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Synlett 2023; 34(06): 673-677
DOI: 10.1055/a-1881-0529
DOI: 10.1055/a-1881-0529
cluster
Chemical Synthesis and Catalysis in India
Synthesis of the Key Skeleton of Phosphoeleganin
Financial support from the Science and Engineering Research Board, India (Project no. CRG/2019/001664), for carrying out this work is gratefully acknowledged.
Abstract
The asymmetric synthesis of the key skeleton of phosphoeleganin has been achieved for the first time by using a convergent approach. The salient features of this synthesis include amidation to install a glycine amide at the C-1 position, Wittig olefination to access the C5–C6 bond, Julia–Kocienski olefinations to prepare the C9–C10 and C13–C14 bonds, and a Takai olefination and a Sonogashira coupling to construct the C17–C18 and C18–C19 bonds, respectively. The route disclosed is highly modular, which will permit the synthesis of various analogues, useful for structure–activity relationship studies on phosphoeleganins.
Supporting Information
- Supporting information for this article is available online at https://doi.org/10.1055/a-1881-0529.
- Supporting Information
Publication History
Received: 13 May 2022
Accepted after revision: 21 June 2022
Accepted Manuscript online:
21 June 2022
Article published online:
19 July 2022
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- 16 Compound 2 10% Pd/C (111 mg) was added to a stirred solution of 3 (370 mg, 0.4 mmol) in EtOAc (10 mL), under H2 (balloon) at rt, and the mixture was stirred for 40 h. The mixture was then filtered through a short pad of Celite that was washed with EtOAc (30 mL). The combined organic layers were concentrated under reduced pressure and purified by flash column chromatography [silica gel (100–200 mesh), 20% EtOAc–hexane] to give the corresponding saturated compound as a colorless oil; yield: (202 mg, 58%). Diphenylphosphoryl chloride (30 μl, 0.11 mmol) was added slowly to a solution of the saturated compound (50 mg, 0.055 mmol) in anhyd pyridine (5 mL) at 0 °C under argon, and the mixture was stirred at rt for 48 h. The reaction was quenched with ice–water, and the mixture was extracted with EtOAc (20 mL). The combined organic layers were washed successively with ice–water, 1 N aq HCl, sat. aq NaHCO3, and brine, then dried (Na2SO4) and concentrated in vacuo. The residue was purified by column chromatography [silica gel (100–200 mesh), 15–20% EtOAc–hexane] to give compound 2 as a liquid; yield: 47 mg (72%); [α]D 25 +7 (c 0.8, CHCl3). IR (neat): 3302, 2931 2872, 1733, 1612, 1454, 1388, 1067, 993 cm–1. 1H NMR (300 MHz, CDCl3): δ = 7.42–7.05 (m, 12 H), 6.15 (s, 1 H), 4.64–4.46 (m, 1 H), 3.93 (dt, J = 13.0, 5.1 Hz, 4 H), 3.74–3.47 (m, 2 H), 2.62 (t, J = 7.5 Hz, 2 H), 1.77–1.66 (m, 5 H), 1.42–1.20 (m, 62 H), 0.89–0.86 (m, 15 H), 0.15–0.06 (m, 12 H). 13C NMR (75 MHz, CDCl3): δ = 158.0, 155.8, 151.0, 150.9, 150.8, 129.8, 125.3, 125.2, 120.4, 120.3, 120.2, 108.0, 107.6, 84.9, 84.8, 83.4, 78.6, 78.4, 77.4, 74.4, 74.3, 72.3, 37.4, 33.8, 32.1, 30.4, 30.3, 30.2, 29.9, 29.8, 29.8, 29.7, 29.6, 29.5, 29.3, 28.8, 28.7, 28.2, 27.0, 26.4, 26.1, 26.1, 25.9, 25.5, 25.2, 22.9, 18.4, 18.3, 14.3, 1.2, 0.2, –4.1, –4.2, –4.3, –4.4. HRMS (ESI): m/z [M + H + Na]+ calcd for C63H112NNaO11PSi2: 1169.7487; found: 1169.779.