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Journal of the American Chemical Society
1
2
3
4
5
6
7
8
9
Yamamoto, Springer-Verlag, New York, 1999; Chapter 31; (c)
Gini, F.; Hessen, B.; Feringa, B. L.; Minnaard, A. J. Chem. Com-
R.; Takeda, M.; Nishimura, T.; Hayashi, T. Angew. Chem., Int. Ed.
2010, 49, 3969–3971.
11
mun. 2007, 710–712.
For excellent review articles, see: (a) Gutnov, A. Eur. J. Org.
2
For reviews, see: (a) Harutyunyan, S. R.; den Hartog, T.; Geurts,
Chem. 2008, 4547–4554. (b) Christoffers, J.; Koripelly, G.; Rosiak,
A.; Rössle, M. Synthesis 2007, 1279–1300.
K.; Minnaard, A. J.; Feringa, B. L. Chem. Rev. 2008, 108,
2824–2882. (b) Alexakis, A.; Backvall, J. E.; Krause, N.; Pamies,
O.; Dieguez, M. Chem. Rev. 2008, 108, 2796–2893. (c) Lopez, F.;
Minnarard, A. J.; Feringa, B. L. Acc. Chem. Res. 2007, 40,
179–188. (d) Hayashi, T.; Yamasaki, K. Chem. Rev. 2003, 103,
2829–2844. (e) Feringa, B. L. Acc. Chem. Res. 2000, 33,
346–353. (f) Rossiter, B. E.; Swingle, N. M. Chem. Rev. 1992, 92,
12 Lin, S.; Lu, X. Org. Lett. 2010, 12, 2536–2539.
13
Kikushima, K.; Holder, J. C.; Gatti, M.; Stoltz, B. M. J. Am.
Chem. Soc. 2011, 133, 6902–6905.
14
PyOx ligand scaffolds are increasingly common in asymmetric
catalysis, see: (a) Podhajsky, S. M.; Iwai, Y.; Cook-Sneathen, A.;
Sigman, M. S. Tetrahedron 2011, 67, 4435–4441. (b) Aranda, C.;
Cornejo, A.; Fraile, J. M.; García-Verdugo, E.; Gil, M. J.; Luis, S.
V.; Mayoral, J. A.; Martínez-Merino, V.; Ochoa, Z. Green Chem.
2011, 13, 983–990. (d) Pathak, T. P.; Gligorich, K. M.; Welm, B.
E.; Sigman, M. S. J. Am. Chem. Soc. 2010, 132, 7870–7871. (d)
Jiang, F.; Wu, Z.; Zhang, W. Tetrahedron Lett. 2010, 51,
5124–5126. (e) Jensen, K. H.; Pathak, T. P.; Zhang, Y.; Sigman, M.
S. J. Am. Chem. Soc. 2009, 131, 17074–17075. (f) He, W.; Yip, K.-
T.; Zhu, N.-Y.; Yang, D. Org. Lett. 2009, 11, 5626–5628. (g) Dai,
H.; Lu, X. Tetrahedron Lett. 2009, 50, 3478–3481. (h) Linder, D.;
Buron, F.; Constant, S.; Lacour, J. Eur. J. Org. Chem. 2008,
5778–5785. (i) Schiffner, J. A.; Machotta, A. B.; Oestreich, M.
Synlett 2008, 2271–2274. (j) Koskinen, A. M. P.; Oila, M. J.; Tois,
J. E. Lett. Org. Chem. 2008, 5, 11–16. (k) Zhang, Y.; Sigman, M.
S. J. Am. Chem. Soc. 2007, 129, 3076–3077. (l) Yoo, K. S.; Park,
C. P.; Yoon, C. H.; Sakaguchi, S.; O’Neill, J.; Jung, K. W. Org.
Lett. 2007, 9, 3933–3935. (m) Dhawan, R.; Dghaym, R. D.; St.
Cyr, D. J.; Arndtsen, B. A. Org. Lett. 2006, 8, 3927–3930. (n) Xu,
W.; Kong, A.; Lu, X. J. Org. Chem. 2006, 71, 3854–3858. (o)
Malkov, A. V.; Stewart Liddon, A. J. P.; Ramírez-López, P.; Ben-
dová, L.; Haigh, D.; Kocovsky, P. Angew. Chem., Int. Ed. 2006, 45,
1432–1435. (p) Abrunhosa, I.; Delain-Bioton, L.; Gaumont, A.-C.;
Gulea, M.; Masson, S. Tetrahedron 2004, 60, 9263–9272. (q)
Brunner, H.; Kagan, H. B.; Kreutzer, G. Tetrahedron: Asymmetry
2003, 14, 2177–2187. (r) Cornejo, A.; Fraile, J. M.; García, J. I.;
Gil, M. J.; Herrerías, C. I.; Legarreta, G.; Martínez-Merino, V.;
Mayoral, J. A. J. Mol. Catal. A: Chem. 2003, 196, 101–108. (s)
Zhang, Q.; Lu, X.; Han, X. J. Org. Chem. 2001, 66, 7676–7684. (t)
Zhang, Q.; Lu, X. J. Am. Chem. Soc. 2000, 122, 7604–7605. (u)
Perch, N. S.; Pei, T.; Widenhoefer, R. A. J. Org. Chem. 2000, 65,
3836–3845. (v) Bremberg, U.; Rahm, F.; Moberg, C. Tetrahedron:
Asymmetry 1998, 9, 3437–3443. (w) Brunner, H.; Obermann, U.;
Wimmer, P. Organometallics 1989, 8, 821–826.
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
771–806.
3
(a) Shintani, R.; Duan, W.-L.; Hayashi, T. J. Am. Chem. Soc.
2006, 128, 5628–5629. (b) Hayashi, T.; Takahashi, M.; Takaya, Y.;
Ogasawara, M.; J. Am. Chem. Soc. 2002, 124, 5052–5058. (c)
Takaya, Y.; Ogasawara, M.; Hayashi, T. J. Am. Chem. Soc. 1998,
120, 5579–5580.
4
(a) Nishikata, T.; Yamamoto, Y.; Miyaura, N. Angew. Chem., Int.
Ed. 2003, 42, 2768–2770. (b) Nishitaka, T.; Yamamoto, Y.; Mi-
yaura, N. Chem. Lett. 2007, 36, 1442–1443. (c) Nishitaka, T.; Ki-
yomura, S.; Yamamoto, Y.; Miyaura, N. Synlett 2008, 2487–2490.
5
Gini, F.; Hessen, B.; Minnaard, A. J. Org. Lett. 2005, 7,
5309–5312.
6
For reviews on the synthesis of quaternary stereocenters, see: (a)
Denissova, I.; Barriault, L. Tetrahedron 2003, 59, 10105–10146.
(b) Douglas, C. J.; Overman, L. E. Proc. Natl. Acad. Sci. U.S.A.
2004, 101, 5363–5267. (c) Christoffers, J.; Baro, A. Adv. Synth.
Catal. 2005, 347, 1473–1482. (d) Trost, B. M.; Jiang, C. Synthesis
2006, 369–396. (e) Mohr, J. T.; Stoltz, B. M. Chem. Asian J. 2007,
21, 1476–1491. (f) Cozzi, P. G.; Hilgraf, R.; Zimmermann, N. Eur.
J. Org. Chem. 2007, 5969–5994.
6
For an excellent comprehensive review, see: Hawner, C.; Alex-
akis, A. Chem. Commun. 2010, 46, 7295–7306.
7
(a) Wu, J.; Mampreian D. M.; Hoveyda, A. H. J. Am. Chem. Soc.
2005, 127, 4584–4585. (b) Hird, A. W.; Hoveyda, A. H. J. Am.
Chem. Soc. 2005, 127, 14988–14989. (c) Lee, K.-S.; Brown, M. K.;
Hird, A. W.; Hoveyda, A. H. J. Am. Chem. Soc. 2006, 128,
7182–7184. (d) Brown, M. K.; May, T. L.; Baxter, C. A.; Hoveyda,
A. H. Angew. Chem., Int. Ed. 2007, 46, 1097–1100. (e) Fillion, E.;
Wilsily, A. J. Am. Chem. Soc. 2006, 128, 2774–2775. (f) Wilsily,
A.; Fillion, E. J. Org. Chem. 2009, 74, 8583–8594. (g) Dumas, A.
M.; Fillion, E. Acc. Chem. Res. 2010, 43, 440–454. (h) Wilsily, A.;
Fillion, E. Org. Lett. 2008, 10, 2801–2804.
8 (a) d’Augustin, M.; Palais, L.; Alexakis, A. Angew. Chem., Int. Ed.
2005, 44, 1376–1378. (b) Vuagnoux-d’Augustin, M.; Alexakis, A.
Chem.–Eur. J. 2007, 13, 9647–9662. (c) Palais, L.; Alexakis, A.
Chem.–Eur. J. 2009, 15, 10473–10485. (d) Fuchs, N.; d’Augustin,
M.; Humam, M.; Alexakis, A.; Taras, R.; Gladiali, S. Tetrahedron:
Asymmetry 2005, 16, 3143–3146. (e) Vuagnoux-d’Augustin, M.;
Kehrli, S.; Alexakis, A. Synlett, 2007, 2057–2060. (f) May, T. L.;
Brown, M. K.; Hoveyda, A. H. Angew. Chem., Int. Ed. 2008, 47,
7358–7362. (g) Ladjel, C.; Fuchs, N.; Zhao, J.; Bernardinelli, G.
Alexakis, A. Eur. J. Org. Chem. 2009, 4949–4955. (h) Palais, L.;
Mikhel, I. S.; Bournaud, C.; Micouin, L.; Falciola, C. A.; Vuag-
noux-d’Augustin, M.; Rosset, S.; Bernardinelli, G.; Alexakis, A.
Angew. Chem., Int. Ed. 2007, 46, 7462–7465. (i) Hawner, C.; Li,
K.; Cirriez, V.; Alexakis, A. Angew. Chem., Int. Ed. 2008, 47,
8211–8214. (j) Müller, D.; Hawner, C.; Tissot, M.; Palais, L.; Alex-
akis, A. Synlett 2010, 1694–1698. (k) Hawner, C.; Müller, D.;
Gremaud, L.; Felouat, A.; Woodward, S.; Alexakis, A. Angew.
15 The ligand was prepared as described in the literature, see: Brun-
ner, H.; Obermann, U. Chem. Ber. 1989, 122, 499–507. See Sup-
porting Information for experimental details.
16
(a) Xu, Q.; Zhang, R.; Zhang, T.; Shi, M. J. Org. Chem. 2010,
75, 3935–3937; (b) Zhang, T.; Shi, M. Chem.–Eur. J. 2008, 14,
3759–3764; (c) Gottummukkala, A. L.; Matcha, K.; Lutz, M.; de
Vries, J. G. ; Minnaard, A. J. Chem.–Eur. J. 2012, 18, 6907–6914.
17
Holder, J. C., Marziale, A. N., Gatti, M.; Mao, B.; Stoltz, B. M.
Chem.–Eur. J. 2013, 19, 74–77.
18
We believe the small amount of deuterium incorporation at the
methylene adjacent the enone occurs via substrate enolization dur-
ing the extended reaction times under the mild reaction conditions.
19
Duan, W.-L.; Iwamura, H.; Shintani, R.; Hayashi, T. J. Am.
Chem. Soc. 2007, 129, 2130–2138.
20 Guillaneux, D.; Zhao, S.-H.; Samuel, O.; Rainford, D.; Kagan, H.
B. J. Am. Chem. Soc. 1994, 116, 9430–9439. Further evidence for
the monomeric nature of the Pd/PyOx catalyst was provided by
comparison of diffusion rates of various PyOx/Pd complexes by
diffusion oriented spectroscopy (DOSY NMR). These studies sug-
gest an upper bound for the molecular weight of the solution species
of the catalyst, demonstrating that dimeric (ML)2 complexes are not
Chem., Int. Ed. 2010, 49, 7769–7772.
9
(a) Martin, D.; Kehrli, S.; d’Augustin, M.; Clavier, H.; Mauduit,
M.; Alexakis, A. J. Am. Chem. Soc. 2006, 128, 8416–8417. (b)
Kehrli, S.; Martin, D.; Rix, D.; Mauduit, M.; Alexakis, A.
Chem.–Eur. J. 2010, 16, 9890–9904. (c) Hénon, H.; Mauduit, M.;
Alexakis, A. Angew. Chem., Int. Ed. 2008, 47, 9122–9124. (d)
Matsumoto, Y.; Yamada, K.-I.; Tomioka, K. J. Org. Chem. 2008,
present. See Supporting Information.
21
(a) Inanaga, J.; Furuno, H.; Hayano, T. Chem. Rev. 2002, 102,
2211–2226. (b) Kagan, H. B. Synlett 2001, 888–899. (c) Girard, C.;
Kagan H. B. Angew. Chem., Int. Ed. 1998, 37, 2922–2959.
73, 4578–4581.
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(a) Shintani, R.; Tsutsumi, Y.; Nagaosa, M.; Nishimura, T.; Ha-
For preparation and use of (PyOx)Pd(OCOCF3)2 see Supporting
yashi, T. J. Am. Chem. Soc. 2009, 131, 13588–13589. (b) Shintani,
Information.
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