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Synlett 2019; 30(02): 185-188
DOI: 10.1055/s-0037-1610344
DOI: 10.1055/s-0037-1610344
letter
Enantioselective Stereodivergent Synthesis of Jaspine B and 4-epi-Jaspine B from Axially Chiral Allenols
This work was supported by grants (AH) from research projects at the Lebanese University.Further Information
Publication History
Received: 16 October 2018
Accepted after revision: 07 November 2018
Publication Date:
06 December 2018 (online)
Abstract
A short enantioselective synthetic route to the cytotoxic marine natural product jaspine B has been developed. A chiral non-racemic primary α-allenol, obtained from pentadecanal, gave access to an enantioenriched 2-tetradecyl-2,5-dihydrofuran as key intermediate. A stereodivergent functionalization of this dihydrofuran allowed access in a few steps to jaspine B and its 4-epimer.
Supporting Information
- Supporting information for this article is available online at https://doi.org/10.1055/s-0037-1610344.
- Supporting Information
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References and Notes
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- 17 (1S,2S,5R)-2-Tetradecyl-3,6-dioxabicyclo[3.1.0]hexane (trans-6) and (1R,2S,5S)-2-tetradecyl-3,6-dioxabicyclo[3.1.0]hexane (cis-6): Trifluoroacetic acid (1.29 mL, 9 mmol) was added slowly to a solution of (S)-2-tetradecyl-2,5-dihydrofuran (400 mg, 1.50 mmol) and urea-hydrogen peroxide complex (2.8 g, 22.5 mmol) in CH2Cl2 (20 mL). After 15 min stirring at r.t., the reaction mixture was diluted with an aqueous solution of Na2SO3 (1 M, 15 mL) and extracted with CH2Cl2 (3 × 20 mL). The organic phases were collected, dried over magnesium sulfate, and concentrated to dryness to give a residue, which was purified by flash chromatography on neutral alumina (EtOAc/petroleum ether 2:98) to give the epoxide trans-6 (188 mg, 44%) and epoxide cis-6 (149 mg, 35%). trans-6: 1H NMR (CDCl3, 300 MHz): δ = 4.1–4.0 (m, 1 H, H2), 3.97 (d, J = 10.6 Hz, 1 H, H5a), 3.75 (dd, J = 3.0, 0.7 Hz, 1 H, H4), 3.70 (d, J = 10.6 Hz, 1 H, H5b), 3.58 (d, J = 3.0 Hz, 1 H, H3), 1.5–1.35 (m, 2 H, H1′), 1.35–1.2 (m, 24 H, H2′–H13′), 0.95–0.8 (m, 3 H, H14′). 13C NMR (CDCl3, 75 MHz): δ = 77.8 (C2), 66.1 (C5), 59.1 (C3), 56.0 (C4), 32.1, 31.1, 29.8, 29.7, 29.6, 29.5, 25.6, 22.8 (C1′–C13′), 14.3 (C14′). HRMS: m/z [M+H]+ calcd for C18H35O2: 283.2637; found: 283.2645. [α]D 25= –11.8 (c 1.23, CHCl3). cis-6: 1H NMR (CDCl3, 300 MHz): δ = 4.04 (d, J = 10.6 Hz, 1 H, H5a); 3.76 (t, J = 6.7 Hz, 1 H, H2), 3.72 (dd, J = 3.1, 0.5 Hz, 1 H, H4), 3.66 (dd, J = 10.6, 0.6 Hz, 1 H, H5b), 3.64 (d, J = 3.2 Hz, 1 H, H3), 1.75–1.6 (m, 2 H, H1′), 1.5–1.2 (m, 24 H, H2′–H13′), 0.95–0.8 (m, 3 H, H14′). 13C NMR (CDCl3, 75 MHz): δ = 77.8 (C2), 67.6 (C5), 57.6 (C3), 56.0 (C4), 32.1, 31.1, 30.3, 29.8, 29.7, 29.5, 26.3, 22.8 (C1′–C13′), 14.3 (C14′). HRMS: m/z [M+H]+ calcd for C18H35O2: 283.2637; found: 283.2624. [α]D 25= +17.6 (c 1.48, CHCl3).
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- 19 All analyses were in agreement with the data reported in the literature (ref. 3f). [α]D 25 = +18.1 (c 0.80, EtOH). Lit. (ref. 3f) [α]D 25 = +18.8 (c 0.85, EtOH).
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- 21 All analyses were in agreement with the data reported in the literature (ref. 3h). [α]D 25 = –7.1 (c 0.46, MeOH). Lit. (ref. 3h) [α]D 25= –7.3 (c 0.46, MeOH).