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Synlett 2017; 28(20): 2928-2932
DOI: 10.1055/s-0036-1590858
DOI: 10.1055/s-0036-1590858
letter
Synthesis of (–)-Muricatacin and (–)-(R,R)-L-Factor Involving an Organocatalytic Direct Vinylogous Aldol Reaction
Financial support from the Natural Sciences and Engineering Research Council of Canada and the Canada Foundation for Innovation is gratefully acknowledged. Christopher Cooze is the recipient of a NSERC Undergraduate Student Research Award.Further Information
Publication History
Received: 13 June 2017
Accepted after revision: 07 July 2017
Publication Date:
14 August 2017 (online)
Dedicated to Professor Victor Snieckus on the occasion of his 80th birthday
Abstract
Concise syntheses of the polyketide natural product (–)-muricatacin and (–)-(R,R)-L-factor (natural product enantiomer) were achieved in four steps by employing an organocatalytic asymmetric direct vinylogous aldol reaction of γ-crotonolactone and suitable aliphatic aldehydes as the key step.
Supporting Information
- Supporting information for this article is available online at https://doi.org/10.1055/s-0036-1590858.
- Supporting Information
-
References and Notes
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- 21 General Procedure for the Reduction of 20 and 21 To a solution of the ketone (1 equiv) in dry THF was added K-Selectride (1.5 equiv, 1 M in THF) at –78 °C, and the mixture was stirred at –78 °C for 1 h. Saturated NH4Cl (5 mL) was added at –78 °C, and the mixture was warmed to r.t. The mixture was then extracted with EtOAc (3 × 5 mL), and the combined extracts were dried (Na2SO4) and concentrated. The crude product was purified by flash chromatography on silica gel. (R)-5-[(R)-1-Hydroxytridecyl]dihydrofuran-2(3H)-one – (–)-Muricatacin (1) The reaction of ketone 20 (50 mg, 0.18 mmol) and K-Selectride (0.27 mL, 0.27 mmol, 1.0 M in THF) in dry THF (1 mL) for 30 min according to the general procedure provided, after purification by flash chromatography on silica gel (CH2Cl2/EtOAc, 9:1), 37 mg (74%) of 1 as a white solid. Rf = 0.30 (CH2Cl2/EtOAc, 9:1); [α]D 23–18.6 (c 1.77, CH2Cl2), mp 65.5–69.1 °C; lit.8a [α]D 23–17.5 (c 1.0, CH2Cl2), mp 66–68 °C; lit.8o [α]D 23–19 (c 1.8, CH2Cl2), mp 68–70 °C. IR (neat): 3415(br), 2957, 2916, 2847, 1761, 1471, 1462, 1267, 1189, 1331, 1104, 1082, 1011 cm–1. 1H NMR (300 MHz, CDCl3): δ = 4.42 (td, 1 H, J = 7.3, 4.6 Hz, OCH), 3.58 (quint, 1 H, J = 5.3 Hz, CHOH), 2.69–2.46 (m, 2 H, CH2), 2.33–2.04 (m, 2 H, CH2), 1.95–1.85 [br m, 1 H, OH (D2O exchange)], 1.64–1.20 (m, 22 H, CH2), 0.88 (t, 3 H, J = 6.6 Hz, CH3). 13C NMR (75 MHz, CDCl3): δ = 177.2 (C(O)O), 83.0 (OCH), 73.7 (CHOH), 33.0 (CH2), 31.9 (CH2), 29.7 (CH2), 29.64 (2 × CH2), 29.58 (CH2), 29.51 (CH2), 29.50 (CH2), 29.4 (CH2), 28.7 (CH2), 25.5 (CH2), 24.1 (CH2), 22.7 (CH2), 14.1 (CH3). HRMS (ESI, pos): m/z calcd for C17H32O3 [M]+: 284.2351; found: 284.2340; m/z calcd for C17H33O3 [M + Na]+: 307.2249; found: 307.2232. (R)-5-[(R)-1-Hydroxyhexyl]dihydrofuran-2(3H)-one – (–)-L-Factor (3) The reaction of ketone 21 (60 mg, 0.33 mmol) and K-Selectride (0.48 mL, 0.49 mmol) in dry THF (2 mL) for 1 h according to the general procedure provided, after purification by flash chromatography on silica gel (CH2Cl2/EtOAc, 9:1), 48 mg (78%) of 3 as a white solid. Rf = 0.22 (CH2Cl2/EtOAc, 4:1); [α]D 23 –29.3 (c 1.27, CHCl3), mp 41–43 °C; lit.8a [α]D 25–27.1 (c 0.6, CHCl3), mp 42–44 °C; lit.8b [α]D 23 –32.8 (c 1.54, CHCl3), mp 45–48 °C. IR: 3450 (br), 2954, 2928, 2858, 1765, 1185, 1133, 1075, 1057, 1023, 992, 929, 907 cm–1. 1H NMR (300 MHz, CDCl3): δ = 4.42 (td, 1 H, J = 7.3, 4.4 Hz, OCH), 3.62–3.52 (br m, 1 H, CHOH), 2.69–2.46 (m, 2 H, CH2), 2.32–2.01 [m, 3 H, CH2, OH (D2O exchange)], 1.62–1.21 (m, 8 H, CH2), 0.89 (t, 3 H, J = 6.7 Hz, CH3). 13C NMR (75 MHz, CDCl3): δ = 177.3 (C(O)O), 83.0 (OCH), 73.6 (CHOH), 32.9 (CH2), 31.7 (CH2), 28.7 (CH2), 25.1 (CH2), 24.1 (CH2), 22.5 (CH2), 14.0 (CH3). HRMS (APPI, pos): m/z calcd for C10H18O3 [M]+: 186.1256; found: 186.1252; m/z calcd for C10H19O3 [M + H]+: 187.1334; found: 187.1325.
For a review on the synthesis and the biological activity of muricatacin and related γ-butanolides, prior to 2010, see:
Selected syntheses:
Organocatalytic vinylogous aldol reactions of unsubstituted γ-crotonolactone:
Organocatalytic vinylogous aldol reactions of substituted γ-crotonolactones: