Journal of the American Chemical Society
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aminoazetidin-2-one 7, which is a common building block for
(5) For recent selected examples, see: (a) Peng, C.; Wang, Y.;
Wang, J. J. Am. Chem. Soc. 2008, 130, 1566; (b) Kudirka, R.; Devine,
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synthesis of a variety of antibiotics, such as Penicillins and
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Cephalosporins.
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(
i) Yao, T.; Hirano, K.; Satoh, T.; Miura, M. Angew. Chem., Int. Ed.
Scheme 3. Synthetic utility of the α,β-diamino acid ester. (a)
2012, 51, 775; (j) Chan, W.-W.; Lo, S.-F.; Zhao, Z.; Yu, W.-Y. J. Am.
Chem. Soc. 2012, 134, 13565; (k) Selander, N.; Worrell, B. T.;
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134, 14670; (l) Hyster, T. K.; Ruhl, K. E.; Rovis, T. J. Am. Chem. Soc.
o
Pd(dppb)(CH CN) (PF ) (0.1 mol%), 1,4-dioxane, 60 C, 48 h,
3
2
6 2
7
4%. (b) CH ClCHCl , Pd(OH) /C (10 mol%, 20 wt%), MeOH,
2 2 2
o o
H (5 atm), 25 C, 8 h, 93% yield. (c) HCl (6 N), 110 C, 6 h,
2
8
4% yield.
2
013, 135, 5364. (m) Hu, F.; Xia, Y.; Ye, F.; Liu, Z.; Ma, C.; Zhang,
In summary, we have established an unprecedented inser-
Y.; Wang, J. Angew. Chem., Int. Ed. 2014, 53, 1364; (n) Ye, F.; Qu,
S.; Zhou, L.; Peng, C.; Wang, C.; Cheng, J.; Hossain, M. L.; Liu, Y.;
Zhang, Y.; Wang, Z.-X.; Wang, J. J. Am. Chem. Soc. 2015, 137, 4435.
tion of carbenoids into C-N bond of aminals on the basis of
palladium catalyzed C-N bond activation, which provided a
valuable and efficient method for synthesis of α,β-diamino
acid esters under mild conditions. Various aminals and diaz-
oesters are compatible with the reaction conditions to give a
broad range of α,β-diaminoacid esters with a quaternary car-
bon-center. Further investigation will be focused on the
asymmetric catalysis and other types of C-X bond insertion
reactions involving transition-metal-catalyzed C-X bond acti-
vation.
(
6) For selected examples, see: (a) Murahashi, S.-l.; Imada, Y.;
Nishimura, K. J. Chem. Soc., Chem. Commun. 1988, 1578; (b) Alper,
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M.; Alper, H. J. Am. Chem. Soc. 1992, 114, 7018; (f) Piotti, M. E.;
Alper, H. J. Am. Chem. Soc. 1996, 118, 111; (g) Mahadevan,V.;
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(
7) (a) Xie, Y.; Hu, J.; Wang, Y.; Xia, C.; Huang, H. J. Am. Chem.
ASSOCIATED CONTENT
Supporting Information. Experimental details and full spectroscopic
data for all new compounds. This material is available free of charge
via the Internet at http://pubs.acs.org.
Soc. 2012, 134, 20613; (b) Xie, Y.; Hu, J.; Xie, P.; Qian, B.; Huang,
H. J. Am. Chem. Soc. 2013, 135, 18327; (c) Zhang, G.; Gao, B.;
Huang, H. Angew. Chem., Int. Ed. 2015, 54, 7657.
(
8) For selected reports on palladium carbene, see: (a) Albéniz A.
C.; Espinet, P.; Manrique, R.; Pérez-Mateo, A. Angew. Chem., Int. Ed.
002, 41, 2363; (b) Bröring, M.; Brandt, C. D.; Stellwag, S. Chem.
AUTHOR INFORMATION
2
Commun. 2003, 2344; (c) Fillion, E.; Taylor, N. J. J. Am. Chem. Soc.
2003, 125, 12700; (d) Solé, D.; Vallverdú, L.; Solans, X.; Font-
Bardia, M.; Bonjoch, J. Organometallics 2004, 23, 1438; (e) Albéniz,
A. C.; Espinet, P.; Pérez-Mateo, A.; Nova, A.; Ujaque, G. Organome-
tallics 2006, 25, 1293; (f) Trépanier, V. É; Fillion, E. Organometal-
lics 2007, 26, 30; (g) Meana, I.; Albéniz, A. C.; Espinet, P. Organo-
metallics 2012, 31, 5494.
Corresponding Author
* hmhuang@licp.cas.cn
ACKNOWLEDGMENT
This research was supported by the Chinese Academy of Sciences,
the National Natural Science Foundation of China (21222203,
(9) Viso, A.; Pradilla, R. F.; García, A.; Aida, F. Chem. Rev. 2005,
105, 3167.
2
1172226 and 21133011).
(
10) CCDC 1405248 contains the supplementary crystallographic
data for this paper. This data can be obtained free of charge from The
(11) Many commercially available chiral phosphine ligands have
been tried, only (R)-(6,6'-dimethoxy-[1,1'-biphenyl]-2,2'-
diyl)bis(diisopropylphosphine) can give the desired product 3ab in
7% ee. Further studies to establish a highly enantioselective reaction
is needed.
(12) A stoichiometric reaction monitored with in-situ NMR further
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