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ChemComm
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DOI: 10.1039/C7CC00003K
COMMUNICATION
Journal Name
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S. A. Lawrence, Amines: Synthesis, Properties and
Applications; Cambridge University: Cambridge, UK, 2004.
Selected recent examples: (a) A. Mukherjee, D. Srimani, S.
Chakraborty, Y. Ben-David and D. Milstein, J. Am. Chem. Soc.,
2015, 137, 8888; (b) S. Imm, S. Bähn, M. Zhang, L. Neubert,
H. Neumann, F. Klasovsky, J. Pfeffer, T. Haas and M. Beller,
Angew. Chem. Int. Ed., 2011, 50, 7599; (c) M. Fan, W. Zhou,
Y. Jiang and D. Ma, Org. Lett., 2015, 17, 5934.
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Peter G. M. Wuts, Theodora W. Greene. Greene's Protective
Groups in Organic Synthesis, Fourth Edition. John Wiley &
Sons, Inc. 2007.
(a) R. V. Jagadeesh, T. Stemmler, A.-E. Surkus, H. Junge, K.
Junge and M. Beller, Nat. Protocols., 2015, 10, 548; (b) R. J.
Detz, Z. Abiri, R. le Griel, H. Hiemstra and J. H. van
Maarseveen, Chem. Eur. J., 2011, 17, 5921.
Scheme 6 Proposed intermediate of the reaction of EDA,
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(a) “methylamines”: A. B. van Gysel, W. Musin in Ullmann's
Encyclopedia of Industrial Chemistry, 7th ed. Online, Wiley,
New York; (b) “ammonia” K. J. McCullough in Encyclopedia of
reagents for Organic Synthesis 2nd ed. Wiely, Chichester, UK,
2009.
(a) B. Zimmermann, J. Herwig and M. Beller, Angew. Chem.
Int. Ed., 1999, 38, 2372; (b)T. Gross, A. M. Seayad, M. Ahmad
and M. Beller, Org. Lett., 2002, 4, 2055; (c) C. Gunanathan
ammonia and N-benzylisatin in THF
A plausible mechanism was proposed (Scheme 7). At the
beginning, Fe(TPP)Cl was reduced to Fe(TPP) by diazo
compound,17 followed by the treatment of diazocompound to
produce iron carbene. The carbene complex then suffered
from a nucleophilic attack of ammonia to produce ylide
intermediate. Trapping of this reactive species afforded the
target multi-functional unprotected primary amine.
and D. Milstein, Angew. Chem. Int. Ed., 2008, 47, 8661; (d) T.
Nagano and S. Kobayashi, J. Am. Chem. Soc., 2009, 131, 4200;
(e) M. J. Pouy, L. M. Stanley and J. F. Hartwig, J. Am. Chem.
Soc., 2009, 131, 11312; (f) V. Lavallo, G. D. Frey, B.
Donnadieu, M. Soleilhavoup and G. Bertrand, Angew. Chem.
Int. Ed., 2008, 47, 5224; (g) Q. Shen and J. F. Hartwig, J. Am.
Chem. Soc., 2006, 128, 10028.
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For selected examples of the trapping of ylides, see: (a) W.-
H. Hu, X.-F. Xu, J. Zhou, W.-J. Liu, H.-X. Huang, J. Hu, L.-P.
Yang and L.-Z. Gong, J. Am. Chem. Soc., 2008, 130, 7782; (b)
X. Guan, L. Yang and W.-H. Hu, Angew. Chem., Int. Ed., 2010,
49, 2190; (c) C. Ma, D. Xing, C. Zhai, J. Che, S. Liu, J. Wang
and W. Hu, Org. Lett., 2013, 15, 6140; (d) X. Guo and W.-H.
Hu, Acc. Chem. Res., 2013, 46, 2427; (e) X. Guo, Y. Yue, G. Hu,
J. Zhou, Y. Zhao, L. Yang and W. Hu, Synlett., 2009, 2009
2109.
,
10 (a) H. Qiu, M. Li, L.-Q. Jiang, F.-P. Lv, L. Zan, C.-W. Zhai, M. P.
Doyle and W.-H. Hu, Nat. Chem., 2012, , 733; (b) D. Zhang,
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H. Qiu, L.-Q. Jiang, F.-P. Lv, C.-Q. Ma and W.-H. Hu, Angew.
Chem., Int. Ed., 2013, 52, 13356; (c) S. Jia, D. Xing, D. Zhang
and W.-H. Hu, Angew. Chem., Int. Ed., 2014, 53, 13098.
11 I. Aviv and Z. Gross, Chem. Commun., 2006, 4477.
Scheme 7 Proposed mechanism
In summary, we have developed an efficient process of
construction of poly-functional primary amines, which 12 For recent reviews, see: (a) G. S. Singh and Z. Y. Desta, Chem.
Rev., 2012, 112, 6104; (b) R. Dalpozzo, G. Bartoli and G.
Bencivenni, Chem. Soc. Rev., 2012, 41, 7247; (c) F. Zhou, Y.-L.
Liu and J. Zhou, Adv. Syn. Catal., 2010, 352, 1381.
proceeds via trapping of ammonium ylides generated from
diazocompounds and ammonia. The reaction works efficiently
with excellent chemoselectivity for producing unprotected
amines under mild reaction conditions. We expect this
transformation will be of use to synthesize poly-functional
primary amines.
13 For selected examples, see: (a) Y.-L. Liu, B.-L. Wang, J.-J. Cao,
L. Chen, Y.-X. Zhang, C. Wang and J. Zhou, J. Am. Chem. Soc.,
2010, 132, 15176; (b) G. Bergonzini and P. Melchiorre,
Angew. Chem. Int. Ed. , 2012, 51, 971; (c) R. Niu, J. Xiao, T.
Liang and X. Li, Org. Lett., 2012, 14, 676; (d) A. Kumar and S.
We are grateful for financial support from NSF of China
(21332003, 21402051).
S. Chimni, RSC Adv., 2012,
Jagt, J. G. de Vries, B. L. Feringa and A. J. Minnaard, Org.
Lett., 2006, , 2715.
2, 9748; (e) P. Y. Toullec, R. B. C.
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14 (a) B. Viswambharan, D. Gori, R. Guillot, C. Kouklovsky and V.
Alezra, Org. Lett. , 2014, 16, 788; (b) X. Jiang, Y. Cao, Y.
Wang, L. Liu, F. Shen and R. Wang, J. Am. Chem. Soc. , 2010,
132, 15328.
15 S.-K. Jia, Y.-B. Lei, L.-L. Song, S.-Y. Liu and W.-H. Hu, Chin.
16 Fe(TPFPP)Cl is soluble whereas Fe(TPP)Cl is insoluble in
methanol. Fe(TPFPP)Cl also efficiently catalyze three-
component reactions in THF.
Notes and references
1
“ammonia”: M. Appl in Ullmann's Encyclopedia of Industrial
Chemistry, 7th ed. Online, Wiley, New York.
2
(a) D. M. Roundhill, Chem. Rev., 1992, 92, 1; (b) J. L.
Klinkenberg and J. F. Hartwig, Angew. Chem. Int. Ed., 2011,
50, 86; (c) J. I. van der Vlugt, Chem. Soc. Rev., 2010, 39, 2302;
(d) J. Kim, H. J. Kim and S. Chang, Eur. J. Org. Chem., 2013,
2013, 3201.
17 J. R. Wolf, C. G. Hamaker, J.-P. Djukic, T. Kodadek and L. K.
Woo, J. Am. Chem. Soc., 1995, 117, 9194.
4 | J. Name., 2012, 00, 1-3
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