1248
S. Saito et al.
LETTER
Kobayashi, S.; Sano, T. Tetrahedron 1984, 46, 4653.
Vol 2 1989, 39, 25. (k) Mahrwald, R.; Gundogan, B. J. Am.
Chem. Soc. 1998, 120, 413. (l) Mascarenhas, C. M.; Duffey,
M. O.; Liu, S.-Y.; Morken, J. P. Org. Lett. 1999, 1, 1427.
(m) Loh, T.-P.; Wei, L.-L.; Feng, L.-C. Synlett 1999, 1059.
(n) Taylor, S. J.; Duffey, M. O.; Morken, J. P. J. Am. Chem.
Soc. 2000, 122, 4528.
(d) Mukaiyama, T. Tetrahedron 1981, 37, 4111.
(e) Mukaiyama, T.; Iwasawa, N.; Stevens, R. W.; Haga, T.
Tetrahedron 1984, 40, 1381. (f) Yuste, F.; Ortiz, B.; Carrasco,
A.; Peralta, M.; Quintero, L.; Schez-Obregon, R.; Walls, F.;
Ruano, J. L. G. Tetrahedron: Asymmetry 2000, 11, 3079.
(8) Typical Procedure for the Aldol Reaction Using a Protonic
acid and a Diamine in Acetone. The following procedure for
the reaction of p-nitrobenzaldehyde (1a) in acetone using acid
19 and diamine 4 (1 mol% each) is representative. To a
mixture of diamine 4 (3.3 L, 0.02 mmol) and acid 19 (5.4 mg,
0.02 mmol) in acetone (4.0 mL) was added 1a (2.0 mmol) at
23 °C under air in a closed system. The reaction mixture was
stirred at 43 °C for 30 h. n-Oct3SiMe (47.1 L, 0.1 mmol) was
added as an internal standard just before quenching with aq.
NaCl. The organic layer was extracted with EtOAc, dried over
Na2SO4, and concentrated. The residue was analyzed by 1H
NMR to give 1b in an NMR yield of 73%, together with 1c in
12% yield. After purification by column chromatography on
silica gel (EtOAc/hexane = 1/1 as the eluent), the
(2) Saito, S.; Yamamoto, H. Chem. Eur. J. 1999, 5, 1959, and
references cited therein.
(3) For metal- and organo-catalysts, see: (a) Cole, B. M.;
Shimizu, K. D.; Krueger, C. A.; Harrity, J. P. A.; Snapper, M.
L.; Hoveyda, A. H. Angew. Chem. Int. Ed. Engl. 1996, 35,
1668.
(b) Shimizu, K. D.; Cole, B. M.; Krueger, C. A.; Kuntz, K. V.;
Snapper, M. L.; Hoveyda, A. H. Angew. Chem. Int. Ed. Engl.
1997, 36, 1704. (c) Sigman, M. S.; Jacobsen, E. N. J. Am.
Chem. Soc. 1998, 120, 4901. (d) Francis, M.; Jacobsen, E. N.;
Angew. Chem. Int. Ed. Engl. 1999, 38, 937.
(4) (a) Koshechkina, L. P.; Mel’nichenko, I. V. Ukr. Khim. Zhur.
1974, 40, 172. (b) Koshechkina, L. P.; Yasnikov, A. A. Ukr.
Khim. Zhur. 1974, 40, 948, and references cited therein. Class
I aldolases and catalytic antibodies which involve a protonic
acid and two (amino) basic groups are remarkably useful for
the asymmetric direct aldol reaction, see: (c) Hoffmann, T.;
Zhong, G.; List, B.; Shabat, D.; Anderson, J.; Gramatikova,
S.; Lerner, R. A.; Barbas III, C. F.; J. Am. Chem. Soc. 1998,
120, 2779. (d) Barbas III, C.; Heine, A.; Zhong, G.;
Hoffmann, T.; Gramatikova, S.; Björnestedt, R.; List, B.;
Anderson, J.; Stura, E. A.; Wilson, I. A.; Lerner, R. A. Science
1997, 278, 2085. (e) Wagner, J.; Lerner, R. A.; Barbas III, C.
F. Science 1995, 270, 1797, and references cited therein. For
small diamine protonic acid modules directed to the effective
formation of iminium-salts: (f) Hine, J.; Chou, Y. J. Org.
Chem. 1981, 46, 649, and references cited therein. Diamines
alone resulted mainly in the formation of dehydration prod-
ucts, see: (g) Choudary, B. M.; Kantam, M. L.; Sreekanth, P.;
Bandopadhay, T.; Figueras, F.; Tuel, A. J. Mol. Cat. A: Chem.
1999, 142, 361. (h) Sercheli, R.; Vargas, R. M.; Sheldon, R.
A.; Schechardt, U. J. Mol. Cat. A: Chem. 1999, 148, 173. In
addition, dehydrated homo-aldol adducts were formed in the
presence of catalytic pyrrolidine and PhCO2H, see:
(i) Ishikawa, T.; Uedo, E.; Okada, S.; Saito, S. Synlett 1999,
450.
(5) Diamine-protonic acid catalyst 21 4 was reported to promote
the asymmetric three-component Mannich-type reaction and,
very recently, the direct aldol reaction by Barbas III, see:
(a) Notz, W.; Sakthivel, K.; Bui, T.; Zhong, G.; Barbas III, C.
F. Tetrahedron Lett. 2001, 42, 199. See also ref. 1h. Diamine
4 alone was also tested for the Mannich-type reaction by List,
see Supporting Information of: (b) List, B. J. Am. Chem. Soc.
2000, 122, 9336.
(6) List, Lerner and Barbas III et al. reported the asymmetric
direct aldol reaction of acetone using proline or its analogues
with a TON of ca. 1~4 with moderate to high (ca. 60~96%) ee.
See references 1b and 1h.
enantiomeric excess (ee) of 1b was determined to be 77% ee
by chiral HPLC analysis. The chiral HPLC analytical data
(column OB-H) of 1b: retention times: tR = 28.49 min ((R):
major isomer) and tR = 33.39 min ((S): minor isomer) using i-
PrOH/hexane (1/6) as an eluent at a flow rate of 1.0 mL/min.
The ee of 2b was similarly determined by chiral HPLC
analysis. The chiral HPLC analytical data (column OB-H) of
2b: retention times: tR = 37.32 min ((S)-isomer: major isomer
using D-phenylalanine-derived diamines; minor isomer using
L-proline-derived diamines) and tR = 42.26 min ((R)- isomer:
minor isomer using D-phenylalanine-derived diamines; major
isomer using L-proline-derived diamines) using i-PrOH/
hexane (1/40) as eluent at a flow rate of 1.0 mL/min. The ee of
2c was determined by converting it to the trifluoroacetate
derivative (trifluoroacetic anhydride, Py, cat. DMAP,
ClCH2CH2Cl, r.t.) and subsequent chiral GC analysis using a
chiral column -TA (astec). The chiral GC analytical data
(column -TA) of the trifluoroacetate of 2c: retention times:
tR = 33.26 min ((S): major isomer using D-phenylalanine-
derived diamines; minor isomer using L-proline-derived
diamines) and tR = 36.07 min ((R): minor isomer using D-
phenylalanine-derived diamines; major isomer using L-
proline-derived diamines) at a column temperature of 92 °C
(injection temperature: 150 °C) at a carrier gas (N2) pressure
of 75 hPa. The absolute configuration of 2a-c was determined
by comparison with the known [ ]D data. See ref. 1h. The
temperature was selected for each run (23 °C, 30 °C, or 40 °C)
to obtain sufficient reactivity, which depends heavily on
aldehydes and catalysts employed.
(9) Several aldehydes were exposed to similar reaction conditions
(23 °C or 40 °C, 3~10 mol% of 19 4 or 19 5 catalyst), which
resulted in the considerable formation of the corresponding
dehydrated product: p-BrC6H4CHO, 57%; p-F-C6H4CHO,
74%; 3,5-F2-C6H3CHO, 43%; valeraldehyde, 63%; 2-furfural,
80%.
(7) These diamines were prepared by the methods previously
described, see: (a) Kobayashi, S.; Uchiro, H.; Fujishita, Y.;
Shiina, I.; Mukaiyama, T. J. Am. Chem. Soc. 1991, 113, 4247.
(b) Mukaiyama, T.; Soai, K.; Sato, T.; Shimizu, H.; Suzuki, K.
J. Am. Chem. Soc. 1979, 101, 1455. (c) Mukaiyama, T.;
Article Identifier:
1437-2096,E;2001,0,08,1245,1248,ftx,en;G09201ST.pdf
Synlett 2001, No. 8, 1245–1248 ISSN 0936-5214 © Thieme Stuttgart · New York