SPOTLIGHT 465

SYNLETT Selenium Dioxide (SeO2) – A Versatile

Spotlight 227 Reagent
Compiled by Annada C. Maity
This feature focuses on a re-
agent chosen by a postgradu-
Annada C. Maity was born in Midnapore, India in 1979 and began
ate, highlighting the uses and studying chemistry at the Vidyasagar University in 1997. He re-
preparation of the reagent in ceived his M.Sc. in chemistry from this university in 2002 and
current research passed the National Eligibility Test (CSIR-UGC-NET) in 2003. He
joined the research group of Prof. S. P. Goswami and is currently
working towards his PhD at the Bengal Engineering and Science
University. His primary research interests are focused on the vicinal
polycarbonyl chemistry, pterin chemistry, total synthesis, and reac-
tion engineering.
Senior Research Fellow, Department of Chemistry, Bengal Engi-
neering and Science University, Howrah 711103, India
E-mail: [email protected]

This document was downloaded for personal use only. Unauthorized distribution is strictly prohibited.
Dedicated to my PhD advisor Prof. S. P. Goswami on his 55th birth-
day

Introduction Beckman rearrangement,7 benzylic oxidizing agent,8 and

as an allylic hydroxylating agent9 of organic molecules.
Selenium dioxide (SeO2) is a very useful and versatile re- Selenium dioxide is made by burning the element of Se in
agent for the synthesis of various types of organic com- air. It is a white crystalline solid at room temperature with
pounds. Among several oxidizing agents described for use a sublimation temperature of 315 °C. The solid forms in-
in organic synthesis, SeO2 has received interest as a supe- finite polymeric chains (syndiotactic) which are not pla-
rior oxidizing agent,1 as dienophile agent,2 oxidative bond nar, but the polymeric structure breaks down in the gas
cleaving agent,3 in the synthesis of organometallic re- phase to the monomeric covalent form, symmetrically
agents,4 as catalyst for synthesis of urea derivatives5, oxi- bent like SO2.
dative demethylating agent,6 an important agent in

Abstracts

(A) Superior Oxidizing Agent: SeO2 is a superior oxidizing agent for O

the synthesis of azobenzene and nitrosoarene from aromatic aniline SeO2 (0.05 equiv) N COOMe
MeOOC N +
using catalytic amounts of hydrogen peroxide.1 30% H2O2, MeOH
(A)
100%
MeOOC NH2

SeO2 (0.10 equiv)

MeOOC NO + (A)
30% H2O2, CH2Cl2
80% 20%

(B) Dienophile Agent: Selenium dioxide acts as a dienophile for the O O

synthesis of selenophane. Selenophane 2 can easily be synthesized in SeO2

Se
high yields in a single operation from 1,3-dienes containing a carbo-
dioxane–pyridine (5:1)
nyl group at the C-1 position of compound 1 and selenium dioxide via 1 2
a [4+2] cycloaddition, whereas an analogous diene containing a TBS-
ether gives 1,4-diol cyclic selenite 4 and 1,2-diol cyclic selenite 5.2
OTBS OTBS O OTBS
H
SeO2 O Se
O
O + Se O
O
Ph
Ph
3 4 5 Ph

SYNLETT 2008, No. 3, pp 0465–0466xx. 208

Advanced online publication: 23.01.2008
DOI: 10.1055/s-2008-1032130; Art ID: V23507ST
© Georg Thieme Verlag Stuttgart · New York
466 SPOTLIGHT

(C) Oxidative Bond Cleaving Agent: SeO2 can lead to oxidative bond OH

cleavages of allyl and propargyl ethers. Aryl allyl ether or aryl prop- O + H2C CH CHO

argyl ether undergoes oxidation at the vinyl or alkynyl position to af- SeO2
79%
ford phenol and acraldehyde or propargyl aldehyde, respectively.3 O
AcOH, dioxane OH
reflux
+ HC C CHO

57%

(D) In the Synthesis of an Organometallic Reagent: Triselenium di-

cyanide (TSD) is used as a selenocyanating reagent for the synthesis CN SeO2
of aromatic and aliphatic metallo-organic selenocyanates. Triseleni- H2C NC Se Se Se CN
CN DMSO
um dicyanide is formed by the reaction of malononitrile and selenium (TSD)

dioxide in dimethylsulfoxide.4

(E) Catalyst: Selenium dioxide is a good catalyst and exhibits re-

O
markable chemoselectivity for the formation of new unsymmetric NO2
SeO2
N,N¢-dipyridyl urea derivatives by reductive carbonylation of substi- + + 3 CO MeO N N
Et3N, toluene H H
tuted nitropyridine using carbon monoxide and amino pyridine deriv- MeO N N NH2
77%
N N

This document was downloaded for personal use only. Unauthorized distribution is strictly prohibited.
atives as co-reagents.5 + CO2

(F) Oxidative Demethylating Agent: Goswami and Maity have shown

N Me SeO2 N H
that SeO2 acts not only as oxidizing agent but also as demethylating
agent leading to the formation of 2(1H)-quinoxalinone from 3-meth- N O MW, 15 min, 450 W N O
yl-2(1H)-quinoxalinone in good yield under microwave irradiation.6 H
73%
H

(G) In a Beckman Rearrangement: SeO2 is a versatile reagent for the

conversion of aldoximes into nitriles in high yield with both aliphatic H SeO2
N OH R
and aromatic aldoximes. While the reaction proceeds with aliphatic R CHCl3
C N

aldoxims at room temperature in three hours, the reaction with aro-

R = aliphatic or aromatic
matic aldoximes is achieved in boiling chloroform.7

(H) Benzylic Oxidizing Agent: Goswami and Adak8 have shown that Het
SeO2
Me Het CHO
SeO2 can act as benzylic oxidizing agent for the synthesis of 2-piv- MW

aloylamino-6-formyl pterin, a new functionalized pyridine aldehyde Het = 2-pivaloylaminopterin-6-

= 2-pivaloylpyridine-6-
(2-pivaloylamino-pyridine-6-carboxaldehyde) and a series of other = quinoxaline-2-
important heterocyclic mono- and di-aldehydes (60–90%) under mi-
SeO2
crowave irradiation. Me Het Me OHC Het CHO
MW

Het = 1,8-naphthyridine-2,7-di-
= 1,10-phenanthyridine-2,9-di-

(I) Allylic Hydroxylating Agent: Treatment of alkenes with selenium SeO2

dioxide introduces a hydroxyl group in allylic position.9a SeO2 oxida- OH
tion of (Z)-3-tributylstannyl-1-alkenyl carbamates leads to easy for-
mation of the corresponding 3-hydroxy-1-alkenyl carbamates in high Bu3Sn
R3 SeO2 HO OCb
yield.9b
R1 R 2 r.t. R 1
OCb R2
R3
OCb = OC(O)N(i-Pr)2 70–90%

References
(1) Priewisch, B.; Braun, K. R. J. Org. Chem. 2005, 70, 2350. (5) Chen, J.; Ling, G.; Lu, S. Tetrahedron 2003, 59, 8251.
(2) (a) Nguyen, T. M.; Guzei, I. A.; Lee, D. J. Org. Chem. 2002, (6) Goswami, S. P.; Maity, A. C. Chem. Lett. 2007, 36, 1118.
67, 6553. (b) Nguyen, T. M.; Lee, D. Org. Lett. 2001, 3, (7) Sosnovsky, G.; Krogh, J. A. Synthesis 1978, 703.
3161. (8) Goswami, S. P.; Adak, A. K. Synth. Commun. 2003, 33, 475.
(3) Kariyone, K.; Yazawa, H. Tetrahedron Lett. 1970, 11, 2885. (9) (a) Tauber, A. Y.; Hynninen, P. H. Tetrahedron Lett. 1993,
(4) (a) Kachanov, A. V.; Slabko, O. Y.; Baranova, O. V.; 34, 2979. (b) Madec, D.; Ferezou, J. P. Synlett 1996, 867.
Shilova, E. V.; Kaminskii, V. A. Tetrahedron Lett. 2004, 45,
4461. (b) Goswami, S. P.; Maity, A. C.; García-Granda, S.;
Torre-Fernández, L. Acta Crystallogr., Sect. E 2007, 63,
o1741.

Synlett 2008, No. 3, 465–466 © Thieme Stuttgart · New York