Journal of the American Chemical Society
Page 4 of 4
1
2
3
Notes
The authors declare no competing financial interests.
4
5
6
7
8
9
icon Relat. Elem. 2005, 180, 729–740. (d) Browne, D. M.; Wirth, T.
Curr. Org. Chem. 2006, 10, 1893–1903.
ACKNOWLEDGMENT
This work was supported by the NIGMS (GMꢀ43214). S. L. is
grateful for a predoctoral fellowship by Eli Lilly. We thank Dr.
Robert Knowles for helpful discussions and Dr. ShaoꢀLiang
Zheng for Xꢀray crystallographic characterization of compound
3k.
(5) For recent reports on catalytic enantioselective selenofunctionalizaꢀ
tion reaction: (a) Denmark, S. E.; Kalyani, D.; Collins, W. R. J. Am.
Chem. Soc. 2010, 132, 15752–15765. (b) Guan, H.; Wang, H.;
Huang, D.; Shi, Y. Tetrahedron 2012, 68, 2728ꢀ2735; (c) Wei Q.;
Wang, Y; Du, Y. L.; and Gong, L. Beilstein J. Org. Chem. 2013, 9,
1559–1564.
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
(6) (a) Denmark, S. E.; Collins, W. R.; Cullen, M.D. J. Am. Chem. Soc.
2009, 131, 3490–3492. (b) Denmark, S. E.; Edwards, M. G. J. Org.
Chem, 2006, 71, 7293ꢀ7306
REFERENCES
(7) (a) Nicolaou, K. C.; Claremon, D. A. Barnette, W. E.; Seitz, S. P. J.
Am. Chem. Soc., 1979, 101, 3704–3706. (b) Nicolaou, K. C.; Petaꢀ
sis, N. A.; Claremon, D. A. Tetrahedron, 1985, 41, 4835–4841.
(8) For comparison of anionꢀbinding strength between squaramides and
ureas, see: (a) Amendola, V.; Bergamaschi, G.; Boiocchi, M.; Fabꢀ
brizzi, L.; Milani, M.; Chem. Eur. J., 2010, 4368–4380. (b)
Amendola, V.; Fabbrizzi, L.; Mosca, L.; Schmidtchen, F.ꢀP.; Chem.
Eur. J., 2011, 5972–5981. (c) Lu, T.; Wheeler, S. E. Chem. Eur. J.,
2013, 15141–15147.
(1)
(a) Zhang, Z. G.; Schreiner, P. R. Chem. Soc. Rev. 2009, 38, 1187–
1198. (b) Robert J. Phipps, R. J.; Hamilton, G. L.; Toste, F. D. Na-
ture Chem. 2012, 4, 603–614 (b) Mahlau, M; List, B. Angew.
Chem., Int. Ed. 2013, 52, 518–533; (c) Brak, K.; Jacobsen, E. N.
Angew. Chem., Int. Ed. 2013, 52, 534–561. (d) Evans, N. H.; Beer,
P. D. Angew. Chem. Int. Ed. 2014, 53, 11716–11754.
(9) Decomposition is most likely attributable to oxidation of the thiouꢀ
rea by the high valent selenium reagent.
(2) (a) Reisman, S. E.; Doyle, A. G.; Jacobsen, E. N. J. Am. Chem. Soc.
2008, 130, 7198–7199. (b) Klausen, R. S.; Jacobsen, E. N. Org.
Lett. 2009, 11, 887–890. (c) Knowles, R. R.; Lin, S.; Jacobsen, E.
N. J. Am. Chem. Soc. 2010, 132, 5030–5032. (d) Brown, A. R.,
Kuo, W.ꢀH.; Jacobsen, E. N. J. Am. Chem. Soc. 2010, 132, 9286–
9288. (e) De, C. K.; Mittal, N.; Seidel, D. J. Am. Chem.
Soc. 2011, 133, 16802– 16805. (f) Lin, S.; Jacobsen, E. N. Nature
Chem. 2012, 4, 817ꢀ824. (g) Burns, N. Z.; Written, M. R.; Jacobꢀ
sen, E. N. J. Am. Chem. Soc. 2011, 133, 14578ꢀ14581.
(3) For books and reviews on selenofunctionalization and related
chemistry, see: (a) Nicolaou, K. C. and Petasis, N. A. Selenium in
Natural Product Synthesis; CIS: Philadelphia, 1984. (b) Liotta, D.,
Ed. Organoselenium Chemistry; Wiley: New York, 1987; (c) Back,
T. G., Ed. Organoselenium Chemistry–A Practical Approach; Oxꢀ
ford University Press: Oxford, 1999. (d) Topics in Current Chemis-
try: Organoselenium Chemistry; Wirth, T., Ed.; Springer: Heidelꢀ
berg, 2000. (e) Petragnani, N., Stefani, H. A., and Valduga, C. J.
Tetrahedron 2001, 57, 1411–1448 (f) Ranganathan, S., Muraꢀ
leedharan, K. M., Vaish, N. K., and Jayaraman, N. Tetrahedron
2004, 60, 5273–5308. (g) Wirth, T., Ed.; Organoselenium Chemis-
try: Synthesis and Reactions; WileyꢀVCH: Weinheim, 2012. (h)
Santi, C.; Tidei, C. in PATAI’s Chemistry of Functional Groups;
John Wiley & Sons, Ltd.: Online 2009ꢀ2013.
(10) For examples of chiral squaramideꢀcatalyzed enantioselective reacꢀ
tions involving neutral electrophiles: (a) Malerich, J. P.; Hagihaꢀ
ra, K.; Rawal, V. H. J. Am. Chem. Soc. 2008, 130, 14416–14417.
(b) Konishi, H.; Lam, T. Y.; Malerich, J. P.; Rawal, V. H. Org.
Lett. 2010, 12, 2028–2031. (c) Dai, L.; Wang, S.ꢀX.; Chen, F.ꢀE.
Adv. Synth. Catal. 2010, 352, 2137–2141. (d) Zhu, Y.; Malerich, J.
P.; Rawal, V. H. Angew. Chem., Int. Ed. 2010, 49, 153–156. (e)
Yang, K. S.; Nibbs, A. E.; Türkmen, Y. E.; Rawal, V. H. J. Am.
Chem. Soc. 2013, 135, 16050−16053.
(11) Denmark, S. E.; Collins, W. R. Org. Lett. 2007, 9, 3801ꢀ3804
(12) For studies on the bioactivities of flavonoids, see: (a) Flavonoids in
health and disease, 2nd Ed, RiceꢀEvans, C. A.; Packer, L. Eds.;
New York : Marcel Dekker, c2003. (b) Maloney, D. J.; Deng, J. Z.;
Starck, S. R.; Gao, Z.; Hecht, S. M. J. Am. Chem. Soc. 2005, 127,
4140ꢀ4141. (c) Yáñez, J. A.; Remsberg, C. M.; Takemoto, J. K.;
VegaꢀVilla, K. R.; Andrews, P. K.; Sayre, C. L.; Martinez, S. E.;
and Davies, N. M. In Flavonoid pharmacokinetics: Methods of
Analysis, Preclinical and Clinical Pharmacokinetics, Safety, and
Toxicology. Davies, N. M., Yáñez, J. A. eds.; Chicester: Wiley,
2013, Chapter 1, 1–69.
(13) See Supporting Information for the conditions and spectroscopic
data of the NMR experiments.
(14) The small discrepancy between the ee’s under the two conditions is
due to the formation of a trace amount of racemic product in reacꢀ
tion 2 prior to the addition of the chiral catalyst, as established by
NMR analysis.
(4) For reviews on diastereoselective selenofunctionalization using
chiral selenenylating reagents, see: (a) Wirth, T. Tetrahedron 1999,
55, 1–28. Wirth, T. Angew. Chem., Int. Ed. 2000, 39, 3740–3749.
(c) Tiecco, M.; Testaferri, L.; Marini, F.; Bagnoli, L.; Santi, C.;
Temperini, A.; Sternativo, S.; Tomassini, C. Phosphorus, Sulfur Sil-
Table of Contents artwork here
ACS Paragon Plus Environment