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J-GLOBAL ID：200902261011297722   Reference number：07A0419785

DIASTEREOSELECTIVE REDUCTION OF α-IMINO ESTERS WITH TRIS(TRIMETHYLSILYL)ALUMINUM

トリス(トリメチルシリル)アルミニウムによるα-イミノエステルのジアステレオ選択的還元

Author (4)： SHIMIZU Makoto (Mie Univ., Mie, JPN) ,  NIWA Yasuki (Mie Univ., Mie, JPN) ,  NAGAI Takeshi (Mie Univ., Mie, JPN) ,  HACHIYA Iwao (Mie Univ., Mie, JPN)
Material： Heterocycles  (International Journal for Reviews and Communications in Heterocyclic Chemistry)
Volume： 72  Page： 127-132  Publication year： Apr. 13, 2007 
JST Material Number： S0966A  ISSN： 0385-5414  CODEN： HTCYAM  Document type： Article
Article type： 短報  Country of issue： Japan (JPN)  Language： ENGLISH (EN)

Thesaurus term： *reduction (reaction) ,...

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JST classification (2)： Aromatic monocyclic carboxylic esters,carboxylic anhydrides,acid halides  (CF05190E) ,  Oxidation,reduction  (CF02060T)

Substance index (15)： Tris(trimethylsilyl) aluminum ,  α-(p-Anisylimino)benzeneacetic acid ethyl ester ,  (4-Methoxyanilino)phenylacetic acid ethyl ester ,  Phenyl(tert-butylimino)acetic acid ethyl ester ,  Phenyl(phenylimino)acetic acid ethyl ester ,  (2-Thienyl)(4-methoxyphenylimino)acetic acid ethyl ester ,  Cyclohexyl(4-methoxyphenylimino)acetic acid ethyl ester ,  Phenyl(tert-butylamino)acetic acid ethyl ester ,  Anilinophenylacetic acid ethyl ester ,  (2-Thienyl)[(4-methoxyphenyl)amino]acetic acid ethyl ester ,  Cyclohexyl[(4-methoxyphenyl)amino]acetic acid ethyl ester ,  3-Phenyl-5β-isopropyl-5,6-dihydro-2H-1,4-oxazine-2-one ,  (3R,5S)-3-Phenyl-5-isopropylmorpholine-2-one ,  3,5α-Diphenyl-5,6-dihydro-2H-1,4-oxazine-2-one ,  (3S)-3α,5α-Diphenylmorpholin-2-one

Reference (5)：

• (a) G. G. Cox and L. M. Harwood, Tetrahedron: Asymmetry, 1994, 5, 1669.(b) F. Seggat-Dioury, O. Lingibe, B. Graffe, M.-C. Sacquet, and G. Lhommet, Tetrahedron, 2000, 56, 233.
• (a) M. P. Bertrand, L. Feray, R. Nouguier, and P. Perfetti, Synlett, 1999, 1148.(b) K. Uneyama, F. Yan, S. Hirama, and T. Katagiri, Tetrahedron Lett., 1996, 37, 2045.(c) Y. Yamamoto and W. Ito, Tetrahedron, 1988, 44, 5415.(d) M. R. van Vliet, J. T. B. H. Jastrzebski, W. J. Klaver, K. Goubitz, and G. van Koten, Recl. Trav. Chim. Pays-Bas, 1987, 106, 132.(e) J.-C. Fiaud and H. B. Kagan, Tetrahedron Lett., 1971, 12, 1019.
• (a) Y. Niwa and M. Shimizu, J. Am. Chem. Soc., 2003, 125, 3720.(b) M. Shimizu and Y. Niwa, Tetrahedron Lett., 2001, 42, 2829.(c) Y. Niwa, K. Takayama, and M. Shimizu, Bull. Chem. Soc. Jpn., 2002, 75, 1819.(d) Y. Niwa, K. Takayama, and M. Shimizu, Tetrahedron Lett., 2001, 42, 5473.(e) M. Shimizu, H. Itou, and M. Miura, J. Am. Chem. Soc., 2005, 127, 3296.
• (a) M. A. Avery, W. K. M. Chong, and C. Jennings-White, J. Am. Chem. Soc., 1992, 114, 974.(b) M. Nakada, S. Nakamura, S. Kobayashi, and M. Ohno, Tetrahedron Lett., 1991, 32, 4929.(c) G. Altnau and L. Rösch, Tetrahedron Lett., 1983, 24, 45.(d) B. M. Trost, J. Yoshida, and M. Lautens, J. Am. Chem. Soc., 1983, 105, 4494.(e) L. Rösch and G. Altnau, J. Organomet., Chem., 1980, 195, 47.
• The following example represents typical experimental procedure: To a solution of (5S)-5-isopropyl 3-phenyl-5, 6-dihyro-2H-1, 4-oxazine-2-one (32.6 mg, 0.150 mmol)(5) in DME (1.5 mL) was added a solution of BF₃OEt₂ (21.3 mg, 0.150 mmol) in DME (1.5 ml) at-60°C under an argon atmosphere. To the resulting solution was added a solution of tris (trimethylsilyl) aluminum (6)(0.300 mL, 0.150 mmol, 0.5 M in pentane) at-60°C. The mixture was allowed to warm to ambient temperature with stirring for 8.0 h. The reaction was cooled to-60°C and quenched with MeOH (0.122 mL, 3.00 mmol). To the resulting solution was added sat. NaHCO₃ aq, and the whole mixture was extracted with AcOEt. The combined organic layers were washed with brine, dried over anhydrous Na₂SO₄, and concentrated in vacuo. Purification by flash silica gel column (n-hexane-AcOEt=4:1 as an eluent) gave 5-isopropyl-3-phenylmorpholine-2-one (5)(17.8 mg, 54%, a 92:8 mixture of cis and trans isomers) as a colourless oil; ¹H NMR (500 MHz, CDCl₃) δ: 0.98 (d, J=7.3 Hz, 3H), 1.02 (d, J=6.7 Hz, 3H), 1.71-1.75 (m, 1H), 1.92 (brs, 1H), 2.83-2.89 (m, 0.08H), 2.99-3.04 (m, 0.92H), 4.23-4.27 (m, 1H), 4.40-4.45 (m, 1H), 4.72 (s, 0.92H), 4.86 (s, 0.08H), 7.33-7.50 (m, 5H); ¹³C NMR (126 MHz, CDCl₃) δ: 18.7, 18.9, 30.2, 58.0, 63.6, 72.8, 127.2, 128.3, 128.6, 138.4, 169.2; IR (neat) 3329, 3031, 2963, 1739, 1460, 1369, 1294, 1205, 1092, 1028, 968, 867, 743, 700 cm^-1.

Terms in the title (4)： アルミニウム ,  イミノエステル ,  ジアステレオ選択 ,  還元