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ChemComm
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COMMUNICATION
Journal Name
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the stereoselectivity (Scheme 3). The chiral nickel carbene
intermediate A was firstly formed when the Ni(II)/L2-Pi(OiBu)2
complex was mixed with diazo compound 1a along with the loss
of nitrogen gas. The thioindole 2a preferred to attack the
intermediate A from its Re-face because the Si-face was blocked
by the below amide unit of the ligand (Int B and B’). On the other
hand, the steric hindrance of indole unit of 1a with the upward
amide unit of the ligand enabled the discrimination of the
heterotopic lone pairs of sulfur, and resulted in the generation
of sulfonium ylide specie B with R configuration at the sulfur-
center as the major one. According to the mechanism
investigated in our previous works,9a,10 the control of chiral
N,N'-dioxide ligands as well as the induction of chiral sulfur
centre would guide the following proton transfer process in an
enantioselective manner to provide the R,R-configured
intermediate C. Subsequently, the [3,3]-σ rearrangement took
place that C3 of the indole ring attacked the prochiral C3' from
its Re-face to produce intermediate D, thus leading to the (R,E)-
configured product 3aa after isomerization.
175.
(a) S. Yoshida, H. Yorimitsu and K. OsDhOimI:a10, .O10r3g9./DLe0tCtC.,024059009J,
11, 2185; (b) T. Kobatake, S. Yoshida, H. Yorimitsu and K.
Oshima, Angew. Chem., Int. Ed., 2010, 49, 2340; (c) T.
Kobatake, D. Fujino, S. Yoshida, H. Yorimitsu and K. Oshima, J.
Am. Chem. Soc., 2010, 132, 11838.
(a) A. R. Kennedy, M. H. Taday and J. D. Rainier, Org. Lett.,
2001, 3, 2407; (b) A. V. Novikov, A. R. Kennedy and J. D. Rainier,
J. Org. Chem., 2003, 68, 993; (c) A. V. Novikov, A. Sabahi, A. M.
Nyong and J. D. Rainier, Tetrahedron: Asymmetry, 2003, 14,
911; (d) A. M. Nyong and J. D. Rainier, J. Org. Chem., 2005, 70,
746; (e) V. Boyarskikh, A. Nyong and J. D. Rainier, Angew.
Chem., Int. Ed., 2008, 47, 5374.
(a) X. L. Huang and N. Maulide, J. Am. Chem. Soc., 2011, 133,
8510; (b) B. Peng, D. Geerdink, C. Farès and N. Maulide,
Angew. Chem., Int. Ed., 2014, 53, 5462; (c) B. Peng, X. L. Huang,
L.-G. Xie and N. Maulide, Angew. Chem., Int. Ed., 2014, 53,
8718; (d) D. Kaiser, L. F. Veiros and N. Maulide, Chem.–Eur. J.,
2016, 22, 4727; (e) D. Kaldre, B. Maryasin, D. Kaiser, O. Gajsek,
L. González and N. Maulide, Angew. Chem., Int. Ed., 2017, 56,
2212; (f) D. Kaldre, I. Klose and N. Maulide, Science, 2018, 361,
664. (g) A. Pons, J. Michalland, W. Zawodny, Y. Chen, V. Tona
and N. Maulide, Angew. Chem., Int. Ed., 2019, 58, 17303.
(a) A. J. Eberhart, J. E. Imbriglio and D. J. Procter, Org. Lett.,
2011, 13, 5882; (b) A. J. Eberhart, C. Cicoira and D. J. Procter,
Org. Lett., 2013, 15, 3994; (c) A. J. Eberhart and D. J. Procter,
Angew. Chem., Int. Ed., 2013, 52, 4008; (d) A. J. Eberhart, H. J.
Shrives, E. Álvarez, A. Carrër, Y. T. Zhang and D. J. Procter,
Chem.–Eur. J., 2015, 21, 7428.
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Conclusions
In conclusion, we have developed an efficient catalytic
asymmetric
thio-Claisen
rearrangement
of
α-diazo
pyrazoleamides with thioindoles by employing a chiral N,N'-
dioxide-nickel(II) complex catalyst, providing expedient access
to C3-substituted indole derivatives with good to excellent
enantioselectivities. Plausible transition state models were
proposed to elucidate the origin of chiral induction. Further
application of the chiral N,N'-dioxide ligands with metal salts to
other enantioselective synthesis are ongoing in our laboratory.
We appreciate the National Natural Science Foundation of
China (Nos. 21625205 and 21772127) for financial support.
Thanks Dr. Yuqiao Zhou and Dr. Daibing Luo for the assistance
in X-ray analysis.
(a) X. B. Lin, Y. Tang, W. Yang, F. Tan, L. L. Lin, X. H. Liu and X.
M. Feng, J. Am. Chem. Soc., 2018, 140, 3299; (b) Z. K. Zhang,
Z. Sheng, W. Z. Yu, G. J. Wu, R. Zhang, W.-D. Chu, Y. Zhang and
J. B. Wang, Nat. Chem., 2017, 9, 970.
10 X. B. Lin, W. Yang, W. K. Yang, X. H. Liu and X. M. Feng, Angew.
Chem., Int. Ed., 2019, 58, 13492.
11 For reviews of N,N'-dioxide ligands, see: (a) X. H. Liu, L. L. Lin
and X. M. Feng, Acc. Chem. Res., 2011, 44, 574; (b) X. H. Liu, L.
L. Lin and X. M. Feng, Org. Chem. Front., 2014, 1, 298; (c) X. H.
Liu, H. F. Zheng, Y. Xia, L. L. Lin and X. M. Feng, Acc. Chem. Res.,
2017, 50, 2621; (d) X. H. Liu, S. X. Dong, L. L. Lin and X. M. Feng,
Chin. J. Chem., 2018, 36, 791; (e) Z. Wang, X. H. Liu and X. M.
Feng, Aldrichimica Acta, 2020, 53, 3; (f) W. D. Cao, X. H. Liu
and X. M. Feng, Chin. Sci. Bull., (Chin. Ver.) DOI: 10.1360/TB-
2020-0158.
12 The absolute configuration of 4da (CCDC 1974972) was
determined to be R by X-ray crystal analysis and the others
were also determined by comparing the circular dichroism
spectra with that of 4da (see ESI for details).
Conflicts of interest
There are no conflicts to declare
13 F. Wang, L. L. Feng, S. X. Dong, X. H. Liu and X. M. Feng, Chem.
Commun., 2020, 56, 3233. The absolute configuration of 9aa
(CCDC 1998226) was determined to be (R,S) by comparing the
circular dichroism spectra with that of 9da (see ESI for details).
14 For selected asymmetric [3,3]-σ rearrangement developed by
our group, see: (a) Y. B. Liu, X. H. Liu, H. P. Hu, J. Guo, Y. Xia, L.
L. Lin and X. M. Feng, Angew. Chem., Int. Ed., 2016, 55, 4054;
(b) J. Li, L. L. Lin, B. W. Hu, P. F. Zhou, T. Y. Huang, X. H. Liu and
X. M. Feng, Angew. Chem., Int. Ed., 2017, 56, 885; (c) H. F.
Zheng, Y. Wang, C. R. Xu, X. Xu, L. L. Lin, X. H. Liu and X. M.
Feng, Nat. Commun., 2018, 9, 1968; (d) Y. H. Zhou, L. L. Lin, X.
H. Liu, X. Y. Hu, Y. Lu, X. Y. Zhang and X. M. Feng, Angew.
Chem., Int. Ed., 2018, 57, 9113; (e) Y. S. Chen, S. X. Dong, X.
Xu, X. H. Liu and X. M. Feng, Angew. Chem., Int. Ed., 2018, 57,
16554; (f) Q. Tang, K. Fu, P. R. Ruan, S. X. Dong, Z. S. Su, X. H.
Liu and X. M. Feng, Angew. Chem., Int. Ed., 2019, 58, 11846.
15 CCDC 1948996 [Ni(BF4)2·6H2O/L2-Pi(OiBu)2 complex].
Notes and references
1
For selected reviews on thio-Claisen rearrangement, see: (a)
K. C. Majumdar, S. Ghosh and M. Ghoish, Tetrahedron, 2003,
59, 7251; (b) R. F. de la Pradilla and M. T. Alma Viso, Top. Curr.
Chem., 2006, 275, 103; (c) K. C. Majumdar, S. Samanta, B.
Chattopadhyay and N. Pal, Curr. Org. Synth., 2012, 9, 851.
C. M. Hackett and H. Kwart, J. Am. Chem. Soc., 1962, 84, 1754.
For selected examples on traditional thio-Claisen
rearrangement, see: For selected examples on traditional
thio-Claisen rearrangement, see: (a) D. J. Watson, P. N. Devine
and A. I. Meyers, Tetrahedron Letters, 2000, 41, 1367; (b) S.
W. He, S. A. Kozmin and V. H. Rawal, J. Am. Chem. Soc., 2000,
122, 190; (c) Z. H. Liu, H. C. Qu, X. Y. Gu, B. J. Min, J. Nyberg
and V. J. Hruby, Org. Lett., 2008, 10, 4105; (d) S. Nowaczyk, C.
Alayrac, V. Reboul, P. Metzner and M.-T. Averbuch-Pouchot,
J. Org. Chem., 2001, 66, 7841; (e) A. R. Ellwood, A. J. Price
Mortimer, J. M. Goodma and M. J. Porter, Org. Biomol. Chem.,
2013, 11, 7530.
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