| Article ID | Journal | Published Year | Pages | File Type |
|---|---|---|---|---|
| 1347233 | Tetrahedron: Asymmetry | 2014 | 17 Pages |
The total synthesis of the HCl salts of (−)-jaspine B ent-1 and its 4-epi-congener ent-4 was accomplished starting from the common template 13 derived from d-xylose. The cornerstone of our synthesis was [3,3]-heterosigmatropic rearrangements, which effectively provided scaffolds with a chiral amino group. A subsequent Wittig olefination installed a C14 alkyl side chain and acid-mediated ring-closing reaction established the tetrahydrofuran core.
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Methyl {(1R)-1-[(4′R,5′R)-5′-(benzyloxy)-2′,2′-dimethyl-1′,3′-dioxan-4′-yl]allyl}carbamateC18H25NO5[α]D22 = +7.3 (c 0.30, CHCl3)Source of chirality: d-xyloseAbsolute configuration: (1R,4′R,5′R)
(4R)-4-[(4′R,5′R)-5′-(Benzyloxy)-2′,2′-dimethyl-1′,3′-dioxan-4′-yl]oxazolidin-2-oneC16H21NO5[α]D22 = −71.3 (c 0.30, CHCl3)Source of chirality: d-xyloseAbsolute configuration: (4R,4′R,5′R)
(4S)-4-[(4′R,5′R)-5′-(Benzyloxy)-2′,2′-dimethyl-1′,3′-dioxan-4′-yl]oxazolidin-2-oneC16H21NO5[α]D23 = −7.7 (c 0.22, CHCl3)Source of chirality: d-xyloseAbsolute configuration: (4S,4′R,5′R)
(4R)-4-[(1′R,2′R)-1′,2′-Dihydroxyhexadecyl]oxazolidin-2-oneC19H37NO4[α]D22 = +8.7 (c 0.38, CHCl3)Source of chirality: d-xyloseAbsolute configuration: (4R,1′R,2′R)
(4S)-4-[(1′R,2′R)-1′,2′-Dihydroxyhexadecyl]oxazolidin-2-oneC19H37NO4[α]D22 = +24.0 (c 0.20, CHCl3)Source of chirality: d-xyloseAbsolute configuration: (4S,1′R,2′R)
(2R,3R,4R)-4-Amino-2-tetradecyltetrahydrofuran-3-ol hydrochlorideC18H38ClNO2[α]D27 = −2.9 (c 0.28, CH3OH)Source of chirality: d-xyloseAbsolute configuration: (2R,3R,4R)
(2R,3R,4S)-4-Amino-2-tetradecyltetrahydrofuran-3-ol hydrochlorideC18H38ClNO2[α]D27 = +7.5 (c 0.52, CH3OH)Source of chirality: d-xyloseAbsolute configuration: (2R,3R,4S)
(2R,3R,4R)-4-Acetamido-2-tetradecyltetrahydrofuran-3-yl acetateC22H41NO4[α]D23 = +25.0 (c 0.14, CHCl3)Source of chirality: d-xyloseAbsolute configuration: (2R,3R,4R)
(2R,3R)-3-(Benzyloxy)-2,4-dihydroxybutyl benzoateC18H20O5[α]D25 = −30.7 (c 0.28, CHCl3)Source of chirality: d-xyloseAbsolute configuration: (2R,3R)
[(4′R,5′R)-5′-(Benzyloxy)-2′,2′-dimethyl-1′,3′-dioxan-4′-yl]methyl benzoateC21H24O5[α]D22 = −52.7 (c 0.26, CHCl3)Source of chirality: d-xyloseAbsolute configuration: (4′R,5′R)
5-O-Benzoyl-3-O-benzyl-1,2-O-isopropylidene-α-d-xylofuranoseC22H24O6[α]D25 = −46.1 (c 0.28, CHCl3)Source of chirality: d-xyloseAbsolute configuration: (1R,2R,3S,4R)
Ethyl (E)-3-[(4′R,5′R)-5′-(benzyloxy)-2′,2′-dimethyl-1′,3′-dioxan-4′-yl]acrylateC18H24O5[α]D22 = +12.3 (c 0.26, CHCl3)Source of chirality: d-xyloseAbsolute configuration: (E,4′R,5′R)
Ethyl (Z)-3-[(4′R,5′R)-5′-(benzyloxy)-2′,2′-dimethyl-1′,3′-dioxan-4′-yl]acrylateC18H24O5[α]D22 = −203.0 (c 0.28, CHCl3)Source of chirality: d-xyloseAbsolute configuration: (Z,4′R,5′R)
(E)-3-[(4′R,5′R)-5′-(Benzyloxy)-2′,2′-dimethyl-1′,3′-dioxan-4′-yl]prop-2-en-1-olC16H22O4[α]D23 = −31.9 (c 0.26, CHCl3)Source of chirality: d-xyloseAbsolute configuration: (2E,4′R,5′R)
(Z)-3-[(4′R,5′R)-5′-(Benzyloxy)-2′,2′-dimethyl-1′,3′-dioxan-4′-yl]prop-2-en-1-olC16H22O4[α]D18 = −37.3 (c 0.22, CHCl3)Source of chirality: d-xyloseAbsolute configuration: (2Z,4′R,5′R)
(4R,5R)-5-(Benzyloxy)-2,2-dimethyl-4-[(E)-3′-thiocyanatoprop-1′-en-1′-yl]-1,3-dioxanC17H21NO3S[α]D23 = −49.6 (c 0.26, CHCl3)Source of chirality: d-xyloseAbsolute configuration: (1′E,4R,5R)
(4R,5R)-5-(Benzyloxy)-4-[(1′R)-1′-isothiocyanatoallyl]-2,2-dimethyl-1,3-dioxanC17H21NO3S[α]D23 = −61.4 (c 0.28, CHCl3)Source of chirality: d-xyloseAbsolute configuration: (4R,5R,1′R)
(4R,5R)-5-(Benzyloxy)-4-[(1′S)-1′-isothiocyanatoallyl]-2,2-dimethyl-1,3-dioxanC17H21NO3S[α]D25 = −41.9 (c 0.32, CHCl3)Source of chirality: d-xyloseAbsolute configuration: (4R,5R,1′S)
N-{(1′R)-1-[(4″R,5″R)-5″-(Benzyloxy)-2″,2″-dimethyl-1″,3″-dioxan-4″-yl]allyl}-2,2,2-trichloroacetamideC18H22Cl3NO4[α]D24 = +27.3 (c 0.22, CHCl3)Source of chirality: d-xyloseAbsolute configuration: (1′R,4″R,5″R)
N-{(1′S)-1-[(4″R,5″R)-5″-(Benzyloxy)-2″,2″-dimethyl-1″,3″-dioxan-4″-yl]allyl}-2,2,2-trichloroacetamideC18H22Cl3NO4[α]D24 = −28.7 (c 0.30, CHCl3)Source of chirality: d-xyloseAbsolute configuration: (1′S,4″R,5″R)
Methyl {(1R)-1-[(4′R,5′R)-5′-(benzyloxy)-2′,2′-dimethyl-1′,3′-dioxan-4′-yl]-2-hydroxyethyl}carbamateC17H25NO6[α]D23 = −42.3 (c 0.26, CHCl3)Source of chirality: d-xyloseAbsolute configuration: (1R,4′R,5′R)
Methyl {(1S)-1-[(4′R,5′R)-5′-(benzyloxy)-2′,2′-dimethyl-1′,3′-dioxan-4′-yl]allyl}carbamateC18H25NO5[α]D23 = −49.3 (c 0.30, CHCl3)Source of chirality: d-xyloseAbsolute configuration: (1S,4′R,5′R)
Methyl {(1S)-1-[(4′R,5′R)-5′-(benzyloxy)-2′,2′-dimethyl-1′,3′-dioxan-4′-yl]-2-hydroxyethyl}carbamateC17H25NO6[α]D23 = −26.5 (c 0.26, CHCl3)Source of chirality: d-xyloseAbsolute configuration: (1S,4′R,5′R)
N-{(1′R)-1′-[(4″R,5″R)-5″-(Benzyloxy)-2″,2″-dimethyl-1″,3″-dioxan-4″-yl]-2′-hydroxyethyl}-2,2,2-trichloroacetamideC17H22Cl3NO5[α]D24 = −18.0 (c 0.30, CHCl3)Source of chirality: d-xyloseAbsolute configuration: (1′R,4″R,5″R)
N-{(1′S)-1′-[(4″R,5″R)-5″-(Benzyloxy)-2″,2″-dimethyl-1″,3″-dioxan-4″-yl]-2′-hydroxyethyl}-2,2,2-trichloroacetamideC17H22Cl3NO5[α]D24 = −10.0 (c 0.30, CHCl3)Source of chirality: d-xyloseAbsolute configuration: (1′S,4″R,5″R)
(4R)-4-[(1′R,2′R)-2′-(Benzyloxy)-1′,3′-dihydroxypropyl]oxazolidin-2-oneC13H17NO5[α]D23 = −16.7 (c 0.24, CH3OH)Source of chirality: d-xyloseAbsolute configuration: (4R,1′R,2′R)
(4S)-4-[(1′R,2′R)-2′-(Benzyloxy)-1′,3′-dihydroxypropyl]oxazolidin-2-oneC13H17NO5[α]D24 = +3.2 (c 0.36, CH3OH)Source of chirality: d-xyloseAbsolute configuration: (4S,1′R,2′R)
(4R)-4-[(1′R,2′R)-2′-(Benzyloxy)-1′-hydroxy-3′-(trityloxy)propyl]oxazolidin-2-oneC32H31NO5[α]D24 = −33.0 (c 0.30, CHCl3)Source of chirality: d-xyloseAbsolute configuration: (4R,1′R,2′R)
(4S)-4-[(1′R,2′R)-2′-(Benzyloxy)-1′-hydroxy-3′-(trityloxy)propyl]oxazolidin-2-oneC32H31NO5[α]D24 = −20.5 (c 0.38, CHCl3)Source of chirality: d-xyloseAbsolute configuration: (4S,1′R,2′R)
(4R)-3-Benzyl-4-[(1′R,2′R)-1′,2′-bis(benzyloxy)-3′-(trityloxy)propyl]oxazolidin-2-oneC46H43NO5[α]D22 = +13.5 (c 0.20, CHCl3)Source of chirality: d-xyloseAbsolute configuration: (4R,1′R,2′R)
(4S)-3-Benzyl-4-[(1′R,2′R)-1′,2′-bis(benzyloxy)-3′-(trityloxy)propyl]oxazolidin-2-oneC46H43NO5[α]D22 = +10.0 (c 0.24, CHCl3)Source of chirality: d-xyloseAbsolute configuration: (4S,1′R,2′R)
(4R)-3-Benzyl-4-[(1′R,2′R)-1′,2′-bis(benzyloxy)-3′-hydroxypropyl]oxazolidin-2-oneC27H29NO5[α]D22 = +31.7 (c 0.18, CHCl3)Source of chirality: d-xyloseAbsolute configuration: (4R,1′R,2′R)
(4S)-3-Benzyl-4-[(1′R,2′R)-1′,2′-bis(benzyloxy)-3′-hydroxypropyl]oxazolidin-2-oneC27H29NO5[α]D22 = +5.0 (c 0.30, CHCl3)Source of chirality: d-xyloseAbsolute configuration: (4S,1′R,2′R)
(4S)-3-Benzyl-4-[(1′R,2′R,3′Z)-1′,2′-bis(benzyloxy)hexadec-3′-en-1′-yl]oxazolidin-2-oneC40H53NO4[α]D23 = −12.0 (c 0.20, CHCl3)Source of chirality: d-xyloseAbsolute configuration: (4S,1′R,2′R,3′Z)
(4R)-3-(Cyclohexylmethyl)-4-[(1′R,2′R)-1′,2′-dihydroxyhexadecyl]oxazolidin-2-oneC26H49NO4[α]D23 = +14.0 (c 0.20, CHCl3)Source of chirality: d-xyloseAbsolute configuration: (4R,1′R,2′R)
(4R)-3-Benzyl-4-[(1′R,2′R)-1′,2′-dihydroxyhexadecyl]oxazolidin-2-oneC26H43NO4[α]D25 = +4.4 (c 0.52, CHCl3)Source of chirality: d-xyloseAbsolute configuration: (4R,1′R,2′R)
(4S)-3-(Cyclohexylmethyl)-4-[(1′R,2′R)-1′,2′-dihydroxyhexadecyl]oxazolidin-2-oneC26H49NO4[α]D21 = −9.5 (c 0.38, CHCl3)Source of chirality: d-xyloseAbsolute configuration: (4S,1′R,2′R)
(4S)-3-Benzyl-4-[(1′R,2′R)-1′,2′-dihydroxyhexadecyl]oxazolidin-2-oneC26H43NO4[α]D21 = +6.7 (c 0.76, CHCl3)Source of chirality: d-xyloseAbsolute configuration: (4S,1′R,2′R)
(2R,3R,4S)-4-Acetamido-2-tetradecyltetrahydrofuran-3-yl acetateC22H41NO4[α]D23 = +9.9 (c 0.26, CHCl3)Source of chirality: d-xyloseAbsolute configuration: (2R,3R,4S)
