10.1002/anie.202015175
Angewandte Chemie International Edition
COMMUNICATION
P. Garcia-Reynaga, S. Romminger, E. F. Pimenta, D. K. Romney, M. W.
Lodewyk, D. E. Williams, R. J. Andersen, S. J. Miller, D. J. Tantillo, R. G.
S. Berlinck, R. Sarpong, Nature 2014, 509, 318−324.
efficiency and excellent enantioselectivity have been achieved under
mild conditions. This protocol has also been applied in a concise
synthesis of (–)-horsfiline. Mechanistically, this process involves rapid
and reversible halogenation followed by water addition and
rearrangement. Dynamic kinetic resolution of the racemic halide
intermediate is responsible for the observed high enantioselectivity, in
which CPA serves as a bifunctional catalyst.
[6] F. Kolundzic, M. N. Noshi, M. Tjandra, M. Movassaghi, S. J. Miller, J. Am.
Chem. Soc. 2011, 133, 9104−9111.
[7] a) For an example with stoichiometric chiral oxidant: S. Han, M.
Movassaghi, J. Am. Chem. Soc. 2011, 133, 10768−10771; b) For a similar
two-step process with 3-hydroxy-indolenine as intermediate resulting in
either racemic product or low yield/chemoselectivity and ee: E. Schendera,
S. Lerch, T. von Drathen, L.-N. Unkel, M. Brasholz, Eur. J. Org. Chem.
2017, 22, 3134−3138.
Acknowledgements
[8] J. Xu, L. Liang, H. Zheng, Y. R. Chi, R. Tong, Nat. Commun. 2019, 10,
4754.
Financial support was provided by National Natural Science
Foundation of China (91956114) and the Research Grants Council of
Hong Kong (16302617, 16302318). We thank Dr. Herman H. Y. Sung
for help with structure elucidation and Dr. Rongbiao Tong for helpful
discussion. This paper is dedicated to the 10th anniversary of
SUSTech and her Department of Chemistry.
[9] Pioneering studies and recent reviews of CPA-related catalysis: a) T.
Akiyama, J. Itoh, K. Yokota, K. Fuchibe, Angew. Chem., Int. Ed. 2004, 43,
1566−1568; b) D. Uraguchi, M. Terada, J. Am. Chem. Soc. 2004, 126,
5356−5357; c) D. Parmar, E. Sugiono, S. Raja, M. Rueping, Chem. Rev.
2014, 114, 9047−9153. d) T. Akiyama, K. Mori, Chem. Rev. 2015, 115,
9277−9306; e) T. James, M. van Gemmeren, B. List, Chem. Rev. 2015,
115, 9388−9409.
Keywords: asymmetric catalysis • organocatalysis • hydrogen
bonds • heterocycles • rearrangement
[10] Selected reviews and examples involving CPA-catalyzed asymmetric
halogenation: a) X.-W. Liang, C. Zheng, S.-L. You, Chem. Eur. J. 2016, 22,
11918−11933; b) W. Zheng, Z. Zhang, M. J. Kaplan, J. C. Antilla, J. Am.
Chem. Soc. 2011, 133, 3339−3341; c) W. Xie, G. Jiang, H. Liu, J. Hu, X.
Pan, H. Zhang, X. Wan, Y. Lai, D. Ma, Angew. Chem., Int. Ed. 2013, 52,
12924−12927; d) K. Mori, Y. Ichikawa, M. Kobayashi, Y. Shibata, M.
Yamanaka, T. Akiyama, J. Am. Chem. Soc. 2013, 135, 3964−3970.
[11] It is worth noting that aqueous condition was rarely used in CPA catalysis,
presumably due to competing hydrogen bonding. For selected examples of
CPA catalysis in the presence of water, see: a) S. Xu, Z. Wang, X. Zhang,
X. Zhang, K. Ding, Angew. Chem. Int. Ed. 2008, 47, 2840−2843; b) M.
Reuping, T. Theissmann, Chem. Sci. 2010, 1, 473−476; c) K. Yang, Y. Lou,
C. Wang, L.-W. Qi, T. Fang, F. Zhang, H. Xu, L. Zou, W. Li, P. Yu, Q. Song,
Angew. Chem. Int. Ed. 2020, 59,3294−3299.
[1] a) C. Marti, E. M. Carreira, Eur. J. Org. Chem. 2003, 2209−2219; b) C. V.
Galliford, K. A. Scheidt, Angew. Chem. Int. Ed. 2007, 46, 8748−8758; c) N.
Ye, H. Chen, E. A. Wold, P. Y. Shi, J. Zhou, ACS Infect. Dis. 2016, 2,
382−392; d) L.-M. Zhou, R. Y. Qu, G.-F. Yang, Expert Opin. Drug Discov.
2020, 15, 603−625.
[2] a) A. Jossang, P. Jossang, H. A. Hadi, T. Sévenet, B. Bodo, J. Org. Chem.
1991, 56, 6527−6530; b) coerulescine: N. Anderton, P. A. Cockrum, S. M.
Colegate, J. A. Edgar, K. Flower, I. Vit, R. I. Phytochemistry 1998, 48,
437−439; c) C. Pellegrini, M. Weber, H.-J. Borschberg, Helv. Chim. Acta
1996, 79, 151−168; d) S. Shangary, D. Qin, D. McEachern, M. Liu, R. S.
Miller, S. Qiu, Z. Nikolovska-Coleska, K. Ding, G. Wang, J. Chen, D.
Bernard, J. Zhang, Y. Lu, Q. Gu, R. B. Shah, K. J. Pienta, X. Ling, S. Kang,
M. Guo, Y. Sun, D. Yang, S. Wang, Proc. Natl. Acad. Sci. USA 2008, 105,
3933−3938; e) R. C. Elderfield, R. E. Gilman, Phytochemistry 1972, 11,
339−343; f) A.-F. Mohamed, K. Matsumoto, K. Tabata, H. Takayama, M.
Kitajima, N. Aimi, H. Watanabe, J. Pharm. Pharmacol. 2000, 52,
1553−1561; g) C.-B. Cui, H. Kakeya, H. Osada, Tetrahedron 1996, 52,
12651−12666.
[12] a) S. Chowdhury, M. Chafeev, S. Liu, J. Sun, V. Raina, R. Chui, W. Young,
R. Kwan, J. Fu, J. A. Cadieux, Bioorg. Med. Chem. Lett. 2011, 21,
3676−3681; b) W. Shi, Z. Jiang, H. He, F. Xiao, F. Lin, Y. Sun, L. Hou, L.
Shen, L. Han, M. Zeng, K. Lai, Z. Gu, X. Chen, T. Zhao, L. Guo, C. Yang,
J. Li, S. Chen, ACS Med. Chem. Lett. 2018, 9, 94−97; c) C. A. Demerson,
L. G. Humber, Spiroindolones. US Patent, 4226860, 1980.
[13] Pioneering studies, selected applications, and recent developments of the
inverted oxidative rearrangement: a) B. Witkop, A. Ek, J. Am. Chem. Soc.
1951, 5664−5669; b) N. Finch, C. W. Gemenden, I. H.-C. Hsu, A. Kerr, G.
A. Sim, W. Taylor, J. Am. Chem. Soc. 1965, 87, 2229−2235; c) Baran, P.
S.; Corey, E. J. J. Am. Chem. Soc. 2002, 124, 7904−7905; d) R. M. Williams,
R.J. Cox, Acc. Chem. Res. 2003, 36, 127−139; Recent efforts for the
asymmetric variant: e) W. Ding, Q.-Q. Zhou, J. Xuan, T.-R. Li, L.-Q. Lu, W.-
J. Xiao, Tetrahedron Lett. 2014, 55, 4648−4652; f) L. Bu, J. Li, Y. Yin, B.
Qiao, G. Chai, X. Zhao, Z. Jiang, Chem. Asian J. 2018, 13, 2382−2387.
[14] The presence of such a heteroatom in the methylene substituent appeared
to be important for clean rearrangement under the standard conditions. In
the absence of this heteroatom, the halogenation step remains clean, but
the rearrangement step was slow and unselective.
[3] Reviews on the synthesis of siprooxindoles: a) B. M. Trost, M. K. Brennan,
Synthesis 2009, 3003−3025; b) R. Dalpozzo, G. Bartoli, G. Bencivenni,
Chem. Soc. Rev. 2012, 41, 7247−7290; c) M. M. M. Santos, Tetrahedron
2014, 70, 9735−9757; d) D. Cheng, Y. Ishihara, B. Tan, C. F. Barbas, ACS
Catal. 2014, 4, 743−762; e) Z.-Y. Cao, F. Zhou, J. Zhou, Acc. Chem. Res.
2018, 51, 1443−1454.
[4] Pioneering reports: a) N. Finch, W. I. Taylor, J. Am. Chem. Soc. 1962, 84,
1318−1320; b) J. Shavel, H. Zinnes, J. Am. Chem. Soc. 1962, 84,
1320−1321.
[5] Selected applications in alkaloid synthesis, see Refs. 1a, 2 and a) H.
Takayama, K. Masubuchi, M. Kitajima, N. Aimi, S. Sakai, Tetrahedron 1989,
45, 1327−1336; b) C. Pellegrini, C. Strässler, M. Weber, H.-J. Borschberg,
Tetrahedron: Asymmetry 1994, 5, 1979−1992; c) T. D. Cushing, J. F. Sanz-
Cervera, R. M. Williams, J. Am. Chem. Soc. 1996, 118, 557−579; d) S. D.
Edmondson, S. J. Danishefsky, Angew. Chem., Int. Ed. 1998, 37,
1138−1140; e) S. Edmondson, S. J. Danishefsky, L. Sepp-Lorenzino, N.
Rosen, J. Am. Chem. Soc. 1999, 121, 2147−2155; f) M. Ito, C. W. Clark, M.
Mortimore, J. B. Goh, S. F. Martin, J. Am. Chem. Soc. 2001, 123,
8003−8010; g) P. S. Baran, J. M. Richter, J. Am. Chem. Soc. 2005, 127,
15394−15396; h) J.Yang, X. Z. Wearing, P. W. Le Quesne, Deschamps, J.
R. Deschamps, J. M. Cook, J. Nat. Prod. 2008, 71, 1431−1440; i) M. A.
Schmidt, M. Movassaghi, Synlett 2008, 313−324; j) E. V. Mercado-Marin,
[15] An aza-quinone methide intermediate has been previously proposed for this
type of rearrangement: a) J. M. Schkeryantz, J. C. G. Woo, P. Siliphaivanh,
K. M. Depew, S. J. Danishefsky, J. Am. Chem. Soc. 1999, 121,
11964−11975; b) M. Movassaghi, M. A. Schimidt, J. A. Org. Lett. 2008, 10,
4009−4012.
[16] The X-ray data have been deposited at the Cambridge Crystallographic
Data Center (CCDC 2024347 for 2d, CCDC 2024348 for 4a, and CCDC
2024354 for 6b).
4
This article is protected by copyright. All rights reserved.