Erratum to: An Unexpected [1,5]-H Shift in the Synthesis of Nitroanilines

Full text of DOI:10.1021/ol0265362

ORGANIC
LETTERS
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002
Vol. 4, No. 17
017
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Additions and Corrections
Vol. 4, 2002
Ian W. Davies,* Jean-Fran c¸ ois Marcoux, Jeremy D. O.
Taylor, Peter G. Dormer, Robert J. Deeth,
F e´ lix-Antoine Marcotte, David L. Hughes, and
Paul J. Reider
Junhu Zhang and E. J. Corey*
A Simple Enantioselective Synthesis of Serratenediol.
Page 3215, last line. “Z-coupled” should be replaced by
“E-coupled”.
An Unexpected [1,5]-H Shift in the Synthesis of Nitro-
anilines.
Page 3216. Structure 10 also should be the E-vinyl TBS
ether.
Page 439. The outcome of the reaction of methyl acetoac-
etate and nitrovinamidinium salts (1a-d) to give substituted
anilines (2a-c) was rationalized as proceeding through a
OL026337I
[1,5]-H shift. After publication of this work, we began to
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investigate the mechanistic pathway by computational meth-
ods in collaboration with Prof. Ken Houk (UCLA). All 1,5-
hydrogen shifts have barriers of greater than 45 kcal/mol
according to B3LYP/6-31G* calculations for both neutral
and anionic intermediates. Since we were unable to locate a
thermally accessible transition state, these computational
studies prompted us to revisit the structural assignment of
the anilines. The regiochemistry was previously determined
by an HMBC NMR experiment. Extensive NOE studies and
preparation of the authentic alternative regioisomers have
led us to revise the aniline 2a to 2-(dimethylamino)-5-
nitrobenzoic acid methyl ester. Additional support for the
revision is based on X-ray crystallographic analysis of an
analogue. The mechanisitic implication of this revision is a
formal 1,5-dimethylamine shift.
Published on Web 07/04/2002
Supporting Information Available: Revised Scheme 1
and Tables 1 and 2. Revised characterization data with
correct nomenclature. This material is available free of charge
via the Internet at http://pubs.acs.org.
OL0265362
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Published on Web 07/26/2002