1536
S. Balasubramaniam, I. S. Aidhen
LETTER
sion of a stabilized enolate [–CH2CON(OMe)Me] cannot
be excluded. Clean reaction of phenylmagnesium bro-
mide (2.0 equiv) with b-organylseleno WA 10a, wherein
such a possibility does not exists and subsequent obtain-
ment of ketone 3a in better yield (68%), supports this ob-
servation and rationale (Scheme 2). The successful
addition of other ArMgBr (2.0 equiv) in THF at 5–10 °C
onto other b-organylseleno WA 10b,c and obtainment of
the corresponding b-organylseleno ketones 3b (62%) and
3c (65%) in good yields provides the generality of the de-
veloped reaction protocol (Table 2).
(3) (a) Victoria, F. N.; Radatz, C. S.; Sachini, M.; Jacob, R. G.;
Perin, G.; Da Silva, W. P.; Lenardão, E. J. Tetrahedron Lett.
2009, 50, 6761; and references cited therein. (b) Paulmier,
C.; Houllemare, D.; Ponthieux, S.; Outurquin, F. Synthesis
1997, 101. (c) Cossy, J.; Furet, N. Tetrahedron Lett. 1993,
34, 7755. (d) Magnus, P.; Rigollier, P. Tetrahedron Lett.
1992, 33, 6111. (e) Back, T.; Kerr, R. Tetrahedron Lett.
1982, 23, 3241. (f) Sonoda, N.; Miyoshi, N.; Yamamoto, T.;
Kambe, N.; Murai, S. Tetrahedron Lett. 1982, 23, 4813.
(4) Bao, W.; Zhang, Y. Synlett 1996, 1187.
(5) Nishiyama, Y.; Kawamatsu, H.; Funato, S.; Tokunaga, K.;
Sonoda, N. J. Org. Chem. 2003, 68, 3599.
(6) Reich, H. J.; Jasperse, C. P.; Renga, J. M. J. Org. Chem.
1986, 51, 2981.
Finally, towards the targeted glycosylseleno ketones 1 as
a new structural motif, ArMgBr was now added onto the
WA functionality in 10d and 10e having a glycosyl unit as
the organic residue on selenium. Successful Grignard ad-
dition onto these representative examples, furnishing the
corresponding b-glycosylseleno ketones 3d (60%) and 3e
(62%) in good yields aptly demonstrated the usefulness of
these building blocks and the associated strategy for in-
corporating highly functionalized residues on selenium
(Table 2). All products displayed satisfactory spectral and
analytical details.
(7) (a) Meciarova, M.; Toma, S. Lett. Org. Chem. 2006, 3, 794.
(b) Chu, C.-M.; Gao, S.; Sastry, M. N. V.; Kuo, C.-W.; Lu,
C.; Liu, J.-T.; Yao, C.-F. Tetrahedron 2007, 63, 1863; and
references cited therein.
(8) (a) Nahm, S.; Weinreb, S. M. Tetrahedron Lett. 1981, 22,
3815. For reviews on Weinreb amide chemistry, see:
(b) Sivaraman, B.; Aidhen, I. S. Synthesis 2008, 3707.
(c) Singh, J.; Satyamurthi, N.; Aidhen, I. S. J. Prakt. Chem.
2000, 342, 340. (d) Mentzel, M.; Hoffmann, H. M. R.
J. Prakt. Chem. 1997, 339, 517. (e) Sibi, M. P. Org. Prep.
Proced. Int. 1993, 25, 15.
(9) (a) Sivaraman, B.; Harikrishna, K.; Aidhen, I. S.
Tetrahedron Lett. 2011, 52, 2683. (b) Sivaraman, B.;
Aidhen, I. S. Eur. J. Org. Chem. 2010, 4991.
To conclude, new synthetic equivalents 4 and 5 based on
WA functionality have been realized and successfully uti-
lized to synthesize a- and b-organylseleno aryl ketones. In
the context of reactivity, the building block 5 gave better
results. The objective of synthesizing glycosylseleno ke-
tones 1 was successfully achieved using our building
block 5 and was demonstrated by preparing b-glycosylse-
leno aryl ketones having the glycosyl residue on selenium.
The visualized concept is not limited to a- or b-positions.
The concept and strategy should allow incorporation of
organylseleno unit at any other positions such as g-, d-,
and beyond. Hence the work presented herein holds prom-
ise and amenable for further exploitation according to the
need and objectives of the synthetic endeavors.
(c) Sivaraman, B.; Senthilmurugan, A.; Aidhen, I. S. Synlett
2007, 2841. (d) Sivaraman, B.; Aidhen, I. S. Synlett 2007,
959.
(10) Logan, G.; Igunbor, C.; Chen, G.-X.; Davis, H.; Simon, A.;
Salon, J. Synlett 2006, 1554.
(11) Klayman, D. L.; Griffin, T. S. J. Am. Chem. Soc. 1973, 95,
197.
(12) Ghosh, A. K.; Banerjee, S.; Sinha, S.; Kang, S. B.; Zajc, B.
J. Org. Chem. 2009, 74, 3689.
(13) Selvamurugan, V.; Aidhen, I. S. Synthesis 2001, 2239.
(14) 2,2¢-Diselenediylbis(N-methoxy-N-methylacetamide) (4)
Yield 45%. Rf = 0.20 (hexanes–EtOAc = 6:4), yellow
colored liquid. 1H NMR (400 MHz, CDCl3): d = 3.14 (s, 3 H,
NCH3), 3.52 (s, 2 H, SeCH2), 3.68 (s, 3 H, OCH3). 13C NMR
(100 MHz, CDCl3): d = 29.6, 32.5, 61.5, 171.2. IR (CHCl3):
2929, 2850, 1637, 1445, 1155 cm–1. ESI-HRMS: m/z calcd
for C8H16N2O4NaSe2 [M + Na]+: 386.9338; found:
386.9344.
Supporting Information for this article is available online at
3,3¢-Diselenediylbis(N-methoxy-N-methylpropan-
amide) (5)
Yield 65%. Rf =0.25 (hexanes–EtOAc = 6:4), yellow colored
liquid. 1H NMR (400 MHz, CDCl3): d = 2.94–2.98 (m, 2 H,
COCH2), 3.12–3.15 (m, 2 H, SeCH2), 3.19 (s, 3 H, NCH3),
3.70 (s, 3 H, OCH3). 13C NMR (100 MHz, CDCl3): d = 22.1,
29.1, 32.4, 61.5, 171.5. IR (CHCl3): 2921, 2847, 1626, 1458,
1166 cm–1. ESI-HRMS: m/z calcd for C10H21N2O4Se2 [M +
H]+: 392.9832; found: 392.9833.
Acknowledgment
The authors thank DST-New Delhi for the funding towards 400
MHz NMR machine to the Department of Chemistry, IIT-Madras
under the IRHPA scheme and ESI-MS facility under the FIST pro-
gram. Board of Research in Nuclear Sciences (BRNS) is acknowl-
edged for funding of project 2008/37/21/BRNS. BSR is thankful to
CSIR for a Fellowship.
(15) The sugar halides 13 and 14 were prepared through multistep
reaction sequence from commercially available
monosacchride D-(+)-glucono-1,5-lactone.
(16) Déziel, R.; Malenfant, E.; Thibault, C.; Fréchette, S.; Gravel,
M. Tetrahedron Lett. 1997, 38, 4753.
References and Notes
(1) Freudendahl, D. M.; Shahzad, S. A.; Wirth, T. Eur. Org.
Chem. 2009, 1649.
(2) (a) Braga, H. C.; Stefani, H. A.; Paixao, M. W.; Santos, F.
W.; Ludtke, D. S. Tetrahedron 2010, 66, 3441. (b) Braga,
H. C.; Wouters, A. D.; Zerillo, F. B.; Ludtke, D. S.
Carbohydr. Res. 2010, 345, 2328.
(17) Campbell, T. W.; McCullough, J. D. J. Am. Chem. Soc.
1945, 67, 1965.
Synlett 2011, No. 11, 1533–1536 © Thieme Stuttgart · New York