One advantage of the current technology is the facile cleavage
and recovery of the chiral alcohol. For instance, methanolysis of
amine 6 produced methylcarbamate 20 in good yields and high
enantiomeric excess (Scheme 3).17 (R)-1-Phenyl-2,2,2-trichloro-
ethanol was also recovered in good yields and enantiomeric
excess, thus making the chiral reagent recyclable.
5 (a) P. Dauban and R. H. Dodd, Synlett, 2003, 1571; (b) T. Wirth,
Angew. Chem., Int. Ed., 2005, 44, 3656; (c) J. W. W. Chang, T. M.
U. Ton and P. W. H. Chan, Chem. Rec., 2011, 11, 331.
6 For a recent example of a metal-free C–H amination reaction, see:
(a) M. Ochiai, K. Miyamoto, T. Kaneaki, S. Hayashi and
W. Nakanishi, Science, 2011, 332, 448; (b) M. Ochiai,
S. Yamane, M. M. Hoque, M. Saito and K. Miyamoto, Chem.
Commun., 2012, 48, 5280.
To further extend the substrate scope, the propargylic
amination of alkynes was studied (Table 2). We were pleased
to find that propargylic amine 21 was produced with 27 : 1
crude dr (entry 1). The desired product was isolated as a single
diastereomer in 50% yield. Similarly, amine 22 was isolated in
62% and 52 : 1 dr (entry 2). To the best of our knowledge, this is
the first example of a metal nitrene propargylic intermolecular
C–H amination reaction.18 It was possible to reduce the alkyne
to the Z-allylic amine 23 in 92% yield (Scheme 4).
7 (a) J. L. Liang, S. X. Yuan, J. S. Huang, W. Y. Yu and C. M. Che,
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Paradine and M. C. White, J. Am. Chem. Soc., 2012, 134, 2036.
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¨
T. Katsuki, Tetrahedron Lett., 2001, 42, 3339; (c) J. L. Liang,
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Scheme 4 Hydrogenation of chiral carbamate 21.
In conclusion, readily available chiral N-mesyloxycarbamate 2
was used to perform stereoselective C–H amination reactions. The
scope of the process was extended to produce benzylic and pro-
pargylic amines in good yields and dr. The reaction was performed
in ethyl acetate and produced biodegradable by-products. After
cleavage, both chiral amine and the chiral alcohol derived from
reagent 2 were recovered in high yields and ee.
P. Muller, R. H. Dodd and P. Dauban, Angew. Chem., Int. Ed., 2006,
¨
45, 4641; (g) R. P. Reddy and H. M. L. Davies, Org. Lett., 2006,
8, 5013; (h) K. W. Fiori and J. Du Bois, J. Am. Chem. Soc., 2007,
129, 562; (i) C. Liang, F. Collet, F. Robert-Peillard, P. Muller,
¨
R. H. Dodd and P. Dauban, J. Am. Chem. Soc., 2008, 130, 343;
(j) H. J. Lu, V. Subbarayan, J. R. Tao and X. P. Zhang, Organo-
This research was supported by NSERC (Canada), Johnson
& Johnson, the Canada Foundation for Innovation, the
metallics, 2010, 29, 389; (k) A. Norder, P. Herrmann, E. Herdtweck and
¨
T. Bach, Org. Lett., 2010, 12, 3690; (l) V. Lyaskovskyy, A. I. O. Suarez,
H. J. Lu, H. L. Jiang, X. P. Zhang and B. de Bruin, J. Am. Chem. Soc.,
2011, 133, 12264; (m) Q. Michaudel, D. Thevenet and P. S. Baran,
J. Am. Chem. Soc., 2012, 134, 2547.
Canada Research Chair Program, the Universite
and the Centre in Green Chemistry and Catalysis (CGCC). We
thank Francine Belanger-Gariepy for resolution of X-ray
crystal structures as well as Phan viet Minh Tan and Cedric
Malveau from the Universite de Montreal NMR Center.
de Montreal
´ ´
´
´
9 Reaction run at À35 1C for
3 d under Ar in anhydrous
´
TCE/MeOH; not recoverable chiral auxiliary used; PhI(O2Ct-Bu)2
(MW = 406) used to generate the corresponding iminoiodinane.
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11 H. Lebel, C. Spitz, O. Leogane, C. Trudel and M. Parmentier,
Org. Lett., 2011, 13, 5460.
´
´
Notes and references
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c
This journal is The Royal Society of Chemistry 2012
Chem. Commun., 2012, 48, 7799–7801 7801