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DOI: 10.1055/s-0042-1751547
Stereoselective Synthesis of Volicitin and 9-D 1-Volicitin
This work was supported by Research Project Grant B from the Institute of Science and Technology, Meiji University, and Meiji University Graduate School Joint Research Project (MU-GS-JRP2023-04).
Abstract
The synthesis of volicitin involved the condensation of l-(+)-glutamine with 17(S)-hydroxylinolenoic acid, derived from a Wittig reaction between the C10–C18 phosphonium salt and the C1–C9 aldehyde. The phosphonium salt was prepared through the alkynylation of a (Z)-allylic phosphate with an alkyne derived from (2S)-but-3-yn-2-ol. The deuterated aldehyde was derived with a 96% deuteration ratio by reduction of the C1–C9 methyl ester with NaBD4, followed by oxidation. Subsequently, 9-D 1-volicitin was synthesized from the monodeuterated aldehyde by using the Wittig reaction and condensation with l-(+)-glutamine.
Supporting Information
- Supporting information for this article is available online at https://doi.org/10.1055/s-0042-1751547.
- Supporting Information
Publication History
Received: 07 November 2023
Accepted after revision: 04 December 2023
Article published online:
15 January 2024
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- 15 Volicitin (1) To an ice-cold solution of carboxylic acid 2 (83.1 mg 0.282 mmol) in THF (2.8 mL) was added Et3N (0.047 mL, 0.34 mmol). After 1 h at 0 °C, ClCO2Et (0.032 mL, 0.034 mmol) was added to the mixture. After a further 1 h at 0 °C, a solution of l-(+)-glutamine (53.5 mg, 0.367 mmol) in aq NaOH was added to the mixture. After 1.5 h at r.t., the mixture was diluted with 3 N aq HCl and extracted with EtOAc (×3). The combined extracts were dried (MgSO4) and concentrated. The residue was semi-purified by chromatography (silica gel, EtOAc to EtOAc–MeOH) to give crude 1. The crude 1 was purified by chromatography (Wakosil 50C18, MeCN–H2O) to give a white amorphous solid; yield: 81.8 mg (69%); Rf = 0.09 (EtOAc–MeOH, 2:1); [α]D 27 +8 (c 0.095, MeOH), [α]D 26 +2 (c 0.26, CH2Cl2) [Lit.3a [α]D 22 +3 (c 0.83, CH2Cl2)]. IR (neat): 3472, 1715, 1670, 1450, 670 cm–1. 1H NMR (400 MHz, CD3OD): δ = 1.11 (d, J = 6.4 Hz, 3 H), 1.21–1.31 (m, 8 H), 1.54 (t, J = 7.2 Hz, 2 H), 1.81–1.90 (m, 1 H), 1.99 (q, J = 6.4 Hz, 2 H), 2.03–2.13 (m, 1 H), 2.16 (t, J = 7.6 Hz, 2 H), 2.18–2.23 (m, 2 H), 2.73 (t, J = 6.0 Hz, 2 H), 2.78 (t, J = 6.0 Hz, 2 H), 4.26 (dd, J = 8.8, 5.2 Hz, 1 H), 4.54 (quint, J = 6.4 Hz, 1 H), 5.20–5.36 (m, 6 H). 13C NMR (100 MHz, CD3OD): δ = 24.0, 26.5, 26.8, 26.9, 28.1, 28.8, 30.21, 30.26, 30.32, 30.7, 32.8, 36.9, 53.6, 64.3, 128.6, 129.1, 129.6, 131.2, 135.4, 175.6, 176.2, 177.8. HRMS (FD): m/z [M+] calcd for C23H38N2O5: 422.27807; found: 422.27801.