10.1002/chem.201901020
Chemistry - A European Journal
COMMUNICATION
2012, 68, 7663-7669. g) L.-H. Sun, Z.-Q. Liang, W.-Q. Jia, S. Ye, Angew.
Chem. Int. Ed. 2013, 52, 5803-5806; Angew. Chem. 2013, 125, 5915-
5918. h) K. Morisaki, M. Sawa, J. Nomaguchi, H. Morimoto, Y. Takeuchi,
K. Mashima, T. Ohshima, Chem. Eur. J. 2013, 19, 8417-8420. i) G.
Huang, Z. Yin, X. Zhang, Chem. Eur. J. 2013, 19, 11992-11998.
[12] For example of enantioselective reduction of N-unprotected
trifluoromethyl ketimine, see: F. Gosselin, P. D. O’Shea, S. Roy, R. A.
Reamer, C. Chen, R. P. Volante, Org. Lett. 2005, 7, 355-358.
[13] For examples of enantioselective nucleophilic addition to N-unprotected
trifluoromethyl ketimine, see: a) V. A. Sukach, N. M. Golovach, V. V.
Pirozhenko, E. B. Rusanov, M. V. Vovk, Tetrahedron: Asymmetry, 2008,
19, 761-764. b) N. Hara, R. Tamura, Y. Funahashi, S. Nakamura, Org.
Lett. 2011, 13, 1662-1665. c) R. Yonesaki, Y. Kondo, W. Akkad, M. Sawa,
K. Morisaki, H. Morimoto, T. Ohshima, Chem. Eur. J. 2018, 24, 15211-
15214.
[7]
For examples of nucleophilic addition to cyclic trifluoromethyl ketimine,
see: a) G. S. Kauffman, G. D. Harris, R. L. Dorow, B. R. P. Stone, R. L.
Parsons Jr., J. A. Pesti, N. A. Magnus, J. M. Fortunak, P. N. Confalone,
W. A. Nugent, Org. Lett. 2000, 2, 3119-3121. b) F.-G. Zhang, X.-Y. Zhu,
S. Li, J. Nie, J.-A. Ma, Chem. Commun. 2012, 48, 11552-11554. c) K.-F.
Zhang, J. Nie, R. Guo, Y. Zheng, J.-A. Ma, Adv. Synth. Catal. 2013, 355,
3497-3502. d) H.-N. Yuan, S. Wang, J. Nie, W. Meng, Q. Yao, J.-A. Ma,
Angew. Chem. Int. Ed. 2013, 52, 3869-3873; Angew. Chem. 2013, 125,
3961-3965. e) Y. Duan, X.-Y. Zhu, J.-A. Ma, Y.-G. Zhou, Tetrahedron
Lett. 2013, 54, 6161-6163. f) H.-N. Yuan, S. Li, J. Nie, Y. Zheng, J.-A.
Ma, Chem. Eur. J. 2013, 19, 15856-15860. g) M.-X. Zhao, H.-L. Bi, R.-H.
Jiang, X.-W. Xu, M. Shi, Org. Lett. 2014, 16, 4566-4569. h) D. Chen, M.-
H. Xu, J. Org. Chem. 2014, 79, 7746-7751. i) S. Zhang, L. Li, Y. Hu, Y.
Li, Y. Yang, Z. Zha, Z. Wang, Org. Lett. 2015, 17, 5036-5039. j) D. Zhou,
Z. Huang, X. Yu, Y. Wang, J. Li, W. Wang, H. Xie, Org. Lett. 2015, 17,
5554-5557. k) D. Zhou, X. Yu, J. Zhang, W. Wang, H. Xie, Org. Biomol.
Chem. 2016, 14, 6193-6196. l) J. Dai, D. Xiong, T. Yuan, J. Liu, T. Chen,
Z. Shao, Angew. Chem. Int. Ed. 2017, 56, 12697-12701; Angew. Chem.
2017, 129, 12871-12875. m) S. G. Lee, S.-G. Kim, RSC Adv. 2017, 7,
34283-34286.
[14] For enantioselective reduction of N-PMP ketimines by means of chiral
phosphoric acid, see: a) A. Henseler, M. Kato, K. Mori, T. Akiyama,
Angew. Chem. Int. Ed. 2011, 50, 8180–8183; Angew. Chem. 2011, 123,
8330–8333. b) C. Zhu, K. Saito, M. Yamanaka, T. Akiyama, Acc. Chem.
Res. 2015, 48, 388-398. c) M. Miyagawa, K. Takashima, T. Akiyama,
Synlett 2018, 29, 1607-1610.
[15] For seminal works on the chiral phosphoric acid catalysis, see: a) T.
Akiyama, J. Itoh, K. Yokota, K. Fuchibe, Angew. Chem. Int. Ed. 2004, 43,
1566-1568; Angew. Chem. 2004, 116, 1592–1594. b) D. Uraguchi, M.
Terada, J. Am. Chem. Soc. 2004, 126, 5356-5357. For selected reviews
on chiral phosphoric acid catalysis, see: c) T. Akiyama, J. Itoh, K.
Fuchibe, Adv. Synth. Catal. 2006, 348, 999-1010. d) T. Akiyama, Chem.
Rev. 2007, 107, 5744-5758. e) M. Terada, Chem. Commun. 2008, 4097-
4112. f) M. Terada, Synthesis 2010, 1929-1982. g) A. Zamfir, S.
Schenker, M. Freund, S. M. Tsogoeva, Org. Biomol. Chem. 2010, 8,
5262-5276. h) D. Parmar, E. Sugiono, S. Raja, M. Rueping, Chem. Rev.
2014, 114, 9047-9153. i) T. Akiyama, K. Mori, Chem. Rev. 2015, 115,
9277-9306. j) D. Parmar, E. Sugiono, S. Raja, M. Rueping, Chem. Rev.
2017, 117, 10608–10620. k) J. Merad, C. Lalli, G. Bernadat, J. Maury, G.
Masson, Chem. Eur. J. 2018, 24, 3925-2943.
[8]
[9]
For examples of catalytic enantioselective umpolung nucleophilic
addition, see: a) Y. Wu, L. Hu, Z. Li, L. Deng, Nature 2015, 523, 445-450.
b) P. Chen, Z. Yue, J. Zhang, X. Lv, L. Wang, J. Zhang, Angew. Chem.
Int. Ed. 2016, 55, 13316-13320; Angew. Chem. 2016, 128, 13510-13514.
c) P. Chen, J. Zhang, Org. Lett. 2017, 19, 6550-6553. d) B. Hu, L. Deng,
Angew. Chem. Int. Ed. 2018, 57, 2233-2237; Angew. Chem. 2018, 130,
2255-2259.
[16] Nucleophilicity of indole is reported to be higher than that of pyrrole, see:
a) B. Kempf, N. Hampel, A. R. Ofial, H. Mayr, Chem. Eur. J. 2003, 9,
2209-2218. b) T. A. Nigst, M. Westermaier, A. R. Ofial, H. Mayr, Eur. J.
Org. Chem. 2008, 2369-2374.
For examples of nucleophilic addition to N-unprotected trifluoromethyl
ketimines, see: a) B. Dhudshia, J. Tiburcio, A. N. Thadani, Chem.
Commun. 2005, 5551-5553. b) F. Palacios, A. M. O. de Retana, S.
Pascual, G. F. de Trocóniz, J. M. Ezpeleta, Eur. J. Org. Chem. 2010,
6618-6626. c) F. Palacios, A. M. O. de Retana, S. Pascual, G. F. de
Trocóniz, Tetrahedron 2011, 67, 1575-1579. c) K. Morisaki, H. Morimoto,
T. Ohshima, Chem. Commun. 2017, 53, 6319-6322. d) M. Sawa, K.
Morisaki, Y. Kondo, H. Morimoto, T. Ohshima, Chem. Eur. J. 2017, 23,
17022-17028.
[17] For selected examples of nucleophilic addition reaction of pyrrole to C=N
bond, see: a) G. Li, G. B. Rowland, E. B. Rowland, J. C. Antilla, Org. Lett.
2007, 9, 4065-4068. b) Q. Kang, X.-J. Zheng, S.-L. You, Chem. Eur. J.
2008, 14, 3539-3542. c) S. Nakamura, Y. Sakurai, H. Nakashima, N.
Shibata, T. Toru, Synlett 2009, 10, 1639-1642. d) J. Feng, W. Yan, D.
Wang, P. Li, Q. Sun, R. Wang, Chem. Commun. 2012, 48, 8003-8005.
e) S.-G. Wang, S.-L. You, Angew. Chem. Int. Ed. 2014, 53, 2194-2197;
Angew. Chem. 2014, 126, 2226-2229. f) H. Lou, Y. Wang, E. Jin, X. Lin,
J. Org. Chem. 2016, 81, 2019-2026. g) L. Wang, A. Rahman, X. Lin, Org.
Biomol. Chem. 2017, 15, 6033-6041. h) A. Rahman, E. Xie, X. Lin, Org.
Biomol. Chem. 2018, 16, 1367-1374.
[10] For example of enantioselective reduction of N-unprotected ketimines
(not trifluoromethyl ketimines), see: a) T. B. Ngyuene, H. Bousserouel,
Q. Wang, F. Guéritte, Org. Lett. 2010, 12, 4705-4707. b) G. Hou, F.
Gosselin, W. Li, J. C. McWilliams, Y. Sun, M. Weisel, P. D. O’Shea, C.-
y. Chen, I. W. Davies, X. Zhang, J. Am. Chem. Soc. 2009, 131, 9882-
9883. c) Q. Zhao, J. Wen, R. Tan, K. Huang, P. Metola, R. Wang, E. V.
Anslyn, X. Zhang, Angew. Chem. Int. Ed. 2014, 53, 8467-8470; Angew.
Chem. 2014, 126, 8607-8610.
[18] The detailed reaction conditions are described in Supporting Information.
[19] The reversal of enantioselectivity is based on the 3.3’-substituents of
chiral BINOL phosphoric acid. For examples of reversal of induction by
3,3’-substituents of chiral BINOL phosphoric acid, see: a) T. Akiyama, T.
Suzuki, K. Mori, Org. Lett. 2009, 11, 2445-2447. b) K. Saito, Y. Moriya,
T. Akiyama, Org. Lett. 2015, 17, 3202-3205.
[11] For examples of enantioselective catalytic nucleophilic addition to N-
unprotected ketimines (not trifluoromethyl ketimines), see: a) D. N. Tran,
N. Cramer, Angew. Chem. Int. Ed. 2011, 50, 11098-11102; Angew.
Chem. 2011, 123, 11294-11298. b) D. N. Tran, N. Cramer, Angew. Chem.
Int. Ed. 2013, 52, 10630-10634; Angew. Chem. 2013, 125, 10824-10828.
[20] The Friedel-Crafts alkylation reaction of indole and pyrrole with N-PMP
trifluoromethyl ketimine 1a has not been reported to the best of our
knowledge.
This article is protected by copyright. All rights reserved.