Angewandte Chemie International Edition
10.1002/anie.202013568
COMMUNICATION
2013, 135, 16344-16347; k) X.-F. Cheng, Y. Li, Y.-M. Su, F. Yin, J.-Y.
Wang, J. Sheng, H. U. Vora, X.-S. Wang, J.-Q. Yu, J. Am. Chem. Soc.
013, 135, 1236-1239; l) B.-F. Shi, Y.-H. Zhang, J. K. Lam, D.-H. Wang,
2
J.-Q. Yu, J. Am. Chem. Soc. 2010, 132, 460-461; m) B.-F. Shi, N. Maugel,
Y.-H. Zhang, J.-Q. Yu, Angew. Chem. Int. Ed. 2008, 47, 4882-4886.
S. Anas, A. Cordi, H. B. Kagan, Chem. Commun. 2011, 47, 11483-11485.
a) M. Nakanishi, D. Katayev, C. Besnard, E. P. Kündig, Angew. Chem.
Int. Ed. 2011, 50, 7438; b) D. Katayev, M. Nakanishi, T. Bürgi, E. P.
Kündig, Chem. Sci. 2012, 3, 1422; c) E. Larionov, M. Nakanishi, D.
Katayev, C. Besnard, E. P. Kündig, Chem. Sci. 2013, 4, 1995-2005.
a) N. Martin, C. Pierre, M. Davi, R. Jazzar, O. Baudoin, Chem. –Eur. J.
[
[
3]
4]
[
5]
6]
2012, 18, 4480-4484; b) D. Dailler, R. Rocaboy, O. Baudoin, Angew.
Chem. Int. Ed. 2017, 56, 7218; c) P. M. Holstein, M. Vogler, P. Larini, G.
Pilet, E. Clot, O. Baudoin, ACS Catal. 2015, 5, 4300-4308; d) L. Yang, R.
Melot, M. Neuburger, O. Baudoin, Chem. Sci. 2017, 8, 1344-1349; e) L.
Yang, M. Neuburger, O. Baudoin, Angew. Chem. Int. Ed. 2018, 57, 1394-
1398.
[
a) T. Saget, N. Cramer, Angew. Chem. Int. Ed. 2012, 51, 12842-12845;
b) T. Saget, N. Cramer, Angew. Chem. Int. Ed. 2013, 52, 7865-7868; c)
J. Pedroni, T. Saget, P. A. Donets, N. Cramer, Chem. Sci. 2015, 6, 5164-
5171; d) J. Pedroni, N. Cramer, J. Am. Chem. Soc. 2017, 139, 12398-
12401; e) J. Pedroni, N. Cramer, Angew. Chem. Int. Ed. 2015, 54, 11826-
11829.
Figure 2. Gram-scale borylation of 1 and Transformations of borylated product
55. For the sake of clarity, all the hydrogen atoms are omitted for the single
crystal structure of 56.
[
[
7]
8]
A. P. Smalley, J. D. Cuthbertson, M. J. Gaunt, J. Am. Chem. Soc. 2017,
139, 1412-1415.
T. Lee, J. F. Hartiwig, Angew. Chem. Int. Ed. 2016, 55, 8723-8727; b) T.
Lee, T. W. Wilson, R. Berg, P. Ryberg, J. F. Hartwig, J. Am. Chem. Soc.
In summary, we have developed the CBL/Ir-catalyzed
enantioselective β-C(sp )-H borylation of acyclic amides,
3
2015, 137, 6742-6745.
affording a variety of β-functionalized amides with good to
excellent enantioselectivities under mild reaction conditions. The
C-B bond of the borylated product could undergo a series of
stereospecific transformations to furnish chiral β-substituted
amides. Further applications of CBLs in other contexts of
asymmetric catalysis are currently underway in our laboratory.
[
[
9]
G. Chen, W. Gong, Z. Zhuang, M. S. Andrä, Y.-Q. Chen, X. Hong, Y.-F.
Yang, T. Liu, K. N. Houk, J.-Q. Yu, Science 2016, 353, 1023-1027.
10] a) Y.-Q. Han, Y. Ding, T. Zhou, S.-Y. Yan, H. Song, B.-F. Shi, J. Am.
Chem. Soc. 2019, 141, 4558-4563; b) Y. Ding, Y.-Q. Han, L.-S. Wu, T.
Zhou, Q.-J. Yao, Y.-L. Feng, Y. Li, K.-X. Kong, B.-F. Shi, Angew. Chem.
Int. Ed. 2020, 59, 14060-14064; c) S.-Y. Yan, Y.-Q. Han, Q.-J. Yao, X.-
L. Nie, L. Liu, B.-F. Shi, Angew. Chem. Int. Ed. 2018, 57, 9093-9097.
11] S.-B. Yan, S. Zhang, W.-L. Duan, Org. Lett. 2015, 17, 2458-2461.
12] V. T. Tran, S. K. Nimmagadda, M. Liu, K. M. Engle, Org. Biomol. Chem.
2020, 18, 618-637.
[
[
Acknowledgements
[
13] a) D. Leonori, V. K. Aggarwal, Reagent-Controlled Lithiation–Borylation.
In Synthesis and Application of Organoboron Compounds (Eds.: E.
Fernandez, A. Whiting), Springer International Publishing: Cham, 2015,
pp. 271-295; b) H.-Y. Sun, D. G. Hall, At the Forefront of the
Suzuki−Miyaura Reaction: Advances in Stereoselective Cross-
Couplings. In Synthesis and Application of Organoboron Compounds
We thank National Natural Science Foundation of China
(
21873261 and 91956116), Natural Science Foundation of
Jiangsu Province (BK20170422), Hangzhou Normal University,
and Lanzhou Institute of Chemical Physics for generous financial
support.
(Eds.: E. Fernandez, A. Whiting), Springer International: Cham,
Switzerland, 2015, pp. 221−242.
[
14] B. S. L. Collins, C. M. Wilson, E. L. Myers, V. K. Aggarwal, Angew. Chem.
Inte. Ed. 2017, 56, 11700-11733.
Keywords: C-H activation • organoboron • iridium • synthetic
methods • asymmetric catalysis
[15] a) J.-E. Lee, J. Yun, Angew. Chem. Int. Ed. 2008, 47, 145-147; b) H.
Chea, H.-S. Sim, J. Yun, Adv. Synth. Catal. 2009, 351, 855-858.
[
16] a) T. Ishiyama, J. Takagi, K. Ishida, N. Miyaura, N. R. Anastasi, J. F.
Hartwig, J. Am. Chem. Soc. 2002, 124, 390-391; b) J.-Y. Cho, M. K. Tse,
D. Holmes, R. E. Maleczka, M. R., Smith, Science 2002, 295, 305-308;
c) I. A. I. Mkhalid, J. H. Barnard, T. B. Marder, J. M. Murphy, J. F. Hartwig,
Chem. Rev. 2010, 110, 890-931; d) J. F. Hartwig, Chem. Soc. Rev. 2011,
[
1]
a) H. M. L. Davies, D. Morton, ACS Cent. Sci. 2017, 3, 936-943; b) T. G.
Saint-Denis, R.-Y. Zhu, G. Chen, Q.-F. Wu, J.-Q. Yu, Science 2018, 359,
eaao4798; c) C. G. Newton, S.-G. Wang, C. C. Oliveira, N. Cramer,
Chem. Rev. 2017, 117, 8908-8976; e) R. Giri, B.-F. Shi, K. M. Engle, N.
Maugel, J.-Q. Yu, Chem. Soc. Rev. 2009, 38, 3242-3272.
40, 1992-2002. c) B. Ghaffari, S. M. Preshlock, D. L. Plattner, R. J.
[
2]
a) M. Wasa, K. M. Engle, D. W. Lin, E. J. Yoo, J.-Q. Yu, J. Am. Chem.
Soc. 2011, 133, 19598-19601; b) K. S. L. Chan, H.-Y. Fu, J.-Q. Yu, J.
Am. Chem. Soc. 2015, 137, 2042-2046; c) Q.-F. Wu, P.-X. Shen, J. He,
X.-B. Wang, F. Zhang, Q. Shao, R.-Y. Zhu, C. Mapelli, J. X. Qiao, M. A.
Poss, J.-Q. Yu, Science 2017, 355, 499-503; d) P.-X. Shen, L. Hu, Q.
Shao, K. Hong, J.-Q. Yu, J. Am. Chem. Soc. 2018, 140, 6545-6549; e) L.
Hu, P.-X. Shen, Q. Shao, K. Hong, J. X. Qiao, J.-Q. Yu, Angew. Chem.
Int. Ed. 2019, 58, 2134-2138; f) Z. Zhuang, J.-Q. Yu, J. Am. Chem. Soc.
Staples, P. E. Maligres, S. W. Krska, R. E. Maleczka, M. R., Smith, J.
Am. Chem. Soc. 2014, 136, 14345-14348; d) G. Wang, L. Liu, H. Wang,
Y.-S. Ding, J. Zhou, S. Mao, P. Li, J. Am. Chem. Soc. 2017, 139, 91-94;
e) R. Murakami, K. Tsunoda, T. Iwai, M. Sawamura, Chem. -Eur. J. 2014,
20, 13127-13131.
[
17] a) G. R. Genov, J. L. Douthwaite, A. S. K. Lahdenperä, D. C. Gibson, R.
J. Phipps, Science 2020, 367, 1246-1251; b) R. L. Reyes, M. Sato, T.
Iwai, M. Sawamura, J. Am. Chem. Soc. 2020. 142, 589-597; c) X. Zou,
H. Zhao, Y. Li, Q. Gao, Z. Ke, S. Xu, J. Am. Chem. Soc. 2019, 141, 5334-
2020, 142, 12015-12019; g) Q. Shao, Q.-F. Wu, J. He, J.-Q. Yu, J. Am.
Chem. Soc. 2018, 140, 5322-5325; h) H. Shi, A. N. Herron, Y. Shao, Q.
Shao, J.-Q. Yu, Nature 2018, 558, 581-585; i) R. E. Plata, D. E. Hill, B.
E. Haines, D. G. Musaev, L. Chu, D. P. Hickey, M. S. Sigman, J.-Q. Yu,
D. G. Blackmond, J. Am. Chem. Soc. 2017, 139, 9238-9245; j) L. Chu,
X.-C. Wang, C. E. Moore, A. L. Rheingold, J.-Q. Yu, J. Am. Chem. Soc.
5342; d) Y. Shi, Q. Gao, S. Xu, J. Am. Chem. Soc. 2019, 141, 10599-
10604; e) L. Chen, Y. Yang, L. Liu, Q. Gao, S. Xu, J. Am. Chem. Soc.
2020, 142, 12062-12068; f) J. He, Q. Shao, Q. Wu, J.-Q. Yu, J. Am.
Chem. Soc. 2017, 139, 3344-3347; g) When we were preparing our
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