Bonini,
B. F.; Maccagnani, G.; Masiero, S.; Mazzanti, G.; Zani, P. Tetrahedron
Lett. 1989, 30, 2677.
(4) For a high-yield synthesis of SeCO under mild conditions, see:
Kondo, K.; Yokoyama, S.; Miyoshi, N.; Murai, S.; Sonoda, N. Angew.
Chem., Int. Ed. Engl. 1979, 18, 691.
(5) Kondo, K.; Yokoyama, S.; Miyoshi, N.; Murai, S.; Sonoda, N.
Angew. Chem., Int. Ed. Engl. 1979, 18, 692.
(17) Selenoketones,18 selenoaldehydes,19 selenoformates,20 and isos-
elenocyanates21 react with organolithiums and Grignard reagents at
both the carbon and selenium atoms depending on the nature of the
nucleophile used. Only examples of the carbophilic attack are known
for selenoamides22 and CSe2.23
(6) As for thiocarbonyl compounds, thioketones,7 thioaldehydes,8 and
dithioesters7b,9 react with nucleophiles at both the carbon and sulfur
atoms. Thioamides,10 isothiocyanates,11 and CS2 react at the carbon
12
atom, but thioxoesters,13 trithiocarbonates,7b,14 thioketenes,15 and silyl
thioketones16 react at the sulfur atom.
(18) (a) Okazaki, R.; Ishii, A.; Inamoto, N. Tetrahedron Lett. 1984,
25, 5147. (b) Guziec, F. S., J r.; SanFilippo, L. J .; Murphy, C. J .;
Moustakis, C. A.; Cullen, E. R. Tetrahedron 1985, 41, 4843. (c) Ishii,
A.; Okazaki, R.; Inamoto, N. Bull. Chem. Soc. J pn. 1988, 61, 861.
(19) Okazaki, R.; Kumon, N.; Inamoto, N. J . Am. Chem. Soc. 1989,
111, 5949.
(20) (a) Okazaki, R.; Ishii, A.; Inamoto, N. J . Chem. Soc., Chem.
Commun. 1986, 71. (b) Ishii, A.; Okazaki, R.; Inamoto, N. Bull. Chem.
Soc. J pn. 1986, 59, 2529.
(21) Maeda, H.; Kambe, N.; Sonoda, N.; Fujiwara, S.; Shin-ike, T.
Tetrahedron 1996, 52, 12165.
(22) Sekiguchi, M.; Ogawa, A.; Fujiwara, S.; Ryu, I.; Kambe, N.;
Sonoda, N. Chem. Lett. 1990, 2053.
(23) J ensen, K. A.; Henriksen, L. Acta Chem. Scand. 1970, 24, 3213.
(24) The reaction of SCO with PhLi was examined in detail in order
to compare the reactivities of SeCO and SCO. Thus, SCO was treated
with PhLi under identical conditions as in run 1 of Table 1 by using
MeI instead of BzBr; the corresponding thiol ester 3 was obtained in
95% yield via carbophilic attack without any thiophilic products (eq
i).
(7) (a) Beak, P.; Worley, J . W. J . Am. Chem. Soc. 1970, 92, 4142.
(b) Beak, P.; Worley, J . W. J . Am. Chem. Soc. 1972, 94, 597. (c)
Dagonneau, M.; Vialle, J . Tetrahedron 1974, 30, 415. (d) Dagonneau,
M.; Vialle, J . Tetrahedron 1974, 30, 3119. (e) Ohno, A.; Nakamura,
K.; Shizume, Y.; Oka, S. Bull. Chem. Soc. J pn. 1977, 50, 1003. (f)
Masson, J .; Metzner, P.; Vialle, J . Tetrahedron 1977, 33, 3089. (g)
Paquer, D.; Vazeux, M. J . Organomet. Chem. 1977, 140, 257.
(8) (a) Vedejs, E.; Perry, D. A. J . Am. Chem. Soc. 1983, 105, 1683.
(b) Okazaki, R.; Fukuda, N.; Oyama, H.; Inamoto, N. Chem. Lett. 1984,
101. (c) Vedejs, E.; Perry, D. A.; Wilde, R. G. J . Am. Chem. Soc. 1986,
108, 2985.
(9) Reactions of dithioesters with organolithium and Grignard
reagents proceed in a thiophilic manner: (a) Le´ger, L.; Saquet, M. Bull.
Soc. Chim. Fr. 1975, 657. (b) Burgot, J .-L.; Masson, J .; Vialle, J .
Tetrahedron Lett. 1976, 4775. (c) Olsson, L.-I. Acta Chem. Scand. 1977,
B31, 639. (d) Meyers, A. I.; Tait, T. A.; Comins, D. L. Tetrahedron Lett.
1978, 4657. (e) Metzner, P. J . Chem. Soc., Chem. Commun. 1982, 335.
(f) Bulpin, A. B., Masson, S.; Sene, A. Tetrahedron Lett. 1989, 30, 3415.
Reactions of dithioesters with allyl, benzyl, propagyl, and vinyl
Grignard reagents proceed in a carbophilic manner: (g) Masson, S.;
Saquet, M.; Thuillier, A. Tetrahedron 1977, 33, 2949. (h) Gosselin, P.;
Masson, S.; Thuillier, A. J . Org. Chem. 1979, 44, 2807. Diorganocu-
prates react with dithioesters at the carbon atom: (i) Bertz, S. H.;
Dabbagh, G.; Williams, L. M. J . Org. Chem. 1985, 50, 4414.
i
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Published on Web 02/06/1998