3238
J . Org. Chem. 2001, 66, 3238-3241
substitution via ammonia. Therefore, the employment of
High ly Regio- a n d En a n tioselective
“protected ammonia”, such as phthalimide, p-toluenene-
sulfonamide, di-tert-butyl iminodicarbonate, methylcar-
bamate, or bis(trimethylsilyl)amides, was an alternative
approach to afford allylic primary amines.4 However, the
application of the above reagents has been significantly
limited by the difficulties of deprotection of amino group,
reagent preparation, or low efficiency in terms of “atom
economy”.5 Recently, sodium N,N-diformylamide (SDFA)6
(1) was found to be an advanced alternative to classical
Gabriel reagent for the preparation of primary amines,7
having the advantages of easy availability, facile depro-
tection, and high atom economy. Nevertheless, its reac-
tion with allylic acetate has not been developed. In this
paper, we report the first highly regio- and enantio-
selective palladium-catalyzed amination of allylic ac-
etates using 1 as a nucleophile.
P a lla d iu m -Ca ta lyzed Allylic Am in a tion
w ith Sod iu m Difor m yla m id e
Yi Wang and Kuiling Ding*
Laboratory of Organometallic Chemistry, Shanghai Institute
of Organic Chemistry, Chinese Academy of Sciences,
354 Fenglin Road, Shanghai 200032, P. R. China
kding@pub.sioc.ac.cn
Received February 2, 2001
Palladium-catalyzed asymmetric amination of allylic
substrates for the preparation of enantiomerically en-
riched allylic amine derivatives has not been so well
developed in comparison with allylic alkylation of carbon
nucleophiles.1 Although both secondary and tertiary
allylic amines were obtained with excellent results
through palladium-catalyzed amination,2,3 primary allylic
amines were difficult to obtain directly from nucleophilic
The investigation was initiated by using 1,3-diphenyl-
allylic acetate (2a ) as substrate and dimeric allylpalla-
dium chloride as catalyst precursor to test the reactivity
of 1 and to find the matched ligands for the catalyst (eq
1). A variety of ligands ranging from monodentate PPh3
* To whom correspondence should be addressed. Fax: 86-21-
64166128.
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10.1021/jo015553m CCC: $20.00 © 2001 American Chemical Society
Published on Web 04/07/2001