Synthesis and absolute configuration of four diastereoisomeric 1-(2-furyl)-2-aminobutane-1,3-diols

Szechner, Barbara; Achmatowicz, O.; Gałdecki, Z.; Fruziński, Andrzej

doi:10.1016/s0040-4020(01)90488-0

“…Although the organometallic addition reaction could produce a diastereomeric mixture, the desired syn-configured alcohol, 79, was obtained with a 5:1 ratio and in 80% isolated yield. This stereoselectivity was caused by the chirality of threonine amino acid via Cram-chelation control of the nucleophilic addition [53]. The newly generated stereogenic center served as a key stereocenter in C-6 within legionamic acid (81).…”

Section: Chiral Pool: Threoninementioning

confidence: 99%

Recent Advances in Substrate-Controlled Asymmetric Induction Derived from Chiral Pool α-Amino Acids for Natural Product Synthesis

Paek

¹

,

Jeong

²

,

Jo

³

et al. 2016

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Chiral pool α-amino acids have been used as powerful tools for the total synthesis of structurally diverse natural products. Some common naturally occurring α-amino acids are readily available in both enantiomerically pure forms. The applications of the chiral pool in asymmetric synthesis can be categorized prudently as chiral sources, devices, and inducers. This review specifically examines recent advances in substrate-controlled asymmetric reactions induced by the chirality of α-amino acid templates in natural product synthesis research and related areas.

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“…The residue was purified by flash chromatography (90:10:0.1:0.5 to 90:10:1.5:0.5 chloroform:ethyl acetate:methanol:triethylamine eluent) to yield dimethyl glycoside (-)-20 (0.429 g, 94% yield) as a colorless oil: R F 0.45 (90:10 chloroform:methanol eluent); 1 Tosyl Arene SI6. To a solution of SI5 2 (10.15 g, 60.4 mmol) in dichloromethane (60 mL) were added triethylamine (8.4 mL, 60.4 mmol) and p-toluenesulfonyl chloride (11.5 g, 60.4 mmol).…”

Section: Special Refinement Detailsmentioning

confidence: 99%

“…The reaction was pressurized to 1000 psi with hydrogen in a stainless steel reaction vessel for 28 h. The reaction was then diluted with water (175 mL), saturated aqueous sodium bicarbonate (175 mL), and saturated aqueous sodium chloride (175 mL), and extracted with ethyl acetate (150 mL, 2 x 100 mL). The combined organics were dried over sodium sulfate, concentrated, and purified by flash chromatography (100 chloroform to 5:95 triethylamine:chloroform eluent) to provide (-)-14 (1.345 g, 72% yield) and a colorless oil: R F 0.52 (10:90 methanol:chloroform); 1 1.62 (ddd, J = 12.8, 6.6, 6.6 Hz, 1H), 1.07 (br s, 21H); 1 3 C NMR (75 MHz, CDCl 3 ) d 173. 5, 156.1, 150.9, 145.5, 138.9, 133.2, 129.9, 128.5, 127.3, 125.7, 122.2, 66.3, 61.0, 60.8, 60.3, 60.0, 58.8, 38.6, 35.2, 33.0, 22.1, 18.4, 12.2, 10.3;IR (NaCl/film) 2943, 2866, 1678, 1483, 1377, 1178, 1109 9, 156.2, 153.8, 151.2, 145.4, 139.0, 136.3, 133.5, 129.8, 128.6, 128.5, 128.2, 128.0, 127.3, 125.1, 122.1, 67.5, 65.7, 60.9, 60.7, 59.1, 58.8, 56.4, 39.1, 34.0, 32.6, 21.9, 18.3, 12.3, 10.3;IR (NaCl/film) 2943, 2866, 1709, 1685, 1378, 1178, 1109 Phenol (-)-2.…”

Section: Special Refinement Detailsmentioning

confidence: 99%

“…To a cooled (0 °C) solution of (-)-SI12 (250 mg, 300 mmol) in methanol (6 mL) was added acetyl chloride (427 mL, 6 mmol) dropwise over 30 sec. The reaction was warmed to 20 °C for 9 h, concentrated, and purified by preparative HPLC to provide (-)-15 trifluoroacetate (175 mg, 98% yield) as a colorless, highly viscous oil: R F 0.11 (10:90 methanol:chloroform); 1 7, 149.2, 145.8, 145.4, 136.3, 128.0, 127.4, 127.0, 124.0, 123.3, 115.2, 66.1, 63.0, 62.1, 60.9, 59.9, 59.1, 58.5, 54.6, 30.3, 28.4, 9.2;IR (NaCl/film) 3272, 2946, 2896, 1694, 1674, 1418, 1204, 1134 1.93 (ddd, J = 21.9, 11.3, 10.8 Hz, 1H), 1.44 (d, J = 6.9 Hz, 3H), 1.19 (s, 3H); 1 3 C NMR (75 MHz, CD 3 OD, 50 °C) d 159. 5, 150.1, 146.8, 144.4, 137.4, 129.7, 129.4, 128.9, 126.0, 124.0, 115.5, 98.1, 72.1, 69.5, 67.9, 66.8, 64.9, 64.5, 63.9, 63.5, 61.7, 61.3, 61.2, 57.5, 55.4, 44.8, 39.9, 30.8, 30.5, 21.9, 18.6, 10.0;IR (NaCl/film) 3307, 3064, 2945, 1682, 1204, 1180 Tetrahydroisoquinoline (-)-SI13.…”

Section: Special Refinement Detailsmentioning

confidence: 99%

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The Total Synthesis of (‐)‐Lemonomycin.

Ashley

¹

,

Cruz

²

,

Stoltz

³

2004

ChemInform

0

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Material and Methods. Unless otherwise stated, reactions were performed at ambient temperature (typically 20 °C) in flame-dried glassware under a nitrogen or argon atmosphere using dry, deoxygenated solvents. Solvents were dried by passage through an activated alumina column under argon. Acrolein was distilled under nitrogen immediately prior to use. All other commercially obtained reagents were used as received. Reaction temperatures were controlled by an IKAmag temperature modulator. Thin-layer chromatography (TLC) was performed using E. Merck silica gel 60 F254 precoated plates (0.25 mm) and visualized by UV, anisaldehyde, permanganate, or CAM staining. ICN Silica gel (particle size 0.032-0.063 mm) was used for flash chromatography. Preparatory reversed-phase HPLC was performed on a Waters HPLC with a Waters Delta-Pak 25 x 100 mm, 15 mm C 1 8 column equipped with a guard, utilizing a flow rate of 10 mL/min and a ramp of 1% B/min (A eluent = 95:5:0.05 water:acetonitrile:trifluoroacetic acid, B eluent = 5:95:0.01 water:acetonitrile:trifluoroacetic acid) with visualization at 270 nm. Analytical chiral HPLC was performed with an Agilent 1100 Series HPLC utilizing a chiralcel AD column (4.6 mm x 25 cm) obtained from Daicel Chemical Industries, Ltd with visualization at 254 nm. Optical rotations were measured with a Jasco P-1010 polarimeter.1 H and 1 3 C NMR spectra were recorded on either a Varian Mercury 300 (at 300 MHz and 75 MHz respectively), Varian Mercury 500 (at 500 MHz and 125 MHz respectively), or on a Varian Mercury 600 (600 MHz for proton only) spectrometer and are reported relative to Me 4 Si (d 0.0). Data for 1 H NMR spectra are reported as follows: chemical shift (d ppm), multiplicity, coupling constant (Hz) and integration. Data for 1 3 C NMR spectra are reported in terms of chemical shift. IR spectra were recorded on a Perkin Elmer Paragon 1000 spectrometer and are reported in frequency of absorption (cm -1 ). UV spectra were measured on a Beckman-Coulter DU 7400 spectrophotometer. High resolution mass spectra were obtained from the Caltech Mass Spectral Facility. Crystallographic data have been deposited at the CCDC, 12 Union Road, Cambridge CB2 1EZ, UK and copies can be obtained on request, free of charge, by quoting the publication citation and the deposition number (see individual structures for deposition number). Am. Chem. Soc. 2002, 124, 7284-7285.

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“…The aqueous phase was extracted with ethyl acetate (50 mL), and the combined organics were dried over magnesium sulfate. Solvent was evaporated and the residue was purified by flash chromatography (10:10:80 to 15:15:70 ethyl acetate:dichloromethane:hexanes eluent) to provide aldol adduct (+)-17 (6.01 g, 96% yield) as a colorless oil: R F 0.61 (50:25:25 hexanes:dichloromethane eluent); 1 9, 140.6, 133.2, 129.1, 128.6, 99.8, 74.9, 72.8, 72.0, 61.0, 42.9, 31.2, 28.8, 24.4, 22.5, 14.4; IR (NaCl/film) 3480,2986,1710,1447,1346,1204 Lactone (-)-SI3. A solution of aldol adduct (+)-17 (0.467g, 1.21 mmol) in tetrahydrofuran (12 mL) was acidified with aqueous hydrochloric acid (0.242 mL, 0.242 mmol).…”

mentioning

confidence: 99%

The Total Synthesis of (−)-Lemonomycin

Ashley

¹

,

Cruz

²

,

Stoltz

³

2003

View full text Add to dashboard Cite

Material and Methods. Unless otherwise stated, reactions were performed at ambient temperature (typically 20 °C) in flame-dried glassware under a nitrogen or argon atmosphere using dry, deoxygenated solvents. Solvents were dried by passage through an activated alumina column under argon. Acrolein was distilled under nitrogen immediately prior to use. All other commercially obtained reagents were used as received. Reaction temperatures were controlled by an IKAmag temperature modulator. Thin-layer chromatography (TLC) was performed using E. Merck silica gel 60 F254 precoated plates (0.25 mm) and visualized by UV, anisaldehyde, permanganate, or CAM staining. ICN Silica gel (particle size 0.032-0.063 mm) was used for flash chromatography. Preparatory reversed-phase HPLC was performed on a Waters HPLC with a Waters Delta-Pak 25 x 100 mm, 15 mm C 1 8 column equipped with a guard, utilizing a flow rate of 10 mL/min and a ramp of 1% B/min (A eluent = 95:5:0.05 water:acetonitrile:trifluoroacetic acid, B eluent = 5:95:0.01 water:acetonitrile:trifluoroacetic acid) with visualization at 270 nm. Analytical chiral HPLC was performed with an Agilent 1100 Series HPLC utilizing a chiralcel AD column (4.6 mm x 25 cm) obtained from Daicel Chemical Industries, Ltd with visualization at 254 nm. Optical rotations were measured with a Jasco P-1010 polarimeter.1 H and 1 3 C NMR spectra were recorded on either a Varian Mercury 300 (at 300 MHz and 75 MHz respectively), Varian Mercury 500 (at 500 MHz and 125 MHz respectively), or on a Varian Mercury 600 (600 MHz for proton only) spectrometer and are reported relative to Me 4 Si (d 0.0). Data for 1 H NMR spectra are reported as follows: chemical shift (d ppm), multiplicity, coupling constant (Hz) and integration. Data for 1 3 C NMR spectra are reported in terms of chemical shift. IR spectra were recorded on a Perkin Elmer Paragon 1000 spectrometer and are reported in frequency of absorption (cm -1 ). UV spectra were measured on a Beckman-Coulter DU 7400 spectrophotometer. High resolution mass spectra were obtained from the Caltech Mass Spectral Facility. Crystallographic data have been deposited at the CCDC, 12 Union Road, Cambridge CB2 1EZ, UK and copies can be obtained on request, free of charge, by quoting the publication citation and the deposition number (see individual structures for deposition number). Am. Chem. Soc. 2002, 124, 7284-7285.

show abstract

Synthesis and absolute configuration of four diastereoisomeric 1-(2-furyl)-2-aminobutane-1,3-diols

Cited by 14 publications

References 11 publications

Recent Advances in Substrate-Controlled Asymmetric Induction Derived from Chiral Pool α-Amino Acids for Natural Product Synthesis

Recent Advances in Substrate-Controlled Asymmetric Induction Derived from Chiral Pool α-Amino Acids for Natural Product Synthesis

The Total Synthesis of (‐)‐Lemonomycin.

The Total Synthesis of (−)-Lemonomycin

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