C O M M U N I C A T I O N S
Table 1. Comparison of BINOL 3a with Sulfones 4/5 (10 mol %)a
Supporting Information Available: Experimental procedures and
characterization data for all new compounds. This material is available
2a (R
yield %
)
Ph)
ee %b
2b (R
yield %
79
)
styryl)
ee %b
entry
BINOL (10 mol %)
1
2
3
3a
77
78
95
82
68c
72c
49
98
59
70
70
88
90
89c
88c
49
68
11
34
References
3a (200 mol %)
4a
4a
4b
4c
4d
4e
5a
85
87
90
97
(1) Nucleophilic addition to imines: (a) Kobayashi, S.; Ishitani, H. Chem.
ReV. 1999, 99, 1069. (b) Bloch, R. Chem. ReV. 1998, 98, 1407. (c) Enders,
D.; Reinhold, U. Tetrahedron: Asymmetry 1997, 8, 1895. (d) Denmark,
S. E.; Nicaise, O. J.-C. Chem. Commun. 1996, 999.
(2) Recent examples of enantioselective imine allylation: (a) Fang, X.;
Johannsen, M.; Yao, S.; Gathergood, N.; Hazell, R. G.; Jørgensen, K. A.
J. Org. Chem. 1999, 64, 4844. (b) Fernandes, R. A.; Stimac, A.;
Yamamoto, Y. J. Am. Chem. Soc. 2003, 125, 14133. (c) Taggi, A. E.;
Hafez, A. M.; Lectka, T. Acc. Chem. Res. 2003, 36, 10. (d) Hamada, T.;
Manabe, K.; Kobayashi, S. Angew. Chem., Int. Ed. 2003, 42, 3927. (e)
Fernandes, R. A.; Yamamoto, Y. J. Org. Chem. 2004, 69, 735. (f) Ding,
H.; Friestad, G. K. Synthesis 2004, 2216. (g) Wada, R.; Shibuguchi, T.;
Makino, S.; Oisaki, K.; Kanai, M.; Shibasaki, M. J. Am. Chem. Soc. 2006,
128, 7687.
4c,d,e
5c
6c
7
71
87
70
44
10
9
8
9
a Conditions as Scheme 1. b Chiral HPLC. c Using allyl bromide. d 100%
conversion, 4 h, 0-4 °C. Same conditions, with 0 mol % 4a, 23% (()-2a.
e No reaction in DMF, CH2Cl2, or MeCN. In 75% aq THF 2a obtained in
20% yield, 33% ee
(3) (a) Berger, R.; Rabbat, P. M. A.; Leighton, J. L. J. Am. Chem. Soc. 2003,
125, 9596. (b) Berger, R.; Duff, K.; Leighton, J. L. J. Am. Chem. Soc.
2004, 126, 5686.
Table 2. Enantioselective Allylation Catalyzed by 4a (10 mol %)a
(4) Kobayashi, S.; Ogawa, C.; Konishi, H.; Sugiura, M. J. Am. Chem. Soc.
2003, 125, 6610. (b) Ferna´ndez, I.; Valdivia, V.; Gori, B.; Alcudia, F.;
AÄ lvarez, E.; Khiar, N. Org. Lett. 2005, 7, 1307. (c) Ogawa, C.; Sugiura,
M.; Kobayashi, S. Angew. Chem., Int. Ed. 2004, 43, 6491.
(5) For indium-mediated allylation of imines, see: (a) Beuchet, P.; Le Marrec,
N.; Mosset, P. Tetrahedron Lett. 1992, 33, 5959. (b) Chan, T. H.; Lu, W.
Tetrahedron Lett. 1998, 39, 8605. (c) Lu, W.; Chan, T. H. J. Org. Chem.
2000, 65, 8589. (d) Kumar, H. M. S.; Anjaneyulu, S.; Reddy, E. J.; Yadav,
J. S. Tetrahedron Lett. 2000, 41, 9311. (e) Lu, W.; Chan, T. H. J. Org.
Chem. 2001, 66, 3467. See also: (f) Prajapati, D.; Laskar, D. D.; Gogoi,
B. J.; Devi, G. Tetrahedron Lett. 2003, 44, 6755. (g) Banik, B. K.; Ghatak,
A.; Becker, F. F. J. Chem. Soc., Perkin Trans. 1 2000, 2179. (h) Ghatak,
A.; Becker, F. F.; Banik, B. K. Heterocycles 2000, 53, 2769. (i)
Skaanderup, P. R.; Madsen, R. J. Org. Chem. 2003, 68, 2115.
(6) (a) Cooper, I. R.; Grigg, R.; MacLachlan, W. S.; Thornton-Pett, M.;
Sridharan, V. Chem. Commun. 2002, 1372. (b) Cooper, I. R.; Grigg, R.;
Hardie, M. J.; MacLachlan, W. S.; Sridharan, V.; Thomas, W. A.
Tetrahedron Lett. 2003, 44, 2283.
(7) (a) Basile, T.; Bocoum, A.; Savoia, D.; Umani-Ronchi, A. J. Org. Chem.
1994, 59, 7766. (b) Loh, T.-P.; Ho, D. S.-C.; Xu, K.-C.; Sim, K.-Y.
Tetrahedron Lett. 1997, 38, 865. (c) Vilaivan, T.; Winotapan, C.;
Banphavichit, V.; Shinada, T.; Ohfune, Y. J. Org. Chem. 2005, 70, 3464.
(8) (a) Lee, J. G.; Choi, K. I.; Pae, A. N.; Koh, H. Y.; Kang, Y.; Cho, Y. S.
J. Chem. Soc., Perkin Trans. 1 2002, 1314. (b) Miyabe, H.; Nishimura,
A.; Ueda, M.; Naito, T. Chem. Commun. 2002, 1454. (c) Miyabe, H.;
Yamaoka, Y.; Naito, T.; Takemoto, Y. J. Org. Chem. 2003, 68, 6745. (d)
Miyabe, H.; Yamaoka, Y.; Naito, T.; Takemoto, Y. J. Org. Chem. 2004,
69, 1415.
(9) Cook, G. R.; Maity, B.; Kargbo, R. Org. Lett. 2004, 6, 1741.
(10) For reviews of diastereoselective allylation of imines using chiral
auxiliaries, see: (a) Lavaro, G.; Savoia, D.; Synlett 2002, 651. (b) Ding,
H.; Friestad, G. K. Synthesis 2005, 2815.
(11) Cook, G. R.; Kargbo, R.; Maity, B. Org. Lett. 2005, 7, 2767.
(12) For enantioselective In-mediated allylation of aldehydes using stoichio-
metric chiral additives, see: (a) Loh, T.-P.; Zhou, J.-R. Tetrahedron Lett.
1999, 40, 9115. (b) Loh, T.-P.; Zhou, J.-R.; Li, X.-R. Tetrahedron Lett.
1999, 40, 9333. (c) Loh, T.-P.; Zhou, J.-R.; Yin, Z. Org. Lett. 1999, 1,
1855. (d) Loh, T.-P.; Lin, M.-J.; Tan, K.-L. Tetrahedron Lett. 2003, 44,
507. (e) Hirayama, L. C.; Gamsey, S.; Knueppel, D.; Steiner, D.;
DeLaTorre, K.; Singaram, B. Tetrahedron Lett. 2005, 46, 2315. (f) using
allylstannanes: (BINOL/InCl3) Teo, Y.-C.; Tan, K.-T.; Loh, T.-P. Chem.
Commun. 2005, 1318. (g) (In(OTf)3/PYBOX) Lu, J.; Ji, S.-J.; Teo, Y.-
C.; Loh, T.-P. Org. Lett. 2005, 7, 159.
a The allylindium/ligand complex was preformed. See Supporting
Information for details. b Yield and ee are the average of at least two runs.
c Chiral HPLC.
(13) Tan, K. L.; Jacobsen, E. N. Angew. Chem., Int. Ed. 2007, 46, 1315.
(14) (a) Chan, T. H.; Yang, Y. J. Am. Chem. Soc. 1999, 121, 3228. (b) Araki,
S.; Ito, H.; Katsumura, N.; Butsugan, Y.; J. Organomet. Chem. 1989,
369, 291.
(15) Hansch, C.; Leo, A.; Taft, R. W. Chem. ReV. 1991, 91, 165.
(16) (a) Charmant, J. P. H.; Dyke, A. M.; Lloyd-Jones, G. C. Chem. Commun.
2003, 380. (b) Zhao, Z.; Messinger, J.; Scho¨n, U.; Wartchow, R.;
Butenscho¨n, H. Chem. Commun. 2006, 3007.
(17) Steensma, R. W.; Galabi, S.; Tagat, J. R.; McCombie, S. W. Tetrahedron
Lett. 2001, 42, 2281.
(18) Kozlowski has reported on arylsulfone-2-naphthol homocoupling to yield
RH ) Ar analogues of 5, in 45-75% ee (98% ee after trituration): Li,
X.; Hewgley, B.; Mulrooney, C. A.; Yang, J.; Kozlowski, M. C. J. Org.
Chem. 2003, 68, 5500.
The bis-SO2RF BINOL 4a facilitates a general and highly enanti-
oselective catalytic indium-mediated imine allylation, affording 2
in up to 99% ee. This represents the highest selectivity to date in
any indium-mediated allylation and the catalyst is easily recovered
(silica-gel chromatography) and recycled (×3) without loss of
activity or selectivity. The SO2RF BINOL systems (4a-c) offer
significant opportunities for exploiting fluorous phase technologies19
in this and other reactions.
(19) For leading references see: (a) The Handbook of Fluorous Chemistry;
Gladysz, J. A., Curran, D. P., Horvath, I. T., Eds.; Wiley-VCH: Weinheim,
Germany, 2004. (b) Pozzi, G.; Shepperson, I. Coord. Chem. ReV. 2003,
242, 115.
Acknowledgment. We are grateful to the National Science
Foundation (Grant NSF-CHM-0616485) and the European Union
(STRP 505167-1 LIGBANK) for financial support. We thank Pfizer
and ND-EPSCoR for graduate fellowships (R.K.).
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