ORGANIC
LETTERS
2003
Vol. 5, No. 23
4501-4504
NaIO -Mediated Selective Oxidative
Halogenation of Alkenes and Aromatics
Using Alkali Metal Halides
4
Gajanan K. Dewkar, Srinivasarao V. Narina, and Arumugam Sudalai*
Chemical Engineering and Process DeVelopment DiVision,
National Chemical Laboratory, Pashan Road, Pune 411008, India
Received September 21, 2003
ABSTRACT
NaIO oxidizes alkali metal halides efficiently in aqueous medium to halogenate alkenes and aromatics and produce the corresponding halo
4
derivatives in excellent regio and stereoselectivity. The system also demonstrates the asymmetric version of bromo hydroxylation using
â-cyclodextrin complexes, resulting in moderate ee.
The 1,2-functionalization of olefins by the selective addition
of two different functional groups, such as water or alcohols
and halogens (halohydroxylation or haloalkoxylation), in a
highly regio- and enantioselective manner, remains important
and challenging to organic chemists.1 Such halo derivatives
are widely used in the synthesis of pharmaceuticals, dyes,
flame-retardants, additives and plasticizers, agrochemicals,
and speciality chemicals.2 Conventional halogenation meth-
ods3 typically use elemental halogens, which are pollutants,
and generate hazardous HX as byproducts. Recently, the
oxidative halogenation of olefins by metal halides has
emerged as an important alternative for the synthesis of such
halo derivatives.4 However, such oxidative halogenations
involve the use of heavier metals in stoichiometric amounts,
often resulting in poor yield and selectivity. Haloperoxidases,
such as vanadium bromoperoxidase (V-BrPO),5 are known
to catalyze the 2e- oxidation of halides by H2O2, resulting
in the concomitant halogenation of organic substrates,
probably accounting for the biosynthesis of numerous
halogenated marine natural products such as terpenes,
indoles, phenols, etc. Several catalytic functional mimics of
V-BrPO have already been reported.6
In this communication, we wish to report that sodium
periodate7 (NaIO4) oxidatively halogenates a variety of
olefins and aromatics with alkali metal halides as halogen
* To whom correspondence should be addressed. Phone: +91-020-
5893300. Fax: + 91-20-5893359.
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10.1021/ol0358206 CCC: $25.00 © 2003 American Chemical Society
Published on Web 10/18/2003