Journal of the American Chemical Society
Scheme 1. Synthetic Transformations of Alkene 1aa
Page 4 of 5
REFERENCES
1
2
EtO2C
CO2Et
H
3
4
5
6
O
2a
EtO2C
EtO2C
EtO2C
CO2Et
O
OH
90% yield
3a
74% yield
7
1 a) Smidt, J.; Hafner, W.; Jira, R.; Sedlmeier, J.; Sieber, R.; Kojer,
H.; Rüttinger, R. Angew. Chem. 1959, 71, 176–182; b) Tsuji, J. Syn-
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New Perspectives for the 21st Century, 2nd ed. Wiley, Hoboken, 2004;
e) Jira, R. Angew. Chem., Int. Ed. 2009, 48, 9034–9037.
85% yield
a
7
8
9
h
g
b
c
EtO2C
CO2Et
EtO2C
CO2Et
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
EtO2C
CO2Et
NHBn
2
a) Mitsudome, T.; Mizumoto, K; Mizugaki, T; Jitsukawa, K;
CN
1a
12
8
Kaneda, K. Angew. Chem., Int. Ed. 2010, 49, 1238–1240; b) Morandi,
B.; Wickens, Z. K.; Grubbs, R. H. Angew. Chem., Int. Ed. 2013, 52,
2944–2948; c) DeLuca, R. J.; Edwards, J. L.; Steffens, L. D.; Michel,
B. W.; Qiao, X.; Zhu, C.; Cook, S. P.; Sigman, M. S. J. Org. Chem.
2013, 78, 1682–1686.
77% yield
86% yield
f
d
e
3
EtO2C
CO2Et
a) Mitsudome, T.; Umetani, T; Nosaka, N.; Mori, K.; Mizugaki,
EtO2C
CO2Et
OEt
T.; Ebitani, K.; Kaneda, K. Angew. Chem., Int. Ed. 2006, 45, 481–
485; b) Cornell, C. N.; Sigman, M. S. Inorg. Chem. 2007, 46, 1903–
1909; c) Gligorich, K. M.; Sigman, M. S. Chem. Commun. 2009,
3854–3867; d) Campbell, A. N.; Stahl, S. S. Acc. Chem. Res. 2012,
45, 851–863.
CO2Me
NH
EtO2C
EtO2C
O
11
9
82% yield
86% yield
10
57% yield
4
aReactions conducted on 0.2 mmol of 1a. Isolated yields.
For nitrite-Wacker conditions, see Table 3. a) nitrite-
Wacker; b) nitrite-Wacker then NaBH4, 1:1 MeOH/CH2Cl2,
0 → 23 °C; c) nitrite-Wacker then BnNH2, TMSCN, THF,
23 °C; d) nitrite-Wacker then Ph3P=CHCO2Me, THF, 0 →
23 °C; e) nitrite-Wacker then PhNHNH2•HCl, 4% aq.
H2SO4, EtOH, 110 °C; f) nitrite-Wacker then Pd(OAc)2,
XPhos, K2CO3, acetone, EtOH, 23 °C; g) nitrite-Wacker
then Ohira–Bestmann reagent, EtOH, 60 °C; h) PdCl2,
CuCl2•2H2O, NaCl, 0.2 M HCl, DMF, O2, 35 → 60 °C.
a) Michel, B. W.; Camelio, A. M.; Cornell, C. N.; Sigman, M. S.
J. Am. Chem. Soc. 2009, 131, 6076–6077; b) Michel, B. W.;
McCombs, J. R.; Winkler, A.; Sigman, M. S. Angew. Chem., Int. Ed.
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5
a) Wickens, Z. W.; Morandi, B.; Grubbs, R. H. Angew. Chem.,
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randi, B.; Grubbs, R. H. J. Am. Chem. Soc. 2014, 136, 890–893. For a
recently reported alternative, see Ning, X.-S.; Wang, M.-M.; Yao, C.-
Z.; Chen, X.-M.; Kang, Y.-B. Org. Lett. 2016, 18, 2700–2703.
6
Behenna, D. C.; Stoltz, B. M. J. Am. Chem. Soc. 2004, 126,
15044–15045. For a review on enantioselective formation of quater-
nary stereocenters, see Liu, Y.; Han, S.-J.; Liu, W.-B.; Stoltz, B. M.
Acc. Chem. Res. 2015, 48, 740–751
ASSOCIATED CONTENT
Supporting Information
7
For reviews on the use of enantioselective decarboxylative allylic
alkylations in total synthesis, see: Hong, A. Y.; Stoltz, B. M. Eur. J.
Org. Chem. 2013, 2745–2759.
The Supporting Information is available free of charge on
the ACS Publications website.
8
Xing, X.; O’Connor, N. R.; Stoltz, B. M. Angew. Chem., Int. Ed.
2015, 54, 11186–11190.
9
For an example of this strategy, see Mandal, M.; Yun, H.; Dud-
Experimental procedures and compound characterization
(PDF)
ley, G. B.; Lin, S.; Tan, D. S.; Danishefsky, S. J. J. Org. Chem. 2005,
70, 10619–10637.
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1414–1423; b) Keith, J. A.; Nielsen, R. J.; Oxgaard, J.; Goddard, W.
A., III J. Am. Chem. Soc. 2007, 129, 12342–12343.
AUTHOR INFORMATION
11
Liu, Y.; Virgil, S. C.; Grubbs, R. H.; Stoltz, B. M. Angew.
Chem., Int. Ed. 2015, 54, 11800–11803.
Corresponding Authors
12
For a general review on hydroamination, see: a) Müller, T. E.;
Hultzsch, K. C.; Yus, M.; Foubelo, F.; Tada, M. Chem. Rev. 2008,
108, 3795–3892
Notes
13
a) Henkel, T.; Brunne, R. M.; Müller, H.; Reichel, F. Angew.
The authors declare no competing financial interest.
Chem., Int. Ed. 1999, 38, 643–647; b) Hili, R.; Yudin, A. K. Nat.
Chem. Biol. 2006, 2, 284–287.
14
ACKNOWLEDGMENT
For selected examples see: a) Ryu, J.-S.; Li, G. Y.; Marks, T. J.
J. Am. Chem. Soc. 2003, 125, 12584–12605; b) Crimmin, M. R.;
Casely, I. J.; Hill, M. S. J. Am. Chem. Soc. 2005, 127, 2042–2043; c)
Bronner, S. M.; Grubbs, R. H. Chem. Sci. 2014, 5, 101–106; d)
Utsunomiya, M.; Kuwano, R.; Kawatsura, M.; Hartwig, J. F. J. Am.
Chem. Soc. 2003, 125, 5608–5609; e) Rucker, R. P.; Whittaker, A.
M.; Dang, H.; Lalic, G. J. Am. Chem. Soc. 2012, 134, 6571–6574; f)
Zhu, S.; Niljianskul, N.; Buchwald, S. L. J. Am. Chem. Soc. 2013,
135, 15746–15749; g) Strom, A. E.; Hartwig, J. F. J. Org. Chem.
2013, 78, 8909–8914.
This work was supported by the NSF under the CCI Center
for Selective C–H Functionalization, CHE-1205646. Addi-
tional financial support was provided by Caltech and No-
vartis. Dr. Mona Shahgholi and Naseem Torian are
acknowledged for assistance with high-resolution mass
spectrometry. Dr. Yiyang Liu, Nicholas R. O’Connor, Dr.
Allen Y. Hong, and Prof. Wen-Bo Liu are acknowledged
for contributions to substrate preparation. Beau P. Pritchett
is thanked for preparation of the Ohira–Bestmann reagent.
15 Tschaen, B. A.; Schmink, J. R.; Molander, G. A. Org. Lett. 2013,
15, 500–503.
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