826
Q. Shao et al.
LETTER
pattern of condensation and dealkylation was followed.
Dealkylation resulted in the fission of the ring, leading to
the corresponding vinyl sulfide 4i with a long chain (entry
8).
References and Notes
(1) (a) Reddy, D. S. Org. Lett. 2004, 6, 3345. (b) Singleton,
D. A.; Hang, C. J. Org. Chem. 2000, 65, 7554. (c) Shibuya,
K. Synth. Commun. 1994, 24, 2923. (d) Tsukamoto, Y.;
Sato, K.; Kinato, T.; Yani, T. Bull. Chem. Soc. Jpn. 1992, 65,
3300. (e) Arigoni, D.; Vasella, A.; Sharpless, K. B.; Jensen,
H. P. J. Am. Chem. Soc. 1973, 95, 7917. (f) Bhalerao, U. T.;
Rapaport, H. J. Am. Chem. Soc. 1971, 93, 4835.
(2) (a) Manktala, R.; Dhillon, R. S.; Chhabra, B. R. Indian J.
Chem., Sect. B: Org. Chem. Incl. Med. Chem. 2006, 45,
1591. (b) Fürstner, A.; Gastner, T. Org. Lett. 2000, 2, 2467.
(c) Corey, E. J.; Wu, L. I. J. Am. Chem. Soc. 1993, 115,
9327. (d) Umbreit, M. A.; Sharpless, K. B. J. Am. Chem.
Soc. 1977, 99, 5526.
Table 3 SeO2-Catalyzed Reaction of Ninhydrin (1) with Sulfonium
Salts 2 to Yield Vinyl Sulfides11
R2
O
O
R2
S+
O
SeO2 (10 mol%)
S
Cs2CO3 (10 mol%)
R2
R1
+
1a
I–
MeCN
R1
O
2
4
I
O
(3) (a) Mehta, G.; Shinde, H. M. Tetrahedron Lett. 2003, 44,
7049. (b) Xu, P.; Chen, Y.; Lin, S.; Lu, T. J. Org. Chem.
2002, 67, 2309. (c) Lee, J. G.; Kim, K. C. Tetrahedron Lett.
1992, 33, 6363. (d) Valechha, N. D.; Sewanee, J. P. J. Indian
Chem. Soc. 1986, 63, 970.
S
R1
O
O
(4) (a) Tagawa, Y.; Yamashita, K.; Higuchi, Y.; Goto, Y.
Heterocycles 2003, 60, 953. (b) Cain, M.; Campos, O.;
Guzman, F.; Cook, J. M. J. Am. Chem. Soc. 1983, 105, 907.
(c) Sakasai, T.; Sakamoto, T.; Yamanaka, H. Heterocycles
1979, 13, 235. (d) Hill, R. K. J. Org. Chem. 1961, 26, 4745.
(5) (a) Naota, T.; Sasao, S.; Tanaka, K.; Yamamoto, H.;
Murahashi, S. I. Tetrahedron Lett. 1993, 34, 4843.
(b) Kariyone, K.; Yazawa, H. Tetrahedron Lett. 1970, 11,
2885. (c) Berge, D. D.; Kale, A. V. Chem. Ind. (London)
1979, 662.
4i
Entry
2
R1
Ph
R2
4
Time Yield
(h)
(%)a
77
66
60
55
72
48
0
1
2
3
4
5
6
7
8
9
2d
2m
2n
2o
2p
2q
2r
2s
Me
4a
4c
4d
4e
4f
4
4-ClC6H4
4-AcOC6H4
4-MeOC6H4
2-MeOC6H4
2-thiophene
Me
Me
Me
Me
Me
Me
Me
4
18
12
24
12
20
20
24
(6) (a) Sosnovsky, G.; Krogh, J. A.; Umhoefer, S. G. Synthesis
1979, 722. (b) Sosnovsky, G.; Krogh, J. A. Synthesis 1978,
703.
(7) Shao, Q.; Li, C. Synlett 2008, 2317.
4g
4h
(8) (a) Rubin, M. B.; Gleiter, R. Chem. Rev. 2000, 100, 1121.
(b) Linda, R. G. II; Jeroncic, L. O.; Danishefsky, S. J. J. Org.
Chem. 1991, 56, 2534.
(9) Kim, H. S.; Kim, Y. J.; Lee, H.; Lee, S. D.; Chin, C. S.
J. Catal. 1999, 184, 526.
(10) Typical Procedure for Preparing Compound 3
A mixture of ninhydrin (1, 178 mg, 1.0 mmol), dipropyl
phenacylsulfonium bromide (2c, 317 mg, 1.0 mmol), SeO2
(22 mg, 0.2 mmol), and Cs2CO3 (33 mg, 0.1 mmol) in MeCN
(10 mL) was stirred for 7 h at r.t. After complete
Ph
–(CH2)4– 4ib
Me 4j
50
0
2t
EtO
a Isolated yields.
b Structure shown above.
consumption of the starting materials (TLC), MeCN was
removed in vacuum to give yellow solid. The residue was
treated with aq H2SO4 (10%, 1 mL) followed by brine (10
mL), and extracted with CH2Cl2 (2 × 50 mL). The combined
organic layers were dried over anhyd Na2SO4. The extracts
were then concentrated under reduced pressure, and the
residue was purified by column chromatography (eluent:
PE–EtOAc) on SiO2 to give a 83% yield of 3a.
In conclusion, we have developed simple procedures for
the synthesis of vinyl alcohols and vinyl sulfides from the
reaction of ninhydrin and sulfonium salts catalyzed by
Cs2CO3 and SeO2. The reactions are highly chemoselec-
tive if the anion or the size of alkyl groups of the sulfo-
nium is properly chosen. From ninhydrin both vinyl
alcohols and vinyl sulfides products could be obtained in
fair to good yields.
1H NMR (500 MHz, CDCl3): d = 8.07 (d, J = 7.4 Hz, 1 H),
7.98 (d, J = 7.5 Hz, 2 H), 7.91–7.84 (m, 3 H), 7.65 (t, J = 7.4
Hz, 1 H), 7.52 (t, J = 7.8 Hz, 2 H) ppm. 13C NMR (125 MHz,
CDCl3): d = 189.24, 186.09, 185.49, 142.78, 139.22, 138.95,
136.21, 136.20, 134.67, 132.37, 131.09, 129.48, 129.06,
124.03, 123.95 ppm. IR (KBr): n = 1737, 1699, 1670, 1622,
1589, 1451, 1354, 1330, 1246, 1121, 1060, 810, 741, 688
cm–1. ESI-MS: m/z (%) = 277.2 (100) [M+ – H]. Anal. Calcd
for C17H10O4: C, 73.38; H, 3.62. Found: C, 73.33; H, 3.61.
(11) Typical Procedure for Preparing Compound 4
A mixture of ninhydrin (1, 178 mg, 1.0 mmol), dimethyl
phenacylsulfonium iodide (2d, 308 mg, 1.0 mmol), SeO2 (11
mg, 0.1 mmol), and Cs2CO3 (33 mg, 0.1 mmol) in MeCN (10
mL) was stirred for 4 h at r.t. After complete consumption of
starting materials (TLC), MeCN was removed in vacuum to
give yellow solid. The residue was treated with brine (10
Supporting Information for this article is available online at
Acknowledgment
We thank NSFC (20572078) for financial support.
Synlett 2009, No. 5, 823–827 © Thieme Stuttgart · New York