Synlett 2016; 27(19): 2734-2736
DOI: 10.1055/s-0035-1562796
letter
© Georg Thieme Verlag Stuttgart · New York

Concise Synthesis of Anserine: Efficient Solvent Tuning in Asymmetric Hydrogenation Reaction

Megumi Yamashita
a  School of Pharmaceutical Sciences, University of Shizuoka, 52-1 Yada, Suruga-ku, Shizuoka 422-8526, Japan   Email: [email protected]
,
Keita Shimizu
a  School of Pharmaceutical Sciences, University of Shizuoka, 52-1 Yada, Suruga-ku, Shizuoka 422-8526, Japan   Email: [email protected]
,
Yasuaki Koizumi
a  School of Pharmaceutical Sciences, University of Shizuoka, 52-1 Yada, Suruga-ku, Shizuoka 422-8526, Japan   Email: [email protected]
,
Toshiyuki Wakimoto
a  School of Pharmaceutical Sciences, University of Shizuoka, 52-1 Yada, Suruga-ku, Shizuoka 422-8526, Japan   Email: [email protected]
b  Faculty of Pharmaceutical Sciences, Hokkaido University, Kita 12, Nishi 6, Kita-ku, Sapporo 060-0812, Japan
,
Yoshitaka Hamashima
a  School of Pharmaceutical Sciences, University of Shizuoka, 52-1 Yada, Suruga-ku, Shizuoka 422-8526, Japan   Email: [email protected]
,
Tomohiro Asakawa
a  School of Pharmaceutical Sciences, University of Shizuoka, 52-1 Yada, Suruga-ku, Shizuoka 422-8526, Japan   Email: [email protected]
,
Makoto Inai
a  School of Pharmaceutical Sciences, University of Shizuoka, 52-1 Yada, Suruga-ku, Shizuoka 422-8526, Japan   Email: [email protected]
,
Toshiyuki Kan*
a  School of Pharmaceutical Sciences, University of Shizuoka, 52-1 Yada, Suruga-ku, Shizuoka 422-8526, Japan   Email: [email protected]
› Author Affiliations
Further Information

Publication History

Received: 28 June 2016

Accepted after revision: 29 July 2016

Publication Date:
23 August 2016 (online)


Abstract

A concise synthesis of anserine and related compounds was accomplished by Et-DuPhos-Rh-catalyzed asymmetric hydrogenation of dehydrohistidine derivatives in 2,2,2-trifluoroethanol, which played a key role in improving the yield and selectivity.

Supporting Information

 
  • References and Notes

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  • 13 When TFE was used as the solvent, it was possible to decrease the hydrogen pressure and the temperature; a slight increase in the enantioselectivity was also observed. Asymmetric Hydrogenation of 6a; Typical Procedure (R,R)-Et-DuPHOS-Rh (7) (14 mg, 10 mol%) was added to a solution of 6a (63 mg, 0.20 mmol) in TFE (6 mL), and the mixture was pressurized with H2 to an initial pressure of 300 psi. The mixture was then heated to 50 °C and stirred for 10 h. The solvent was evaporated in vacuo to give a crude product that was purified by preparative TLC (CHCl3–MeOH, 10:1) to give 8a as a pale-yellow oil; yield: 58 mg (91%); optical purity >99% ee by chiral HPLC [CHIRALPAK-IC, hexane–EtOH–Et2NH (60:40:0.1)]; IR (neat) 1059, 1263, 1529, 1715, 2955 cm–1; 1H NMR (500 MHz, CDCl3): δ = 3.11 (dd, J = 5.7, 15.3 Hz, 1 H), 3.14 (dd, J = 5.7, 15.3 Hz, 1 H), 3.50 (s, 3 H), 3.75 (s, 3 H), 4.61 (td, J = 5.7, 7.4 Hz, 1 H), 5.10 (dd, J = 11.9, 19.8 Hz, 1 H), 5.41 (d, J = 7.4 Hz, 1 H), 6.76 (s, 1 H), 7.33–7.37 (m, 6 H). 13C NMR (125 MHz, CDCl3): δ = 26.7, 31.3, 52.7, 53.4, 67.1, 126.4, 128.2, 128.3, 128.6, 134.1, 136.0, 138.5, 155.6, 171.3. HRMS (ESI): m/z [M + H]+ calcd for C16H20N3O4: 318.1448; found: 318.1451.
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  • 16 Acylation of the HCl salt of histidine with 9 proceeded smoothly without any protection of the imidazole group. Boc protection was therefore selected in the case of carnosine synthesis.
  • 17 The optically rotation of the synthesized carnosine (3) matched that of natural carnosine: [α]D 25 +21.0 (c 0.215, H2O) [Lit.6 [α]D 25 +20.5 (c 2.0, H2O)]. The asymmetric reduction of 11b therefore proceeded with high enantioselectivity.