Organic Letters
Letter
(6) (a) Masri, M. S.; Friedman, M. J. Protein Chem. 1988, 7, 49.
(b) Liu, S.; Zhou, B.; Yang, H.; He, Y.; Jiang, Z.-X.; Kumar, S.; Wu, L.;
Zhang, Z.-Y. J. Am. Chem. Soc. 2008, 130, 8251. (c) Morales-Sanfrutos,
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(7) Boor, J., Jr.; Finch, A. M. T. J. Polym. Sci., Part A-1: Polym. Chem.
1971, 9, 249. Also see ref 5.
Scheme 6. Catalytic Chemo- and Regioselective Fluorescent
Labeling of Amino Diol
(8) We evaluated various ligands. Among them, bis-phosphine ligand
was found to be effective. Without the ligand, inferior result was
obtained, presumably due to the low solubility of silver salt.
̀
(9) Giardina, A.; Giovannini, R.; Petrini, M. Tetrahedron Lett. 1997,
38, 1995. We also confirmed that hydroxy adduct 3aa underwent
retro-reaction under optimal conditions.
ASSOCIATED CONTENT
* Supporting Information
The Supporting Information is available free of charge on the
(10) We checked the reaction profile of KHMDS catalysis (Table 1,
entry 10). Phenyl vinyl sulfone (1a) was completely consumed within
5 min, and the yield of the product 3aa was constant during the course
of the reaction (60 min). We concluded that the addition of soft Lewis
acid efficiently suppressed the undesired polymerization.
(11) Recent review on palladium-catalyzed cross-coupling reaction:
Johansson Seechurn, C. C. C.; Kitching, M. O.; Colacot, T. J.;
Snieckus, V. Angew. Chem., Int. Ed. 2012, 51, 5062.
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S
Experimental details, characterization data, and NMR
spectra of all products (PDF)
(12) Late-stage pyridine functionalization: Fier, P. S.; Hartwig, J. F. J.
Am. Chem. Soc. 2014, 136, 10139.
AUTHOR INFORMATION
Corresponding Authors
(13) For reviews on click chemistry, see: (a) Kolb, H. C.; Finn, M.
G.; Sharpless, K. B. Angew. Chem., Int. Ed. 2001, 40, 2004. (b) Hein, J.
E.; Fokin, V. V. Chem. Soc. Rev. 2010, 39, 1302.
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Notes
(14) Kanno, O.; Nakajima, K.; Aoki, K.; Tanaka, R.; Hirano, S.;
Oizumi, K.; Asano, D. Int. Appl. PCT WO 2010/082563, 2010.
(15) (a) He, H.; Liu, W. B.; Dai, L. X.; You, S. L. J. Am. Chem. Soc.
2009, 131, 8346. (b) Liang, Z.; Ju, L.; Xie, Y.; Huang, L.; Zhang, Y.
Chem. - Eur. J. 2012, 18, 15816. (c) Tang, C.; Jiao, N. J. Am. Chem. Soc.
2012, 134, 18924. (d) Liang, Z.; Feng, R.; Yin, H.; Zhang, Y. Org. Lett.
2013, 15, 4544. (e) Liang, Z.; Yao, J.; Wang, K.; Li, H.; Zhang, Y.
Chem. - Eur. J. 2013, 19, 16825. (f) Suzuki, C.; Morimoto, K.; Hirano,
K.; Satoh, T.; Miura, M. Adv. Synth. Catal. 2014, 356, 1521. (g) Suzuki,
C.; Hirano, K.; Satoh, T.; Miura, M. Org. Lett. 2015, 17, 1597. (h) Zuo,
Z.; Liu, J.; Nan, J.; Fan, L.; Sun, W.; Wang, Y.; Luan, X. Angew. Chem.,
Int. Ed. 2015, 54, 15385.
(16) (a) Lazareva, A.; Daugulis, O. Org. Lett. 2006, 8, 5211.
(b) Morimoto, K.; Itoh, M.; Hirano, K.; Satoh, T.; Shibata, Y.; Tanaka,
K.; Miura, M. Angew. Chem., Int. Ed. 2012, 51, 5359. (c) Miura, M.;
Feng, C.; Ma, S.; Yu, J. Org. Lett. 2013, 15, 5258. (d) Ravi Kumar, D.;
Satyanarayana, G. Org. Lett. 2015, 17, 5894.
(17) Protected amino diol was used for catalytic regioselective
acylation: Yoshida, K.; Shigeta, T.; Furuta, T.; Kawabata, T. Chem.
Commun. 2012, 48, 6981.
(18) We confirmed that the ratio of β-AA/AA was constant (around
70/30) when the reaction was quenched within five minutes using
DPPE as ligand (<30% conversion).
(19) We also evaluated the ratio of AgOAc/rac-BINAP, and a 1:1
ratio was most effective. Thus, we speculated that the AgOAc/rac-
BINAP = 1:1 complex would be an actual catalytic species. For silver
BINAP complexes, see: Momiyama, N.; Yamamoto, H. J. Am. Chem.
Soc. 2004, 126, 5360.
(20) At this stage, the ligand effect was not clear. We speculated that
a slightly more Lewis acidic silver complex would be generated using
rac-BINAP, allowing for rapid bidentate coordination of β-amino
alcohol. Further studies to elucidate the precise reaction mechanism
are in progress.
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
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This work was financially supported by a Grant-in-Aid for
Scientific Research (B) (No. 24390004), Young Scientists (B)
(No. 26860012), and Scientific Research on Innovative Area
2707 Middle Molecular Strategy and Platform for Drug
Discovery, Informatics, and Structural Life Science from
MEXT. We thank the research group of Prof. Hiroshi Suemune
at Kyushu University for the use of a polarimeter.
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