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DOI: 10.1055/s-2003-39394
Development of New Chiral Auxiliary Derived from (S)-(-)-Phenylethylamine for a Synthesis of Enantiopure (R)-2-Propyloctanoic Acid
Publication History
Publication Date:
26 May 2003 (online)

Abstract
A new chiral auxiliary, {[(1S)-1-phenylethyl]amino}phenol, derived from (S)-(-)-1-phenylethylamine was developed for asymmetric synthesis of (R)-2-propyloctanoic acid (1) with moderate diastereoselectivity and good crystalline property.
Key words
asymmetric synthesis - chiral auxiliary - crystallinity - {[(1S)-1-phenylethyl]amino}phenol - (R)-2-propyloctanoic acid
-
2a
Ohuchida S,Kishimoto K,Tateishi N, andOhno H. inventors; EP 632008. ; Chem. Abstr. 1995, 122, 160096 -
2b
Matsui T.Mori T.Tateishi N.Kagamiishi Y.Satoh S.Katsube N.Morikawa E.Morimoto T.Ikuta F.Asano T. J. Cereb. Blood. Flow. Metab. 2002, 22: 711 -
2c
Tateishi N.Mori T.Kagamiishi Y.Satoh S.Katsube N.Morikawa E.Morimoto T.Matsui T.Asano T. J. Cereb. Blood. Flow. Metab. 2002, 22: 723 -
3a
Evans DA.Mcgee LR.Ennis MD.Mathre DJ. J. Am. Chem. Soc. 1981, 103: 2876 -
3b
Evans DA.Ennis MD.Mathre DJ. J. Am. Chem. Soc. 1982, 104: 1737 -
3c
Evans DA. Aldrichimica Acta 1982, 15: 318 -
4a
Oppolzer W.Moretti R.Thomi S. Tetrahedron Lett. 1989, 30: 5603 -
4b
Oppolzer W.Rosset S.De Brabander J. Tetrahedron Lett. 1997, 38: 1539 -
4c
Hasegawa T.Yamamoto H. Synlett 1998, 882 -
4d
Hasegawa T.Yamamoto H. Bull. Chem. Soc. Jpn. 2000, 73: 423 -
4e
Hasegawa, T.; Kawanaka, Y.; Kasamatsu, E.; Iguchi, Y.; Yonekawa, Y.; Okamoto, M.; Ohta, C.; Hashimoto, S.; Ohuchida, S. Org. Process Res. Dev. 2003, in press.
-
5a
Evans DA.Takacs JM. Tetrahedron Lett. 1980, 21: 4233 -
5b
Abiko A.Masamune S.Moriya O.Filla SA. Angew. Chem., Int. Ed. Engl. 1995, 34: 793 -
5c
Myers AG.Yang BH.Chen H.Mckinstry L.Kopecky DJ.Gleason JL. J. Am. Chem. Soc. 1997, 119: 6496 -
7a
Bucher CB.Heimgartner H. Helv. Chim. Acta 1996, 79: 1903 -
7b For aldol reaction using
a N-tosyl derivative with high diastereoselectivity,
see:
Hirai K.Maruyama H. J. Synth. Org. Chem. Jpn. 1999, 5: 382 - All substrates were prepared by amidation with corresponding amines and octanoyl chloride (1.1 equiv) in the presence of Et3N (1.5 equiv) in THF. The references and the synthesis methods of these amines are as follows:
-
8a
Paquette LA.Tae J. J. Org. Chem. 1998, 63: 2022 -
8b
Ludeman SM.Bartlett DL.Zon G. J. Org. Chem. 1979, 44: 1163 -
8c
Bordwell FG.Lynch TY. J. Am. Chem. Soc. 1989, 111: 7558 -
8d
Chloroacetylation of (1S)-1-phenylethylamine (chloroacetyl chloride (1.0 equiv), Et3N (1.2 equiv), THF, 90%), amination with dicyclohexylamine (2 equiv) or 1-methylpiperazine (2 equiv) (K2CO3 (1.2 equiv), NaI (1.2 equiv), acetone, reflux, 98%), and reduction of the amide [LiAlH4 (3 equiv), THF, 73%, 80%].
-
10a
Seebach D. Angew. Chem., Int. Ed. Engl. 1988, 27: 1624 -
10b
Boche G. Angew. Chem., Int. Ed. Engl. 1989, 28: 277 -
11a
Galiano-Roth AS.Kim Y.-J.Gilchrist JH.Harrison AT.Fuller DJ.Collum DB. J. Am. Chem. Soc. 1991, 113: 5053 -
11b
Kim Y.-J.Bernstein Galiano-Roth AS.Romesberg FE.Williard PW.Fuller DJ.Harrison AT.Collum DB. J. Org. Chem. 1991, 56: 4435 -
11c
Hall PL.Gilchrist JH.Harrison AT.Fuller DJ.Collum DB. J. Am. Chem. Soc. 1991, 113: 9575 -
12a
Lucht BL.Collum DB. J. Am. Chem. Soc. 1995, 117: 9863 -
12b
Sugasawara K.Shindo M.Noguchi H.Koga K. Tetrahedron Lett. 1996, 37: 7377 - 14
Hoffman RW. Chem. Rev. 1989, 89: 1841 - 15
Braun M. Angew. Chem., Int. Ed. Engl. 1987, 26: 24 - 16
Tsvetkov EN.Syundyukova VK.Baulin VE. Izv. Akad. Nauk SSSR, Ser. Khim. 1989, 147 ; Chem. Abstr. 1990, 112, 566055 -
17a
Wolfe JP.Wagaw S.Buchwald SL. J. Am. Chem. Soc. 1996, 118: 7215 -
17b
Wagaw S.Rennels RA.Buchwald SL. J. Am. Chem. Soc. 1997, 119: 8451 -
17c
Old DW.Wolfe JP.Buchwald SL. J. Am. Chem. Soc. 1998, 120: 9722
References
Current address: Department of Chemistry, University of Chicago, 5735 South Ellis Avenue Chicago, IL 60637, USA.
6See Ref. [3]
9The absolute configuration of the product was determined after conversion to the carboxylic acid 1. See Ref. [4d]
13The Cerius-2 version 4.0 software package (Accerlys Inc., San Diego, CA.) was used for the conformational analysis. The systematic conformation search was performed utilizing the UNIVERSAL 1.02 force field, which possesses the parameters for lithium atom. A dielectric constant of 8.20 was used to simulate the THF solvent. Two dihedral angles, which construct the enolate face was fixed at 0º or 180º, and the remaining five dihedral angles were varied systematically at 30º steps. Each conformer was energy-minimized, and conformation energy was evaluated.