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(7) (a) Kurti, L.; Czako, B. Strategic Applications of Named Reactions
crystallography (Figure 1). As is evident from the crystal
structure, steric demand of the bicyclic system inhibited
further progress of the reaction to form nitro-norbornene
compound. Although such an observation supports path 2 as
the likely mechanism, at present we could not rule out any
of the two pathways we have depicted in Scheme 8. Using
steady state analysis, it can be shown that both the suggested
mechanisms (Scheme 8) are kinetically equivalent and have
a partial order (0.4) with respect to TEMPO.12 Detail
mechanistic studies are presently undergoing in our
laboratory.
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Jackstell, R.; Vogl, N.; Weckbecker, C.; Beller, M. Adv. Synth.
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Tebben, L.; Studer, A. Angew. Chem. Int. Ed. 2011, 50, 5034; (c)
Hoover, J. M.; Stahl, S. S. J. Am. Chem. Soc. 2011, 133, 16901; (d)
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Int. Ed. 2012, 51, 3699.
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Figure 1. ORTEP diagram of plausible intermediate16
In summary, a highly selective and efficient protocol for
nitration of olefins has been developed by employing
AgNO2/TEMPO under ambient condition.17 This process is
practical and a wide array of substrates including aromatic,
aliphatic and heteroaromatic olefins can be nitrated in regio–
and stereoselective manner. The strategy developed here
can allow olefin nitration as a method for rationalizing
complex molecule synthesis.
(12) See Supporting Information for detailed description.
(13) Climent, M. J.; Corma, A.; Iborra, S. Chem. Rev. 2011, 111, 1072.
(14) Intermediate
A contains a
sp2-radical center (Scheme 8).
Formation of B is likely stereo-determining and may depend on the
substituents present in A. The (E)-β-nitro olefins were generated
exclusively possibly due to the stereo electronic requirement of H-
atom abstraction by TEMPO (trans-elimination) and/or
thermodynamic stability of the product.
Me
Me
Me
Me
Acknowledgment. This activity is supported by DST (R/S1/IC–
24/2011). Financial support received from CSIR-India (fellowship
to S. Maity, S.R., T.N.) and IIT Bombay (S. Manna) is gratefully
acknowledged. D.M. sincerely thanks Dr. Rahul Banerjee (NCL-
Pune), Mr. Manas Sajjan, Prof. I. N. N. Namboothiri (IIT Bombay)
and Reviewers for insightful discussions.
N
O
M
M
NO2
S
NO2
L
L
L
M
S
S
Me
Me
H
.
O
N
L, large; M, medium; S, small
Me
Me
Supporting Information Available:
Experimental
Notably, nitration reactions were found to be stereo-convergent e.g.
(E)-4-octene produced thermodynamically stable (E)-4-nitrooctene
(5h) and (Z)-2-hexene produced (E)-2-nitrohexene (5i).
Observed stereo chemical outcome of nitration leading to
product 7a can be rationalized as follows: orientation of the
incorporated nitro group at the terminal site should be
preferentially exo rather than endo to the sterically encumbered
cavity of fused trans-decalin system. Subsequent elimination/
oxidation of the exo intermediate would provide E- nitroolefin
selectively.
procedures and characterization data for all compounds. This
material is available free of charge via the Internet at
________________________________________________
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