Zhou et al.
JOCArticle
of C2-symmetric ligands which have been widely used in a
great number of asymmetric metal-catalyzed reactions including
Henry reaction.9 Compared with the former C2-symmetric
ligands, the structures and electronic properties of C1-sym-
metric ligands are more feasible to adjust. Nevertheless, the
latter are less developed until very recently. Besides natu-
ral sparteine,10a (þ)-NME ((þ)-N-methylephedrine)10b and
brucine-derived amino alcohol,10c there are a few artificial
C1-symmetric ligands suitable for catalytic asymmetric
Henry reaction such as aminopyridine,10d,e 9-oxabispidine10f
and bipiperidine.10g Generally, the reported C1-symmetric
diamine ligands with two N (sp3) coordinating atoms can
be divided into three types: two tertiary amines,10f,11a one
tertiary amine plus one sulfonylamine,11b,c and one tertiary
amine plus one secondary amine.10g Considering the success-
ful applications of C2-symmetric secondary diamine ligands
derived from chiral 1,2-cyclohexanediamine and 1,2-diphe-
nylethylenediamine in copper-catalyzed asymmetric Henry
reactions,12 we are interested in developing C1-symmetric
diamine ligands with two secondary amines for the ease of
structure modification in order to improve the shortcomings
of the previous asymmetric catalyst systems for Henry reac-
tion such as high catalyst loading, sensitivity to air or
moisture, and narrow substrate variation.
(6) Selected examples for Zn-catalyzed asymmetric Henry reaction:
(a) Zhong, Y.; Tian, P.; Lin, G. Tetrahedron: Asymmetry 2004, 15, 771–
776. (b) Gao, J.; Zigaro, R. A.; Reibenspires, J. H.; Martell, A. Org. Lett.
2004, 6, 2453–2455. (c) Liu, S.; Wolf, C. Org. Lett. 2008, 10, 1831–1834.
€
(d) Bulut, A.; Aslan, A.; Dogan, O. J. Org. Chem. 2008, 73, 7373–7375.
Selected examples for Co-catalyzed asymmetric Henry reaction: (e) Kogami,
Y.; Nakajima, T.; Ashizawa, T.; Kezuka, S.; Ikeno, T.; Yamada, T. Chem.
Lett. 2004, 33, 614–615. (f) Park, J.; Lang, K.; Abboud, K. A.; Hong, S.
J. Am. Chem. Soc. 2008, 130, 16484–16485. Selected examples for Cr-
catalyzed asymmetric Henry reaction: (g) Kowalczyk, R.; Sidorowicz, Ł.;
_
Skarzewski, J. Tetrahedron: Asymmetry 2007, 18, 2581–2586. (h) Kowalczyk,
R.; Kwiatkowski, P.; Skarzewski, J.; Jurczak, J. J. Org. Chem. 2009, 74, 753–
_
756. (i) Zulauf, A.; Mellah, M.; Schulz, E. J. Org. Chem. 2009, 74, 2242–2245.
Selected examples for Mg-catalyzed asymmetric Henry reaction: (j) Choudary,
B. M.; Ranganath, K. V. S.; Kantam, U.; Pal, M. L.; Sreedhar, B. J. Am. Chem.
Soc. 2005, 127, 13167–13171. Selected examples for Cu-catalyzed asymmetric
Henry reaction: (k) Gan, C.; Lai, G.; Zhang, Z.; Wang, Z.; Zhou, M. Tetra-
hedron: Asymmetry 2006, 17, 725–728. (l) Lai, G.; Wang, S.; Wang, Z. Tetra-
Toward this end, we designed and prepared a series of C1-
symmetric diamine ligands from the commercially available
chiral materials such as D-camphor, L-menthone, and natural
amino acids. Herein, we present a highly enantioselective and
practically useful Henry reaction between a variety of alde-
hydes and nitroalkanes catalyzed by a newly developed
ꢀ
hedron: Asymmetry 2008, 19, 1813–1819. (m) Blay, G.; Climent, E.; Fernandez,
I.; Hernandez-Olmos, V.; Pedro, J. R. Tetrahedron: Asymmetry 2006, 17, 2046–
ꢀ
ꢀ
ꢀ
2049. (n) Blay, G.; Climent, E.; Fernandez, I.;Hernandez-Olmos, V.;Pedro, J. R.
Tetrahedron: Asymmetry 2007, 18, 1603–1612. (o) Jiang, J.; Shi, M. Tetrahedron:
Asymmetry 2007, 18, 1376–1382. (p) Ma, K.; You, J. Chem.—Eur. J. 2007, 13,
1863–1871. (q) Bandini, M.; Benaglia, M.; Sinisi, R.; Tommasi, S.; Umani-
Ronchi, A. Org. Lett. 2007, 9, 2151–2153. (r) Qin, B.; Xiao, X.; Liu, X.; Huang,
J.;Wen, Y.;Feng, X. J. Org. Chem. 2007, 72, 9323–9328. (s) Arai, T.; Yokoyama,
N.; Yanagisawa, A. Chem.—Eur. J. 2008, 15, 2052–2059. (t) Rachwalski, M.;
chiral diamine ligand L1/CuCl2 2H2O complex.
3
Results and Discussions
The D-camphor and L-menthone as two classical kinds of
chiral scaffolds have been widely utilized in preparing chiral
reagents and ligands.13 The natural amino acids are another
type of chiral starting material employed usually in devel-
oping various chiral ligands and organocatalysts for asym-
metric catalysis.14 For our purpose, exo-(-)-bornylamine
and (þ)-(1S,2S,5R)-menthylamine were first prepared from
natural D-camphor and L-menthone, respectively (for the
general procedure see Scheme 1). Then, a series of chiral
diamine ligands (L1-L9) were obtained via condensing the
two chiral amines with various Cbz-protected amino acids in
three steps (for the general procedure see Scheme 2). We
found these chiral diamine ligands are stable enough to be
stored at ambient temperature without special precautions
ꢀ
ꢀ
Lesniak, S.; Sznajder, E.; Kiezbasinski,P.Tetrahedron: Asymmetry 2009,20, 1547–
1549. (u) Selvakumar, S.; Sivasankaran, D.; Singh, V. K. Org. Biomol. Chem. 2009,
7, 3156–3162. (v) Mayani, V. J.; Abdi, S. H. R.; Kureshy, R. I.; Khan, N. H.; Das,
A.; Bajaj, H. C. J. Org. Chem. 2010, 75, 6191–6195.
(7) Selected examples for both aromatic and aliphatic aldehydes are
studied systematically: (a) Tanaka, K.; Hachiken, S. Tetrahedron Lett.
2008, 49, 2533–2536. (b) Spangler, K. Y.; Wolf, C. Org. Lett. 2009, 11,
4724–4727; also see refs 6c, 12b, and 12g.
(8) Selected examples for diastereo- and enantioselective Henry reaction:
(a) Sasai, H.; Tokunaga, T.; Watanabe, S.; Suzuki, T.; Itoh, N.; Shibasaki,
M. J. Org. Chem. 1995, 60, 7388–7389. (b) Arai, T.; Yamada, Y. M. A.;
Yamamoto, N.; Sasai, H.; Shibasaki, M. Chem.—Eur. J. 1996, 2, 1368–1372.
(c) Handa, S.; Nagawa, K.; Sohtome, Y.; Matsunaga, S.; Shibasaki, M.
Angew. Chem., Int. Ed. 2008, 47, 3230–3233. (d) Nitabaru, T.; Kumagai, N.;
Shibasaki, M. Tetrahedron Lett. 2008, 49, 272–276. (e) Nitabaru, T.; Nojiri,
A.; Kobayashi, M.; Kumagai, N.; Shibasaki, M. J. Am. Chem. Soc. 2009,
131, 13860–13869. (f) Sohtome, Y.; Hashimoto, Y.; Nagasawa, K. Eur. J.
Org. Chem. 2006, 2894–2897. (g) Sohtome, Y.; Takemura, N.; Takada, K.;
Takagi, R.; Iguchi, T.; Nagasawa, K. Chem. Asian J. 2007, 2, 1150–1160.
(h) Uraguchi, D.; Sakaki, S.; Ooi, T. J. Am. Chem. Soc. 2007, 129, 12392–
12393. (i) Cheng, L.; Dong, J.; You, J.; Gao, G.; Lan, J. Chem.—Eur. J. 2010,
16, 6761–6765. (j) Kanagaraj, K.; Suresh, P.; Pitchumani, K. Org. Lett. 2010,
12, 4070–4073; also see refs 9h, 10d, 10g, 11b, and 12d.
(9) For recent reviews, see: (a) Yoon, T. P.; Jacobsen, E. N. Science 2003,
299, 1691–1693. (b) Desimoni, G.; Faita, G.; Jøgensen, K. A. Chem. Rev.
2006, 106, 3561–3651. (c) Achard, T. R. J.; L. Clutterbuck, A.; North, M.
Synlett 2005, 12, 1828–18470. Selected examples for BOX-type ligand
catalyzed asymmetric Henry reaction: (d) Christensen, C.; Juhl, K.;
Jøgensen, K. A. Chem. Commun. 2001, 2222–2223. (e) Christensen, C.; Juhl,
K.; Hazell, R. G.; Jøgensen, K. A. J. Org. Chem. 2002, 67, 4875–4881.
(f) Risgaard, T.; Gothelf, K. V.; Jøgensen, K. A. Org. Biomol. Chem. 2003, 1,
153–156. (g) Ginotra, S. K.; Singh, V. K. Org. Biomol. Chem. 2007, 5, 3932–
3937. (h) Toussaint, A.; pfaltz, A. Eur. J. Org. Chem. 2008, 4591–4597.
(i) Gaab, M.; Bellemin-Laponnaz, S.; Gade, L. H. Chem.—Eur. J. 2009, 15,
5450–5462. (j) Lang, K.; Park, J.; Hong, S. J. Org. Chem. 2010, 75, 6424–
6435; also see reference 5. Selected examples for salen-type ligand catalyzed
asymmetric Henry reaction: see refs 6f 6g, 6h, and 6i.
(11) (a) Arai, T.; Watanabe, M.; Yanagisawa, A. Org. Lett. 2007, 9, 3595–
3597. (b) Arai, T.; Takashita, R.; Endo, Y.; Watanabe, M.; Yanagisawa, A.
J. Org. Chem. 2008, 73, 4903–4906. (c) Steurer, M.; Bolm, C. J. Org. Chem.
2010, 75, 3301–3310.
(12) (a) Arai, T.;Watanabe, M.; Fujiwara, A.; YokoyamaN.; Yanagisawa,
A. Angew. Chem., Int. Ed. 2006, 45, 5978–5981. (b) Bandini, M.; Piccinelli,
F.; Tommasi, S.; Umani-Ronchi, A.; Ventrici, C. Chem. Commun. 2007,
_
616–618. (c) Kowalczyk, R.; Sidorowicz, Ł.; Skarzewski, J. Tetrahe-
dron: Asymmetry 2008, 19, 2310–2315. (d) Kowalczyk, R.; Skarzewski, J.
_
Tetrahedron: Asymmetry 2009, 20, 2467–2473. (e) Zhang, G.; Yashima, E.;
Woggon, W. D. Adv. Synth. Catal. 2009, 351, 1255–1262. (f) Xiong, Y.;
Wang, F.; Huang, X.; Wen, Y.; Feng, X. Chem.—Eur. J. 2007, 13, 829–833.
(g) Jin, W.; Li, X.; Huang, Y.; Wu, F.; Wan, B. Chem.—Eur. J. 2010, 16, 8259–
8261.
(13) For recent reviews, see: (a) Wolfgang, O. Tetrahedron 1987, 43, 1969–
2004. (b) Gennari, C. Pure Appl. Chem. 1997, 69, 507–512. (c) Giorigio, C.
Chem. Soc. Rev. 2006, 35, 1230–1243. (d) Luo, Y.; Zhang, H.; Wang, Y.; Xu,
P. Acc. Chem. Res. 2010, 43, 1317–1330.
(14) For recent reviews, see: (a) Mori, A.; Abet, H.; Inoue, S. Appl.
Organomet. Chem. 1995, 9, 189–197. (b) Severin, K.; Bergs, R.; Beck, W.
Angew. Chem., Int. Ed. 1998, 37, 1634–1654. (c) Hoveyda, A. H.; Hird, A. W.;
Kacprzynski, M. A. Chem. Commun. 2004, 1779–1785. (d) Javro, E. R.;
Miller, S. J. Tetrahedron 2002, 58, 2481–2495. (e) List, B. Tetrahedron 2002,
58, 5573–5590. (f) Note, W.; Tanaka, F.; Barbas, C. F., III. Acc. Chem. Res.
2004, 37, 580–591. (g) Paradowska, J.; Stodulski, M.; Mlynarski, J. Angew.
Chem., Int. Ed. 2009, 48, 4288–4297. (h) Xu, L.; Luo, J.; Lu, Y. Chem.
Commun. 2009, 1807–1821.
(10) (a) Maheswaran, H.; Prasanth, K. L.; Krishna, G. G.; Ravikumar,
K.; Sridhar, B.; Kantam, M. L. Chem. Commun. 2006, 4066–4068.
(b) Palomo, C.; Oiarbide, M.; Laso, A. Angew. Chem., Int. Ed. 2005, 44,
3881–3884. (c) Kim, H. Y.; Oh, K. Org. Lett. 2009, 11, 5682–5685. (d) Blay,
ꢀ
G.; Domingo, L. R.; Hernandez-Olmos, V.; Pedro, J. R. Chem.—Eur. J.
2008, 14, 4725–4730. (e) Blay, G.; Hernandez-Olmos, V.; Pedro, J. R. Org.
ꢀ
Lett. 2010, 12, 3058–3061. (f) Breuning, M.; Hein, D.; Steiner, M.; Gessner,
V. H.; Strohmann, C. Chem.—Eur. J. 2009, 15, 12764–12769. (g) Noole, A.;
Lippur, K.; Metsala, A.; Lopp, M.; Kanger, T. J. Org. Chem. 2010, 75, 1313–
1316.
J. Org. Chem. Vol. 76, No. 2, 2011 589