Journal of the American Chemical Society
Page 4 of 5
simple olefins. Further mechanistic studies and synthetic
application are ongoing in our laboratory.
1
2
3
ASSOCIATED CONTENT
4
5
127, 2868. (e) Rogers, M. M.; Kotov, V.; Chatwichien, J.; Stahl, S. S.
Org. Lett. 2007, 9, 4331.
Experimental procedures and characterization data. This material
(7) The word “intermolecular aminocarbonylation” has been used
in the reaction of alkynes by Beller and Alper, which invloves a
sequential CO insertion into alkyl-M (M = Pd, Fe) and amine attack
acyl-M species to deliver carboxylic amides. This concept is
completely different with current transformation. For details, see: (a)
Driller, K. M.; Prateeptongkum, S.; Jackstell, R.; Beller, M. Angew.
Chem. Int. Ed. 2011, 50, 537. (b) Li, Y.; Alper, H.; Yu, Z. Org. Lett.
2006, 8, 5199. Also see: (c) Wu, L.; Liu, C.; Zhang, H.; Ye, K.;
Zhang, G.; Zhang, W.; Duan, Z.; You, S.-L.; Lei, A. Angew. Chem.
Int. Ed. 2014, 53, 2443. (d) Xie, P.; Xie, Y.; Qian, B.; Zhou, H.; Xia,
C.; Huang, H. J. Am. Chem. Soc. 2012, 134, 9902.
(8) For some reviews including intramolecular aminocarbonylation
of alkenes, see: (a) Chiusoli, G. P.; Costa, M. Handbook of
Organopalladium Chemistry for Organic Synthesis, Negishi, E.-I.
Eds., Wiley, New York, 2002, P2595. (b) Wu, X.-F.; Fang, X.; Wu,
L.; Jackstell, R.; Neumann, H.; Beller, M. Acc. Chem. Res. 2014, 47,
1041. (c) Wu, X.-F.; Neumann, H.; Beller, M. Chem. Rev. 2013, 113,
1. (d) Wu, X.-F.; Neumann, H.; Beller, M. ChemSusChem 2013, 6,
229. (e) Tamaru, Y.; Kimura, M. Synlett. 1997, 749. For the selective
examples, see: (f) Hegedus, L. S.; Allen, G. F.; Olsen, D. J. J. Am.
Chem. Soc. 1980, 102, 3583. (g) Tamaru, Y.; Kobayashi, T.;
Kawamura, S.-I.; Ochiai, H.; Yoshida, Z.-I. Tetrahedron Lett. 1985,
26, 4479. (h) Tamaru, Y.; Hojo, M.; Higashimura, H.; Yoshida, Z. J.
Am. Chem. Soc. 1988, 110, 3994. (i) Harayama, H.; Abe, A.; Sakado,
T.; Kimura, M.; Fugami, K.; Tanaka, S.; Tamaru, Y. J. Org. Chem.
1997, 62, 2113. (j) Shinohara, T.; Arai, M. A.; Wakita, K.; Arai, T.;
Sasai, H. Tetrahedron Lett. 2003, 44, 711. (k) Tsujihara, T.;
Shinohara, T.; Takenaka, K.; Takizawa, S.; Onitsuka, K.; Hantanaka,
M.; Sasai, H. J. Org. Chem. 2009, 74, 9274.
(9) (a) Pilarski, L. T.; Selander, N.; Böse, D.; Szabó, K. J. Org. Lett.
2009, 11, 5518. (b) Alam, R.; Pilarski, L. T.; Pershagen, E.; Szabó, K.
J. J. Am. Chem. Soc. 2012, 134, 8778. (c)Pilarski, L. T.; Janson, P. G.;
Szabó, K. J. J. Org. Chem. 2011, 76, 1503.
(10) Check, C. T.; Henderson, W. H.; Wray, B. C.;VandenEynden,
M. J.; Stambuli, J. P. J. Am. Chem. Soc. 2011, 133, 18503.
(11) Yin, G.; Wu, Y.; Liu, G. J. Am. Chem. Soc. 2010, 132, 11978.
(12) Bigi, M. A.; White, M. C. J. Am. Chem. Soc. 2013, 135, 7831.
(13) For the cis-aminopalladation of alkenes, see refs 5g, 6d, and (a)
Liu, G.; Stahl, S. S. J. Am. Chem. Soc. 2007, 129, 6328. (b) Bertrand,
M. B.; Neukom, J. D.; Wolfe, J. P. J. Org. Chem. 2008, 73, 8851. (c)
Muñiz, K.; Hövelmann, C. H.; Streuff, J. J. Am. Chem. Soc. 2008, 130,
763. (d) Hanley, P. S.; Markovic, D.; Hartwig, J. F. J. Am. Chem. Soc.
2010, 132, 6302. (e) White, P. B. ; Stahl, S. S. J. Am. Chem.
Soc. 2011, 133, 18594. (f) Zhu, H.; Chen, P.; Liu, G. J. Am. Chem.
Soc. 2014, 136, 1766.
6
7
8
9
AUTHOR INFORMATION
Corresponding Author
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
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENT
We are grateful for financial support from the National Basic
Research Program of China (973-2015CB856600), the National
Nature Science Foundation of China (Nos. 21225210, 21202185,
21421091 and 21472219), and PHC thanks the financial support
from Key Laboratory of Functional Small Organic Molecule (No.
KLFS-KF-201402).
REFERENCES
(1) (a) Lelais, G.; Seebach, D. Biopolymers 2004, 76, 206. (b)
Seebach, D.; Beck, A. K.; Bierbaum, D. J. Chem. Biodiversity. 2004,
1, 1111. (c) Seebach, D.; Matthews, J. L. J. Chem. Soc. Chem.
Commun. 1997, 2015.
(2) (a) Sonnet, P.; Dallemagne, P.; Guillon, J.; Enguehard, C.;
Stiebing, S.; Tanguy, J.; Bureau, R.; Rault, S.; Auvray, P.; Moslemi,
S.; Sourdaine, P.; Séralini, G.-E. Bioorg. Med. Chem. 2000, 8, 945. (b)
Muller, G. W.; Corral, L. G.; Shire, M. G.; Wang, H.; Moreira, A.;
Kaplan, G.; Stirling. D. I. J. Med. Chem. 1996, 39, 3238.
(3) (a) Cheng, R. P.; Gellman, S. H.; DeGrado, W. F. Chem. Rev.
2001, 101, 3219. (b) Sibi, M. P.; Manyem, S. Tetrahedron 2000, 56,
8033.
( 4 ) (a) Enantioselective Synthesis of β-Amino Acids, 2nd ed.;
Juaristi, E.; Soloshonok, A. V. Eds.; John Wiley & Sons: Hoboken,
NJ, 2005. (b) Cardillo, G.; Tomasini, C. Chem. Soc. Rev. 1996, 25,
117. (c) Palomo, C.; Aizpurua, J. M.; Ganboa, I.; Oiarbide, M. Synlett,
2001, 1813. (d) Cole, D. C. Tetrahedron 1994, 50, 9517. (e) Juaristi,
E.; Lopez-Ruiz, H. Curr. Med. Chem. 1999, 6, 983. (f) Seebach, D.;
Beck, A. K.; Capone, S.; Deniau, G.; Grošelj, U.; Zass, E. Synthesis
2009, 1. (g) Ma, J.-A. Angew. Chem. Int. Ed. 2003, 42, 4290. (f)
Weiner, B.; Szymański, W.; Janssen, D. B.; Minnaard, A. J.; Feringa.
B. L. Chem. Soc. Rev. 2010, 39, 1656.
(14) If I(III) only acts as oxidant to regenerate Pd(II) catalyst, the
catalytic reaction should have a slower rate than stoichiometric
reaction.
(5) For some reviews, see: (a) Müller, T. E.; Beller, M. Chem. Rev.
1998, 98, 675. (b) Brunet, J. J.; Neibecker, D. Catalytic Hetero-
functionalization; Togni, A.; Grützmacher, H. Eds.; Wiley-VHC:
New York, 2001; pp 91. (c) Hong, S.; Marks, T. J. Acc. Chem. Res.
2004, 37, 673. (d) Stahl, S. S. Angew. Chem. Int. Ed. 2004, 43, 3400.
(e) Beller, M.; Seayad, J.; Tillack, A.; Jiao, H. Angew. Chem. Int. Ed.
2004, 43, 3368. (f) Kotov, V.; Scarborough, C. C.; Stahl, S. S. Inorg.
Chem. 2007, 46, 1910. (g) McDonald,R. I.; Liu, G.; Stahl, S. S. Chem.
Rev. 2011, 111, 2981. (h) Beccalli, E. M.; Broggini, G.; Martinelli, M.;
Sottocornola, S. Chem. Rev. 2007, 107, 5318.
(6) For the pioneering intermolecular amination of alkenes with
stoichiometric palladium catalyst, see: (a) Backvall, J. –E. Acc. Chem.
Res. 1983, 16, 335. For the catalytic intermolecular amination of
alkenes, see: (b) Timokhin, V. I.; Anastasi, N. R.; Stahl, S. S. J. Am.
Chem. Soc. 2003, 125, 12996. (c) Timokhin, V. I.; Stahl, S. S. J. Am.
Chem. Soc. 2005, 127, 17888. (d) Brice, J. L.; Harang, J. E.;
Timokhin, V. I.; Anastasi, N. R.; Stahl, S. S. J. Am. Chem. Soc. 2005,
+
(15) Nevado recently reported that hypervalent iodine CF3 regent
(Togni’s reagent) could react with I-. Thus, it is possible that
-
PhI(O2CR)2 could react with CF3CO2 of Pd catalyst to release more
reactive cationic Pd(OCCF3)+. For detail, see: Kong, W.; Casimiro,
M.; Fuentes, N.; Merino, E.; Nevado, C. Angew. Chem. Int. Ed. 2013,
52, 13086.
(16) Szabó and coworkers recently proposed that Pd(IV) catalyst
can be initially generated from oxidation of Pd(II) by PhI(OAc)2,
which could activate allylic C-H bond efficiently, see ref. 9b.
(17) For the high-valent palladium chemistry, see: (a) Daugulis, O.;
Do, H.-Q.; Shabashov, D. Acc. Chem. Res. 2009, 42, 1074. (b)
Powers, D. C.; Ritter, T. Acc. Chem. Res. 2012, 45, 840. (c) Neufeldt,
S. R.; Sanford, M. S. Acc. Chem. Res. 2012, 45, 936.
ACS Paragon Plus Environment