Journal of the American Chemical Society
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M.; Xu, K.; Breit, B. Angew. Chem. Int. Ed. 2015, 54, 7149; (g) Xu,
K.; Raimondi, W.; Bury, T.; Breit, B. Chem. Commun. 2015, 10861;
(h) Xu, K.; Gilles, T.; Breit, B. Nature Commun. 2015, 6, 7616; (i)
Chen, Q.ꢀA.; Chen, Z.; Dong, V. M. J. Am. Chem. Soc. 2015, 137,
8392; (j) Liu, J.; Han, Z.; Wang, X.; Wang, Z.; Ding, K. J. Am.
Chem. Soc. 2015, 137, 15346; (k) Xu, K.; Wang, Y.ꢀH.;
Khakyzadeh, V.; Breit, B. Chem. Sci. 2016, 7, 3313.
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In conclusion, we have developed a catalytic enantioselective
terminal addition to allenes by the synergistic enamine/palladium
catalysis with chiral primary amine as the sole chiral source. The
reaction could be generally applied to αꢀbranched aldehydes and
ketones to afford allylic adducts bearing acyclic allꢀcarbon quaꢀ
ternary centers. The strategy features an atomꢀeconomical process
under rather mild conditions and expands the scopes of typical
allylic reagents to include 1,1ꢀdisubstituted and alkyl allyl fragꢀ
ments in CꢀC bond formation.
(6) (a) Pritzius, A. B.; Breit, B. Angew. Chem. Int. Ed. 2015, 54, 3121;
(b) Pritzius, A. B.; Breit, B. Angew. Chem. Int. Ed. 2015, 54, 15818.
(7) (a) Trost, B. M.; Brieden, W.; Baringhaus, K. H. Angew. Chem. Int.
Ed. Engl. 1992, 31, 1335; (b) Yamamoto, Y.; AlꢀMasum, M.; Asao,
N. J. Am. Chem. Soc. 1994, 116, 6019; (c) Trost, B. M.; Gerusz, V.
J. J. Am. Chem. Soc. 1995, 117, 5156; (d) Yamamoto, Y.; Alꢀ
Masum, M.; Fujiwara, N.; Asao, N. Tetrahedron Lett. 1995, 36,
2811; (e) Trost, B. M.; Michellys, P.ꢀY.; Gerusz, V. J. Angew.
Chem., Int. Ed. 1997, 36, 1750; (f) AlꢀMasum, M.; Yamamoto, Y. J.
Am. Chem. Soc. 1998, 120, 3809; (g) Kadota, I.; Shibuya, A.;
Gyoung, Y. S.; Yamamoto, Y. J. Am. Chem. Soc. 1998, 120, 10262;
(h) Patil, N. T.; Pahadi, N. K.; Yamamoto, Y. Synthesis 2004, 2186;
(i) Patil, N. T.; Nawaz Khan, F. Tetrahedron Lett. 2004, 45, 8497; (j)
Patil, N. T.; Pahadi, N. K.; Yamamoto, Y. Can. J. Chem. 2005, 83,
569; (k) Patil, N. T.; Kadota, I.; Shibuya, A.; Gyoung, Y. S.;
Yamamoto, Y. Adv. Synth. Catal. 2004, 346, 800.
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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
ASSOCIATED CONTENT
Supporting Information
Experimental details, characterization of new compounds and
computational studies. This material is available free of charge via
AUTHOR INFORMATION
(8) Coulson, D. R. J. Org. Chem. 1973, 38, 1483.
Corresponding Author
(9) (a) Ballesteros, A.; MoránꢀPoladura, P.; González, J. M. Chem.
Commun. 2016, 52, 2905; (b) FernándezꢀCasado, J.; Nelson, R.;
Mascareňas, J. L.; López, F. Chem. Commun. 2016, 52, 2909. (c)
Zhou, H.; Wei, Z.; Zhang, J.; Yang, H.; Xia, C.; Jiang, G. Angew.
Chem. Int. Ed. 2017, 56, 1077.
(10) For leading examples of asymmetric allylic alkylation with aldeꢀ
hydes to generate αꢀquaternary stereocenters, see: (a) Mukherjee, S.;
List, B. J. Am. Chem. Soc. 2007, 129, 11336; (b) Jiang, G. X.; List,
B. Angew. Chem., Int. Ed., 2011, 50, 9471; (c) Krautwald, S.; Sarꢀ
lah, D.; Schafroth, M. A.; Carreira, E. M. Science, 2013, 340, 1065;
(d) Yoshida, M.; Terumine, T.; Masaki, E.; Hara, S. J. Org. Chem.
2013, 78, 10853; (e) Wang, P.ꢀS.; Lin, H.ꢀC.; Zhai, Y.ꢀJ.; Han, Z.ꢀ
Y.; Gong, L.ꢀZ. Angew. Chem. Int. Ed. 2014, 53, 12218; (e) Wright,
T. B.; Evans, P. A. J. Am. Chem. Soc. 2016, 138, 15303. 7.
(11) For leading examples of the asymmetric allylic alkylation with
ketones to generate αꢀquaternary stereocenters, see: (a) Hayashi, T.;
Kanehira, K.; Tsuchiya, H.; Kumada, M. J. Chem. Soc., Chem.
Commun. 1982, 1162; (b) Sawamura, M.; Nagata, H.; Sakamoto, H.;
Ito, Y. J. Am. Chem. Soc. 1992, 114, 2586; (c) Trost, B. M.; Radiꢀ
nov, R.; Grenzer, E. M. J. Am. Chem. Soc. 1997, 119, 7879; (d)
Kuwano, R.; Ito, Y. J. Am. Chem. Soc. 1999, 121, 3236; (e)
Kuwano, R.; Nishio, R.; Ito, Y. Org. Lett. 1999, 1, 837; (f) Trost, B.
M.; Xu, J. J. Am. Chem. Soc. 2005, 127, 2846; (g) Trost, B. M.; Xu,
J.; Reichle, M. J. Am. Chem. Soc. 2007, 129, 282; (h) Trost, B. M.;
Xu, J.; Schmidt, T. J. Am. Chem. Soc. 2009, 131, 18343; (i) Trost,
B. M.; Thaisrivongs, D. A.; Donckele, E. J. Angew. Chem. Int. Ed.
2012, 52, 1523; (j) Keith, J. A.; Behenna, D. C.; Sherden, N.; Mohr,
J. T.; Ma, S.; Marinescu, S. C.; Nielsen, R.; Oxgaard, J.; Stoltz, B.
M.; Goddardlll, W. A. J. Am. Chem. Soc. 2012, 134, 19050; (k) Liu,
W.ꢀB.; Reeves, C. M.; Virgil, S. C.; Stoltz, B. M. J. Am. Chem. Soc.
2013, 135, 10626; (l) Stoltz, B. M.; Liu, W.ꢀB.; Reeves. C. M. J.
Am. Chem. Soc. 2013, 135, 17298; (m) Chen, W.; Chen, M.; Hartꢀ
wig, J. F. J. Am. Chem. Soc. 2014, 136, 15825; (n) Trost, B. M.;
Donckele, E. J.; Thaisrivongs, D. A.; Osipov, M.; Masters, J. T. J.
Am. Chem. Soc. 2015, 137, 2776. (o) Chen, J.ꢀP.; Peng, Q.; Lei, B.ꢀ
L.; Hou, X.ꢀL.; Wu, Y.ꢀD. J. Am. Chem. Soc. 2011, 133, 14180.
(12) When we prepared the manuscript, Breit and Dong independently
reported the Rhꢀcatalyzed branch selective addition of allenes to βꢀ
diketones and aldehydes: (a) Beck, T. M.; Breit, B. Angew. Chem.
Int. Ed. 2017, 56, 1903; (b) Cruz, F. A.; Dong, V. M. J. Am. Chem.
Soc. 2017, 139, 1029.
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENT
We thank the Natural Science Foundation of China (21390400,
21572232, 21672217 and 21521002) for financial support. S.L. is
supported by the National Program of Topꢀnotch Young Profesꢀ
sionals and CAS Oneꢀhundred Talents Program (D).
REFERENCES
(1) For reviews, see: (a) Yamamoto, Y.; Radhakrishnan, U. Chem. Soc.
Rev. 1999, 28, 199; (b) Zimmer, R.; Dinesh, C. U.; Nandanan, E.;
Khan. F. A. Chem. Rev. 2000, 100, 3067; (c) Ma. S. Acc. Chem.
Res. 2003, 36, 701; (c) Ma. S. Chem. Rev. 2005, 105, 2829ꢀ2872; (d)
Jeganmohan, M.; Cheng, C.ꢀH. Chem. Commun. 2008, 3101; (e) Yu,
S.; Ma. S. Angew. Chem. Int. Ed. 2012, 51, 3074; (f) Soriano, E.;
Fernández, I. Chem. Soc. Rev. 2014, 43, 3041; (g) Ye, J.; Ma, S.
Acc. Chem. Res. 2014, 47, 989; (h) Koschker, P.; Breit, B. Acc.
Chem. Res. 2016, 49, 1524.
(2) For reviews, see: (a) Trost, B. M.; Vranken, D. L. van. Chem. Rev.
1996, 96, 395; (b) Trost, B. M. Acc. Chem. Res. 1996. 29, 355; (c)
Trost, B. M.; Crawley, M. L. Chem. Rev. 2003, 103, 2921; (d)
Trost, B. M.; Machacek, M. R.; Aponick, A. Acc. Chem. Res. 2006.
39, 747; (e) Lu, Z.; Ma, S. Angew. Chem. Int. Ed. 2008, 47, 258.
(3) (a)
Trost, B.
M.; Jäkel, C.; Plietker, B. J.
Am.
Chem.
A. B.
Soc. 2003, 125, 4438;
(b) Trost, B. M.; Simas,
C.; Plietker, B.; Jäkel, C.; Xie, J. Chem. Eur.-J. 2005, 11, 7075; (c)
Trost, B. M.; Xie, J.; Sieber, J. D. J. Am. Chem. Soc. 2011, 133,
20611; (d) Li, M.; Datta, S.; Barber, D. M.; Dixon, D. J. Org. Lett.
2012, 14, 6350; (e) Li, M.; Hawkins, A.; Barber, D. M.; Bultinck,
P.; Herrebout, W.; Dixon, D. J. Chem. Commun. 2013, 49, 5265.
(4) For reviews, see: (a) Muñoz, M. P. Org. Biomol. Chem., 2012, 10,
3584; (b) Muzart, J.; Bras, J. L. Chem. Soc. Rev. 2014, 43, 3003; (c)
Koschker, P.; Lumbroso, A.; Breit, B. J. Am. Chem. Soc. 2011, 133,
20746; (d) Lim, W.; Kim, J.; Rhee, Y. H. J. Am. Chem. Soc. 2014,
136, 13618; (e) Jiang, L.; Jia, T.; Wang, M.; Liao, J.; Cao, P. Org.
Lett. 2015, 17, 1070; (f) Koschker, P.; Kähny, M.; Breit, B. J. Am.
Chem. Soc. 2015, 137, 3131; (g) Haydl, A. M.; Breit, B. Angew.
Chem. Int. Ed. 2015, 54, 15330; (h) Liu, Z.; Breit, B. Angew. Chem.
Int. Ed. 2016, 55, 8440; (i) Ganss, S.; Breit, B. Angew. Chem. Int.
Ed. 2016, 55, 9738.
(13) (a) Zhang, L.; Fu, N. K.; Luo, S. Z. Acc. Chem. Res. 2015, 48, 986;
(b) H. Zhou, L. Zhang, C. Xu, S. Luo, Angew. Chem. Int. Ed. 2015,
54, 12645.
(14) The decreased yield is probably due to the large excess primary
amine catalyst which may poisoned the Pd catalyst.
(5) (a) Kim, H.; Rhee, Y. H. J. Am. Chem. Soc. 2012, 134, 790; (b)
Butler, K. L.; Tragni, M.; Widenhoefer, R. A. Angew. Chem. Int. Ed.
2012, 51, 5175; (c) Kim, H.; Lim, W.; Im, D.; Kim, D.; Rhee, Y. H.
Angew. Chem. Int. Ed. 2012, 51, 12055; (d) Xu, K.; Thieme, N.;
Breit, B. Angew. Chem. Int. Ed. 2014, 53, 2162; (e) Xu, K.; Thieme,
N.; Breit, B. Angew. Chem. Int. Ed. 2014, 53, 7268; (f) Haydl, A.
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