ORGANIC
LETTERS
XXXX
Vol. XX, No. XX
000–000
Stereoselective Nitration of Olefins with
tBuONO and TEMPO: Direct Access to
Nitroolefins under Metal-free Conditions
Soham Maity, Togati Naveen, Upendra Sharma, and Debabrata Maiti*
Department of Chemistry, Indian Institute of Technology Bombay, Powai,
Mumbai-400 076, India
Received May 20, 2013
ABSTRACT
Nitroolefins are essential elements for both synthetic chemistry and medicinal research. Despite significant improvements in nitration of olefin an
efficient metal-free synthesis remains elusive so far. Herein, we disclose a new set of reagents to access nitroolefins in a single step under metal-
free conditions. A wide range of olefins with diverse functionalities has been nitrated in synthetically useful yields. This transformation is
operationally simple and exhibits excellent E-selectivity. Furthermore, site selective nitration in a complex setup makes this method
advantageous.
Nitroolefins are a prominent class of synthetic inter-
mediates, which have found application in the preparation
of a wide variety of biorelevant compounds and pharma-
ceuticals.1 These are usually synthesized by Henry reac-
tion, involving base mediated condensation of nitro-
alkanes with aldehydes or ketones followed by subsequent
dehydration.2 An alternative and relatively simple ap-
proach relies upon widely available olefins as the starting
material, wherein a nitro group directly replaces olefin
hydrogen. This convenient and step economical process
has drawn significant attention in recent decades. To date,
a number of methods have been developed with different
metal based and gaseous nitrating agents (Scheme 1).3
These methods while offering significant improvements
in direct nitration of olefins often have several drawbacks.
Problematic issues include the tendency to form an un-
desired mixture of E/Z isomers,3a,b lack of functional
group tolerance,3e,g and harsh reaction conditions among
others.3d,g Further, stereoselective nitration of olefins with
an easy-to-handle metal-free reagent is yet to be developed.
Notably, from a practical aspect, metal-free syntheses4
are preferred, as the removal of metal contamination can
render a process quite expensive.5 In particular, nitration
under metal-free conditions would be of great significance
due to its close association with the pharmaceutical
industry. Our lab has been involved in developing a
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10.1021/ol401426p
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