Organic Process Research & Development
Communication
6
1
7.4, 68.5, 126.4, 128.7, 129.0, 129.1, 134.8, 135.4, 140.4, 141.7,
68.2, 170.0.
One-Pot Preparation of (S)-Dibenzyl Glutamate p-
(13) Jobbins, M. O.; Miller, M. J. J. Org. Chem. 2014, 79, 1620.
14) Soicke, A.; Reuter, C.; Winter, M.; Neudorfl, J.; Schlorer, N.;
Kuhne, R.; Schmalz, H. Eur. J. Org. Chem. 2014, 6467.
15) Kozikowski, A. P.; Liao, Y.; Tuckmantel, W.; Wang, S.;
Pshenichkin, S.; Surin, A.; Thomsen, C.; Wroblewski, J. T. Bioorg.
Med. Chem. Lett. 1996, 6, 2559.
(
̈
̈
̈
(
̈
Toluenesulfonate [(S)-2·TsOH] on Multigram Scale. A
mixture of L-glutamic acid (20 g, 0.136 mol), p-toluenesulfonic
acid (31 g, 0.163 mol), benzyl alcohol (70.4 mL, 0.680 mmol),
and cyclohexane (160 mL) was heated at reflux with a Dean−
Stark trap under vigorous stirring for 6 h. The reaction mixture
was cooled to 50 °C, and ethyl acetate (240 mL) was added. The
resultant suspension was initially warmed at reflux for a few
minutes and then stirred for 1 h at room temperature and filtered.
The filter cake was washed with ethyl acetate and dried to give
(16) Lynch, J. K.; Holladay, M. W.; Ryther, K. B.; Bai, H.; Hsiao, C.;
Morton, H. E.; Dickman, D. A.; Arnold, W.; King, S. A. Tetrahedron:
Asymmetry 1998, 9, 2791.
(17) Meiresonne, T.; Mangelinckx, S.; De Kimpe, N. Tetrahedron
2012, 68, 9566.
(18) Rudolph, J.; Hannig, F.; Theis, H.; Wischnat, R. Org. Lett. 2001, 3,
3
(
153.
19) Bergmeier, S. C.; Cobas, A. A.; Rapoport, H. J. Org. Chem. 1993,
58, 2369.
(
[
9
S)-2·TsOH (65.8 g, 97%) as a white solid: mp = 141.6 °C;
α]D25 = +7.4 (c 1, MeOH), [lit. [α]D = +7.6 (c 1, MeOH)];
9.4% ee (determined by HPLC analysis on a Phenomenex Lux 3
21
20
(20) Cipera, J. D.; Nicholls, R. V. V Chem. Ind. 1955, 16.
(21) Zervas, L.; Winitz, M.; Greenstein, J. P. J. Org. Chem. 1957, 22,
μ Amylose-2 column, 150 mm × 4.6 mm i.d.; hexane/EtOH 80/
1
515.
1
2
2
5
0; 1.2 mL/min); H NMR (300 MHz, CDCl ) δ 2.18 (m, 2H),
.23 (s, 3H), 2.34−2.58 (m, 2H), 4.13 (t, J = 6.3 Hz, 1H), 4.89−
.07 (m, 4H), 6.96 (d, J = 8.0 Hz, 2H), 7.19−7.28 (m, 10H), 7.72
3
(22) Izumiya, N.; Makisumi, S. Nippon Kagaku Zasshi 1957, 78, 662.
(23) Bose, A. K.; Strube, R. E. J. Pharm. Sci. 1963, 52, 847.
(24) Mazur, H. R. Can. J. Chem. 1962, 40, 1098.
(25) Gibian, H.; Schroeder, E. Justus Liebigs Ann. Chem. 1961, 642, 145.
(26) Laurent, S.; Elst, L. V.; Botteman, F.; Muller, R. N. Eur. J. Inorg.
1
3
(d, J = 8.0 Hz, 2H), 8.37 (bs, 3H); C NMR (75 MHz, CDCl ) δ
3
2
1
1.5, 25.4, 29.6, 52.6, 66.6, 68.2, 126.3, 128.3, 128.5, 128.6, 128.7,
29.1, 134.9, 135.9, 140.5, 141.5, 169.1, 172.2.
Chem. 2008, 4369.
27) Bergmeier, S. C.; Cobas
8, 2369.
28) Chen, A.; Xu, S.; Zhang, J. Preparation method of (S)-β-
azetidinone-4-benzyl carboxylate. CN1569830A, 2005.
29) Olivier, J. Structural and synthetic studies of a new natural
(
́
, A. A.; Rapoport, H. J. Org. Chem. 1993,
5
(
ASSOCIATED CONTENT
■
*
S
Supporting Information
1
13
H NMR, C NMR, and IR spectra and DSC traces of (S)-1·
(
TsOH and (S)-2·TsOH and chiral HPLC chromatograms of (S)-
1
sweetener. Thesis, Johannesburg University, South Africa, 1989.
(30) Olivier, J. Approaches to the synthesis of the natural sweetener
monatin. Ph.D. Thesis, Johannesburg University, South Africa, 1994.
(31) Li, Y. C.; Pang, S. P.; Yu, Y. Z. Chin. Chem. Lett. 2007, 18, 516.
(32) Sato, H.; Ohno, T.; Iwata, S. Optically active amino acid
derivatives and processes for the preparation of the same. US6706916,
004.
33) Smith, H. L.; Brown, E. S.; Smith, J. D.; Andrako, J. J. Pharm. Sci.
965, 54, 1269.
AUTHOR INFORMATION
■
2
(
1
*
Notes
(34) (a) Bolchi, C.; Fumagalli, L.; Moroni, B.; Pallavicini, M.; Valoti, E.
Tetrahedron: Asymmetry 2003, 14, 3779. (b) Pallavicini, M.; Bolchi, C.;
Di Pumpo, R.; Fumagalli, L.; Moroni, B.; Valoti, E.; Demartin, F.
Tetrahedron: Asymmetry 2004, 15, 1659. (c) Pallavicini, M.; Bolchi, C.;
Fumagalli, L.; Piccolo, O.; Valoti, E. Tetrahedron: Asymmetry 2007, 18,
The authors declare no competing financial interest.
REFERENCES
■
(
1) Deng, G.; Liu, Z.; Ye, F.; Luo, X.; Zhu, W.; Shen, X.; Liu, H.; Jiang,
H. Eur. J. Med. Chem. 2008, 43, 2699.
9
06. (d) Bolchi, C.; Pallavicini, M.; Fumagalli, L.; Rusconi, C.; Binda, M.;
Valoti, E. Tetrahedron: Asymmetry 2007, 18, 1038. (e) Pallavicini, M.;
Bolchi, C.; Binda, M.; Ferrara, R.; Fumagalli, L.; Piccolo, O.; Valoti, E.
Tetrahedron: Asymmetry 2008, 19, 1637. (f) Bolchi, C.; Pallavicini, M.;
Fumagalli, L.; Straniero, V.; Valoti, E. Org. Process Res. Dev. 2013, 17,
(
2) D’Acquarica, I.; Cerreto, A.; Delle Monache, G.; Subrizi, F.; Boffi,
A.; Tafi, A.; Forli, S.; Botta, B. J. Org. Chem. 2011, 76, 4396.
3) Okai, H. New peptide derivative and sweetener containing the
same. JPH08109193, 1996.
4) Yang, D. ; Fan, L. ; Tang, X. ; Yan, J. Method for preparing para
(
4
32.
35) Jacques, J.; Collet, A.; Wilen, S. H. Enantiomers, Racemates and
Resolutions; Wiley: New York, 1981; p 91.
36) ACS GCI Pharmaceutical Roundtable Solvent Selection Guide,
on the GCI-PR Web site.
37) Prat, D.; Pardigon, O.; Flemming, H.-W.; Letestu, S.; Ducandas,
(
(
amino benzoic acid quasi-dipeptide ester and application thereof.
CN101445468, 2009.
(
(
5) Tennant-Eyles, R. J.; Fairbanks, A. J. Tetrahedron: Asymmetry 1999,
0, 391.
6) Prakash, I.; Ager, D. J.; Pantaleone, D. P. Regioselective α-
hydrolysis of amino acid diesters using pig liver esterase. US5928909,
999.
7) Schlingmann, M.; Hoppe, H. U.; Du
preparation of 4-benzyl aspartate. US4709086, 1987.
8) Oh, N. M.; Oh, K. T.; Youn, Y. S.; Lee, E. S. Colloids Surf., B 2012,
7, 190.
9) Ji, Y.; Luo, Y.; Jia, X.; Chen, E.; Huang, Y.; Ye, C.; Wang, B.; Zhou,
Q.; Wei, Y. Angew. Chem., Int. Ed. 2005, 44, 6025.
10) Nakanishi, E.; Muroi, T. β-Polypeptide derivatives with good
1
(
(
V.; Isnard, P.; Guntrum, E.; Senac, T.; Ruisseau, S.; Cruciani, P.; Hosek,
P. Org. Process Res. Dev. 2013, 17, 1517.
1
(
(38) Yamaguchi, T.; Blazquez, B.; Hesek, D.; Lee, M.; Llarrull, L. I.;
̈
rsch, W. Process for the
Boggess, B.; Oliver, A. G.; Fisher, J. F.; Mobashery, S. ACS Med. Chem.
Lett. 2012, 3, 238.
(
9
(
(39) Gnichtel, H.; Lautsch, W. Chem. Ber. 1965, 98, 1647.
(40) Du, Z.; Lu, Y.; Dai, X.; Zhang-Negrerie, D.; Gao, Q. J. Chem. Res.
2
013, 37, 181.
(41) Xu, L.; Huang, W.; Zhao, X. Polyethylene glycol-amino acid
(
oligopeptide oligopeptide-irinotecan conjiugate and drug composition
thereof. WO2013067767, 2013.
photoconductivity, manufacture thereof, and photosensitive composi-
tions and moldings therefrom. JP2003327696, 2003.
(
11) McGregor, D. N.; Davidson, T. J. Compositions for inhibiting
aminoglycoside nephrotoxicity. EP0473145, 1992.
12) Marritt, W. Pigment-dispersed aqueous ink-jet ink compositions
JP11279470, 1999.
(
F
Org. Process Res. Dev. XXXX, XXX, XXX−XXX