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[ CAS No. 16846-24-5 ] {[proInfo.proName]}

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Cat. No.: {[proInfo.prAm]}
Chemical Structure| 16846-24-5
Chemical Structure| 16846-24-5
Structure of 16846-24-5 * Storage: {[proInfo.prStorage]}
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Quality Control of [ 16846-24-5 ]

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Product Details of [ 16846-24-5 ]

CAS No. :16846-24-5 MDL No. :MFCD00210320
Formula : C42H69NO15 Boiling Point : -
Linear Structure Formula :- InChI Key :-
M.W : 828.00 Pubchem ID :-
Synonyms :
EN-141;Kitasamycin A3;CCRIS 8511;Turimycin A5;Leucomycin A3

Calculated chemistry of [ 16846-24-5 ]

Physicochemical Properties

Num. heavy atoms : 58
Num. arom. heavy atoms : 0
Fraction Csp3 : 0.81
Num. rotatable bonds : 14
Num. H-bond acceptors : 16.0
Num. H-bond donors : 3.0
Molar Refractivity : 212.62
TPSA : 206.05 Ų

Pharmacokinetics

GI absorption : Low
BBB permeant : No
P-gp substrate : No
CYP1A2 inhibitor : No
CYP2C19 inhibitor : No
CYP2C9 inhibitor : No
CYP2D6 inhibitor : No
CYP3A4 inhibitor : No
Log Kp (skin permeation) : -9.65 cm/s

Lipophilicity

Log Po/w (iLOGP) : 5.55
Log Po/w (XLOGP3) : 2.39
Log Po/w (WLOGP) : 3.01
Log Po/w (MLOGP) : -0.06
Log Po/w (SILICOS-IT) : 1.23
Consensus Log Po/w : 2.43

Druglikeness

Lipinski : 2.0
Ghose : None
Veber : 2.0
Egan : 1.0
Muegge : 3.0
Bioavailability Score : 0.17

Water Solubility

Log S (ESOL) : -5.56
Solubility : 0.00231 mg/ml ; 0.00000278 mol/l
Class : Moderately soluble
Log S (Ali) : -6.36
Solubility : 0.000363 mg/ml ; 0.000000438 mol/l
Class : Poorly soluble
Log S (SILICOS-IT) : -2.17
Solubility : 5.57 mg/ml ; 0.00673 mol/l
Class : Soluble

Medicinal Chemistry

PAINS : 0.0 alert
Brenk : 2.0 alert
Leadlikeness : 2.0
Synthetic accessibility : 9.39

Safety of [ 16846-24-5 ]

Signal Word:Warning Class:N/A
Precautionary Statements:P261-P305+P351+P338 UN#:N/A
Hazard Statements:H302-H315-H319-H335 Packing Group:N/A
GHS Pictogram:

Application In Synthesis of [ 16846-24-5 ]

* All experimental methods are cited from the reference, please refer to the original source for details. We do not guarantee the accuracy of the content in the reference.

  • Downstream synthetic route of [ 16846-24-5 ]

[ 16846-24-5 ] Synthesis Path-Downstream   1~51

  • 1
  • [ 16846-24-5 ]
  • [ 40361-41-9 ]
YieldReaction ConditionsOperation in experiment
92% With lithium tri-t-butoxyaluminum hydride In tetrahydrofuran at 0℃;
With sodium tetrahydroborate In methanol at 20℃; for 2h; (2S,3S,4R,6S)-6-(((2R,3S,4R,5R,6S)-4-(dimethylamino)-5-hydroxy-6-(((3E,5S,6S,7R, 9R,10R,11E,13E,16R)-10-hydroxy-7-(2-hydroxyethyl)-5-methoxy-9,16-dimethyl-2-oxooxacyclohexadeca-3,11,13-trien-6-yl)oxy)-2-methyltetrahydro-2H-pyran-3-yl)oxy)-4-hydroxy-2,4-dimethyltetrahydro-2H-pyran-3-yl 3-methylbutanoate (compound 12): josamycin 1 (200 mg, 0.24 mmol) and sodium borohydride (20 mg, 0.53 mmol) were dissolved in 15 ml of CH3OH. The mixture was stirred in room temperature. After 2 hours CH3OH was evaporated and residue was dissolved in 15 ml of diethyl ether. 5 ml of KOH (0.07M) was added to the mixture and stirred in room temperature. After 2 hours the mixture was extracted with diethyl ether and water. Diethyl ether layer was evaporated to dryness. 185 mg white powder of product 12 was obtained. Yield 97%, mp 112-117 °C, HPLC Rt=10.210 min. Anal. Calcd for C40H67NO13: C, 62.40; H, 8.77; N, 1.82; O, 27.01. Found C, 62.38; H, 8.79; N, 1.80; O, 27.03; HRMS (ESI-TOF) m/z: [M + H]+ Calcd for C40H67NO13 770.4685; Found 770.4665. 1H NMR (600 MHz, CDCl3, 25°C): 6.42 (dd, 1H, 3JH2,H3=15.5 Hz, 3JH3,H4=8.8 Hz, H3), 6.14 (dd, 1H, 3JH10,H11=14.9 Hz, 3JH11,H12=10.6 Hz, H11), 5.97 (dd, 1H, 3JH11,H12=10.4 Hz, 3JH12,H13=14.9 Hz, H12), 5.88 (d, 1H, 3JH2,H3=15.5 Hz, H2), 5.64 (dd, 1H, 3JH9,H10=9.2 Hz, 3JH10,H11=14.9 Hz, H10), 5.53 (ddd, 1H, 3JH12,H13=15.2 Hz, 3JH13,H14a=4.5 Hz, 3JH13,H14b=10.9 Hz, H13), 5.22 (m, 1H, H15), 5.07 (d, 1H, 3JH1’’,H2b’’=3.3 Hz, H1’’), 4.62 (d, 1H, 3JH4’’,H5’’=10.2 Hz, H4’’), 4.48 (m, 1H, H5’’), 4.46 (d, 1H, 3JH1’,H2’=7.6 Hz, H1’), 4.39 (bs, 1H, 3’’-OH), 4.10 (m, 1H, H9), 3.80* (m, 1H, H5), 3.80* (m, 1H, H4), 3.72 (m, 1H, H21a), 3.64 (dd, 1H, 3JH1’,H2’=7.7 Hz, 3JH2’,H3’=10.2 Hz, H2’), 3.51 (bs, 1H, 2’-OH), 3.49 (m, 1H, H21b), 3.31* (m, 1H, H4’), 3.31* (m, 1H, H5’), 3.23 (s, 3H, H19), 2.50 (s, 6H, H7’+H8’), 2.48 (m, 1H, H3’), 2.31 (d, 2H, 3JH9’,H10’’=7.1 Hz, H9’’), 2.14 (m, 1H, H10’’), 2.09 (m, 1H, H14a), 2.00 (d, 1H, 2J =13.8 Hz, H2a’’), 1.92 (bs, 1H, 9-OH), 1.90 (m, 1H, H8), 1.89 (m, 1H, H20b), 1.85 (m, 1H, H14b), 1.83 (dd, 1H, 2J =14.3 Hz, 3JH1”,H2’’=3.9 Hz, H2b’’), 1.75 (bs, 1H, 21-OH), 1.69 (m, 1H, H20a), 1.53 (m, 1H, H7a), 1.47 (m, 1H, H6), 1.34 (d, 3H, 3JH15,H16=6.3 Hz, H16), 1.28 (d, 3H, 3JH5’,H6’=5.7 Hz, H6’), 1.13 (d, 3H, 3JH5’’,H6’’=6.1 Hz, H6’’), 1.11 (s, 3H, H7’’), 0.98 (d, 3H, 3JH8,H22=6.6 Hz, H22), 0.97 (d, 6H, 3J H10’’,H11’’+H12’’=6.6 Hz, H11’’+H12’’), 0.89 (m, 1H, H7b); 13C NMR (600 MHz, CDCl3, 25°C): 173.0 (C8’’), 165.5 (C1), 140.6 (C3), 134.5 (C11), 133.8 (C12), 130.8 (C13), 129.2 (C10), 126.9 (C2), 106.0 (C1’), 96.8 (C1’’), 83.1 (C5), 82.3 (C4), 77.0 (C4’’), 75.0 (C4’), 73.2 (C5’), 72.6 (C9), 71.6 (C2’), 69.4 (C15), 69.3 (C3’), 69.2 (C3’’), 63.4 (C5’’), 60.8 (C21), 56.0 (C19), 43.3 (C9’’), 42.0 (C7’+C8’), 41.7 (C2’’), 41.6 (C14), 33.5 (C8), 32.4 (C6), 30.5 (C20), 29.7 (C7), 25.5 (C10’’), 25.3 (C7’’), 22.4 (C11’’), 22.3 (C12’’), 20.1 (C16), 18.9 (C6’), 17.9 (C6’’), 14.6 (C22), *-overlapped signals.
  • 2
  • [ 16846-24-5 ]
  • 3-methyl-butyric acid 6-{6-[4-acetoxy-10-hydroxy-5-methoxy-9,14-dimethyl-2-oxo-7-(2-oxo-ethyl)-oxacyclotetradec-11-en-6-yloxy]-4-dimethylamino-5-hydroxy-2-methyl-tetrahydro-pyran-3-yloxy}-4-hydroxy-2,4-dimethyl-tetrahydro-pyran-3-yl ester [ No CAS ]
YieldReaction ConditionsOperation in experiment
78% With 1-hexene In dichloromethane for 30h; Heating;
  • 3
  • [ 16846-24-5 ]
  • [ 21238-30-2 ]
YieldReaction ConditionsOperation in experiment
46% With pyridine; chromium(VI) oxide at 20℃; for 3h;
With Dess-Martin periodane In dichloromethane at 20℃;
  • 4
  • [ 16846-24-5 ]
  • Acetic acid (11E,13E)-(4R,5S,6S,7R,9R,16R)-6-((2S,3R,4R,5S,6R)-5-carbamoyloxy-4-dimethylamino-3-hydroxy-6-methyl-tetrahydro-pyran-2-yloxy)-5-methoxy-9,16-dimethyl-2,10-dioxo-7-(2-oxo-ethyl)-oxacyclohexadeca-11,13-dien-4-yl ester [ No CAS ]
YieldReaction ConditionsOperation in experiment
Multi-step reaction with 6 steps 1: 46 percent / aq. CrO3; pyridine / 3 h / 20 °C 2: 100 percent / pyridine / 16 h / 20 °C 3: 79 percent / aq. HCl / 16 h / 20 °C 4: Et3N / CH2Cl2 / 20 °C 5: NaHCO3 / methanol / 0.5 h / 20 °C 6: MeOH / 12 h / 20 °C
  • 5
  • [ 16846-24-5 ]
  • [ 491878-21-8 ]
YieldReaction ConditionsOperation in experiment
Multi-step reaction with 5 steps 1: 46 percent / aq. CrO3; pyridine / 3 h / 20 °C 2: 100 percent / pyridine / 16 h / 20 °C 3: 79 percent / aq. HCl / 16 h / 20 °C 4: Et3N / CH2Cl2 / 20 °C 5: NaHCO3 / methanol / 0.5 h / 20 °C
  • 6
  • [ 16846-24-5 ]
  • Acetic acid (11E,13E)-(4R,5S,6S,7R,9R,16R)-6-((2S,3R,4R,5S,6R)-5-allylcarbamoyloxy-4-dimethylamino-3-hydroxy-6-methyl-tetrahydro-pyran-2-yloxy)-5-methoxy-9,16-dimethyl-2,10-dioxo-7-(2-oxo-ethyl)-oxacyclohexadeca-11,13-dien-4-yl ester [ No CAS ]
YieldReaction ConditionsOperation in experiment
Multi-step reaction with 5 steps 1: 46 percent / aq. CrO3; pyridine / 3 h / 20 °C 2: 100 percent / pyridine / 16 h / 20 °C 3: 79 percent / aq. HCl / 16 h / 20 °C 4: Et3N / CH2Cl2 / 20 °C 5: 100 percent / MeOH / 20 °C
  • 7
  • [ 16846-24-5 ]
  • [ 676997-12-9 ]
YieldReaction ConditionsOperation in experiment
Multi-step reaction with 4 steps 1: 46 percent / aq. CrO3; pyridine / 3 h / 20 °C 2: 100 percent / pyridine / 16 h / 20 °C 3: 79 percent / aq. HCl / 16 h / 20 °C 4: Et3N / CH2Cl2 / 20 °C
  • 8
  • [ 16846-24-5 ]
  • Acetic acid (11E,13E)-(4R,5S,6S,7R,9R,16R)-6-((2S,3R,4R,5S,6R)-4-dimethylamino-3-hydroxy-6-methyl-5-phenylcarbamoyloxy-tetrahydro-pyran-2-yloxy)-5-methoxy-9,16-dimethyl-2,10-dioxo-7-(2-oxo-ethyl)-oxacyclohexadeca-11,13-dien-4-yl ester [ No CAS ]
YieldReaction ConditionsOperation in experiment
Multi-step reaction with 5 steps 1: 46 percent / aq. CrO3; pyridine / 3 h / 20 °C 2: 100 percent / pyridine / 16 h / 20 °C 3: 79 percent / aq. HCl / 16 h / 20 °C 4: Et3N / CH2Cl2 / 20 °C 5: 100 percent / MeOH / 20 °C
  • 9
  • [ 16846-24-5 ]
  • Acetic acid (11E,13E)-(4R,5S,6S,7R,9R,16R)-6-((2S,3R,4R,5S,6R)-5-benzylcarbamoyloxy-4-dimethylamino-3-hydroxy-6-methyl-tetrahydro-pyran-2-yloxy)-5-methoxy-9,16-dimethyl-2,10-dioxo-7-(2-oxo-ethyl)-oxacyclohexadeca-11,13-dien-4-yl ester [ No CAS ]
YieldReaction ConditionsOperation in experiment
Multi-step reaction with 5 steps 1: 46 percent / aq. CrO3; pyridine / 3 h / 20 °C 2: 100 percent / pyridine / 16 h / 20 °C 3: 79 percent / aq. HCl / 16 h / 20 °C 4: Et3N / CH2Cl2 / 20 °C 5: 100 percent / MeOH / 20 °C
  • 10
  • [ 16846-24-5 ]
  • acetic acid 6-(4-dimethylamino-3-hydroxy-6-methyl-5-trichloroacetylcarbamoyloxy-tetrahydro-pyran-2-yloxy)-5-methoxy-9,16-dimethyl-2,10-dioxo-7-(2-oxo-ethyl)-oxacyclohexadeca-11,13-dien-4-yl ester [ No CAS ]
YieldReaction ConditionsOperation in experiment
Multi-step reaction with 5 steps 1: 46 percent / aq. CrO3; pyridine / 3 h / 20 °C 2: 100 percent / pyridine / 16 h / 20 °C 3: 79 percent / aq. HCl / 16 h / 20 °C 4: Et3N / CH2Cl2 / 20 °C 5: 100 percent / MeOH / 20 °C
  • 11
  • [ 16846-24-5 ]
  • [ 676997-02-7 ]
YieldReaction ConditionsOperation in experiment
Multi-step reaction with 4 steps 1: 46 percent / aq. CrO3; pyridine / 3 h / 20 °C 2: 100 percent / pyridine / 16 h / 20 °C 3: 79 percent / aq. HCl / 16 h / 20 °C 4: Et3N / CH2Cl2 / 20 °C
  • 12
  • [ 16846-24-5 ]
  • [ 676997-08-3 ]
YieldReaction ConditionsOperation in experiment
Multi-step reaction with 4 steps 1: 46 percent / aq. CrO3; pyridine / 3 h / 20 °C 2: 100 percent / pyridine / 16 h / 20 °C 3: 79 percent / aq. HCl / 16 h / 20 °C 4: Et3N / CH2Cl2 / 20 °C
  • 13
  • [ 16846-24-5 ]
  • Acetic acid (11E,13E)-(4R,5S,6S,7R,9R,16R)-6-((2S,3R,4R,5S,6R)-4-dimethylamino-3-hydroxy-6-methyl-5-phenethylcarbamoyloxy-tetrahydro-pyran-2-yloxy)-5-methoxy-9,16-dimethyl-2,10-dioxo-7-(2-oxo-ethyl)-oxacyclohexadeca-11,13-dien-4-yl ester [ No CAS ]
YieldReaction ConditionsOperation in experiment
Multi-step reaction with 5 steps 1: 46 percent / aq. CrO3; pyridine / 3 h / 20 °C 2: 100 percent / pyridine / 16 h / 20 °C 3: 79 percent / aq. HCl / 16 h / 20 °C 4: Et3N / CH2Cl2 / 20 °C 5: 100 percent / MeOH / 20 °C
  • 14
  • [ 16846-24-5 ]
  • [ 491878-20-7 ]
YieldReaction ConditionsOperation in experiment
Multi-step reaction with 4 steps 1: 46 percent / aq. CrO3; pyridine / 3 h / 20 °C 2: 100 percent / pyridine / 16 h / 20 °C 3: 79 percent / aq. HCl / 16 h / 20 °C 4: Et3N / CH2Cl2 / 20 °C
  • 15
  • [ 16846-24-5 ]
  • Acetic acid (11E,13E)-(4R,5S,6S,7R,9R,16R)-6-[(2S,3R,4R,5S,6R)-4-dimethylamino-3-hydroxy-5-(4-methoxy-benzylcarbamoyloxy)-6-methyl-tetrahydro-pyran-2-yloxy]-5-methoxy-9,16-dimethyl-2,10-dioxo-7-(2-oxo-ethyl)-oxacyclohexadeca-11,13-dien-4-yl ester [ No CAS ]
YieldReaction ConditionsOperation in experiment
Multi-step reaction with 5 steps 1: 46 percent / aq. CrO3; pyridine / 3 h / 20 °C 2: 100 percent / pyridine / 16 h / 20 °C 3: 79 percent / aq. HCl / 16 h / 20 °C 4: Et3N / CH2Cl2 / 20 °C 5: 100 percent / MeOH / 20 °C
  • 16
  • [ 16846-24-5 ]
  • [ 676997-11-8 ]
YieldReaction ConditionsOperation in experiment
Multi-step reaction with 4 steps 1: 46 percent / aq. CrO3; pyridine / 3 h / 20 °C 2: 100 percent / pyridine / 16 h / 20 °C 3: 79 percent / aq. HCl / 16 h / 20 °C 4: Et3N / CH2Cl2 / 20 °C
  • 17
  • [ 16846-24-5 ]
  • Acetic acid (11E,13E)-(4R,5S,6S,7R,9R,16R)-6-[(2S,3R,4R,5S,6R)-4-dimethylamino-3-hydroxy-6-methyl-5-(4-nitro-benzylcarbamoyloxy)-tetrahydro-pyran-2-yloxy]-5-methoxy-9,16-dimethyl-2,10-dioxo-7-(2-oxo-ethyl)-oxacyclohexadeca-11,13-dien-4-yl ester [ No CAS ]
YieldReaction ConditionsOperation in experiment
Multi-step reaction with 5 steps 1: 46 percent / aq. CrO3; pyridine / 3 h / 20 °C 2: 100 percent / pyridine / 16 h / 20 °C 3: 79 percent / aq. HCl / 16 h / 20 °C 4: Et3N / CH2Cl2 / 20 °C 5: 100 percent / MeOH / 20 °C
  • 18
  • [ 16846-24-5 ]
  • [ 676997-09-4 ]
YieldReaction ConditionsOperation in experiment
Multi-step reaction with 4 steps 1: 46 percent / aq. CrO3; pyridine / 3 h / 20 °C 2: 100 percent / pyridine / 16 h / 20 °C 3: 79 percent / aq. HCl / 16 h / 20 °C 4: Et3N / CH2Cl2 / 20 °C
  • 19
  • [ 16846-24-5 ]
  • [ 676997-10-7 ]
YieldReaction ConditionsOperation in experiment
Multi-step reaction with 4 steps 1: 46 percent / aq. CrO3; pyridine / 3 h / 20 °C 2: 100 percent / pyridine / 16 h / 20 °C 3: 79 percent / aq. HCl / 16 h / 20 °C 4: Et3N / CH2Cl2 / 20 °C
  • 20
  • [ 16846-24-5 ]
  • [ 52442-94-1 ]
YieldReaction ConditionsOperation in experiment
Multi-step reaction with 3 steps 1: 92 percent / LiAl(O-t-Bu)3H / tetrahydrofuran / 0 °C 2: 1.) m-chloroperbenzoic acid, 2.) (CF3CO)2O, pyridine, 3.) K2CO3, CH3OH / 1) CH2Cl2, 0 deg C; 2) CH2Cl2, 0 - 25 deg C; 3) -10 deg C, 10 min 3: 80 percent / DDQ / benzene / 25 °C
  • 21
  • [ 16846-24-5 ]
  • [ 77405-61-9 ]
YieldReaction ConditionsOperation in experiment
Multi-step reaction with 8 steps 1: 92 percent / LiAl(O-t-Bu)3H / tetrahydrofuran / 0 °C 2: 1.) m-chloroperbenzoic acid, 2.) (CF3CO)2O, pyridine, 3.) K2CO3, CH3OH / 1) CH2Cl2, 0 deg C; 2) CH2Cl2, 0 - 25 deg C; 3) -10 deg C, 10 min 3: 80 percent / DDQ / benzene / 25 °C 4: 89 percent Turnov. / p-TsOH / tetrahydrofuran / 60 °C 5: 70 percent / K2CO3, CH3OH / 5 h / 0 °C 6: 90 percent / Et3N, 4-(dimethylamino)pyridine / CH2Cl2 / 25 °C 7: 95 percent / camphorsulfonic acid / acetone / 25 °C 8: 70 percent / HF-pyridine / tetrahydrofuran / 25 °C
  • 22
  • [ 16846-24-5 ]
  • carbenolide B hemiacetal [ No CAS ]
YieldReaction ConditionsOperation in experiment
Multi-step reaction with 8 steps 1: 92 percent / LiAl(O-t-Bu)3H / tetrahydrofuran / 0 °C 2: 1.) m-chloroperbenzoic acid, 2.) (CF3CO)2O, pyridine, 3.) K2CO3, CH3OH / 1) CH2Cl2, 0 deg C; 2) CH2Cl2, 0 - 25 deg C; 3) -10 deg C, 10 min 3: 80 percent / DDQ / benzene / 25 °C 4: 89 percent Turnov. / p-TsOH / tetrahydrofuran / 60 °C 5: 70 percent / K2CO3, CH3OH / 5 h / 0 °C 6: 100 percent / O2 / Pt / 25 °C 7: 50 percent Turnov. / LiAl(O-t-Bu)3H / tetrahydrofuran / 25 °C 8: 86 percent / DDQ / benzene / 25 °C
Multi-step reaction with 14 steps 1: 92 percent / LiAl(O-t-Bu)3H / tetrahydrofuran / 0 °C 2: 1.) m-chloroperbenzoic acid, 2.) (CF3CO)2O, pyridine, 3.) K2CO3, CH3OH / 1) CH2Cl2, 0 deg C; 2) CH2Cl2, 0 - 25 deg C; 3) -10 deg C, 10 min 3: 80 percent / DDQ / benzene / 25 °C 4: 89 percent Turnov. / p-TsOH / tetrahydrofuran / 60 °C 5: 70 percent / K2CO3, CH3OH / 5 h / 0 °C 6: 90 percent / Et3N, 4-(dimethylamino)pyridine / CH2Cl2 / 25 °C 7: 95 percent / camphorsulfonic acid / acetone / 25 °C 8: 70 percent / HF-pyridine / tetrahydrofuran / 25 °C 9: 95 percent / Jones reagent / acetone / 0 °C 11: 70 percent / aq. HCl / tetrahydrofuran / 60 °C 12: 85 percent / pyridine, 4-(dimethylamino)pyridine / CH2Cl2 / 25 °C 13: 50 percent Turnov. / LiAl(O-t-Bu)3H / tetrahydrofuran / 25 °C 14: 86 percent / DDQ / benzene / 25 °C
Multi-step reaction with 13 steps 1: 92 percent / LiAl(O-t-Bu)3H / tetrahydrofuran / 0 °C 2: 1.) m-chloroperbenzoic acid, 2.) (CF3CO)2O, pyridine, 3.) K2CO3, CH3OH / 1) CH2Cl2, 0 deg C; 2) CH2Cl2, 0 - 25 deg C; 3) -10 deg C, 10 min 3: 80 percent / DDQ / benzene / 25 °C 4: 89 percent Turnov. / p-TsOH / tetrahydrofuran / 60 °C 5: 70 percent / K2CO3, CH3OH / 5 h / 0 °C 6: 90 percent / Et3N, 4-(dimethylamino)pyridine / CH2Cl2 / 25 °C 7: 95 percent / camphorsulfonic acid / acetone / 25 °C 8: 70 percent / HF-pyridine / tetrahydrofuran / 25 °C 9: 95 percent / Jones reagent / acetone / 0 °C 10: 70 percent / aq. HCl / tetrahydrofuran / 60 °C 11: 85 percent / pyridine, 4-(dimethylamino)pyridine / CH2Cl2 / 25 °C 12: 50 percent Turnov. / LiAl(O-t-Bu)3H / tetrahydrofuran / 25 °C 13: 86 percent / DDQ / benzene / 25 °C
  • 23
  • [ 16846-24-5 ]
  • [ 77405-60-8 ]
YieldReaction ConditionsOperation in experiment
Multi-step reaction with 6 steps 1: 92 percent / LiAl(O-t-Bu)3H / tetrahydrofuran / 0 °C 2: 1.) m-chloroperbenzoic acid, 2.) (CF3CO)2O, pyridine, 3.) K2CO3, CH3OH / 1) CH2Cl2, 0 deg C; 2) CH2Cl2, 0 - 25 deg C; 3) -10 deg C, 10 min 3: 80 percent / DDQ / benzene / 25 °C 4: 89 percent Turnov. / p-TsOH / tetrahydrofuran / 60 °C 5: 70 percent / K2CO3, CH3OH / 5 h / 0 °C 6: 90 percent / Et3N, 4-(dimethylamino)pyridine / CH2Cl2 / 25 °C
  • 24
  • [ 16846-24-5 ]
  • [ 77405-59-5 ]
YieldReaction ConditionsOperation in experiment
Multi-step reaction with 5 steps 1: 92 percent / LiAl(O-t-Bu)3H / tetrahydrofuran / 0 °C 2: 1.) m-chloroperbenzoic acid, 2.) (CF3CO)2O, pyridine, 3.) K2CO3, CH3OH / 1) CH2Cl2, 0 deg C; 2) CH2Cl2, 0 - 25 deg C; 3) -10 deg C, 10 min 3: 80 percent / DDQ / benzene / 25 °C 4: 89 percent Turnov. / p-TsOH / tetrahydrofuran / 60 °C 5: 70 percent / K2CO3, CH3OH / 5 h / 0 °C
  • 25
  • [ 16846-24-5 ]
  • [ 77405-63-1 ]
YieldReaction ConditionsOperation in experiment
Multi-step reaction with 11 steps 1: 92 percent / LiAl(O-t-Bu)3H / tetrahydrofuran / 0 °C 2: 1.) m-chloroperbenzoic acid, 2.) (CF3CO)2O, pyridine, 3.) K2CO3, CH3OH / 1) CH2Cl2, 0 deg C; 2) CH2Cl2, 0 - 25 deg C; 3) -10 deg C, 10 min 3: 80 percent / DDQ / benzene / 25 °C 4: 89 percent Turnov. / p-TsOH / tetrahydrofuran / 60 °C 5: 70 percent / K2CO3, CH3OH / 5 h / 0 °C 6: 90 percent / Et3N, 4-(dimethylamino)pyridine / CH2Cl2 / 25 °C 7: 95 percent / camphorsulfonic acid / acetone / 25 °C 8: 70 percent / HF-pyridine / tetrahydrofuran / 25 °C 9: 95 percent / Jones reagent / acetone / 0 °C 11: 70 percent / aq. HCl / tetrahydrofuran / 60 °C
Multi-step reaction with 10 steps 1: 92 percent / LiAl(O-t-Bu)3H / tetrahydrofuran / 0 °C 2: 1.) m-chloroperbenzoic acid, 2.) (CF3CO)2O, pyridine, 3.) K2CO3, CH3OH / 1) CH2Cl2, 0 deg C; 2) CH2Cl2, 0 - 25 deg C; 3) -10 deg C, 10 min 3: 80 percent / DDQ / benzene / 25 °C 4: 89 percent Turnov. / p-TsOH / tetrahydrofuran / 60 °C 5: 70 percent / K2CO3, CH3OH / 5 h / 0 °C 6: 90 percent / Et3N, 4-(dimethylamino)pyridine / CH2Cl2 / 25 °C 7: 95 percent / camphorsulfonic acid / acetone / 25 °C 8: 70 percent / HF-pyridine / tetrahydrofuran / 25 °C 9: 95 percent / Jones reagent / acetone / 0 °C 10: 70 percent / aq. HCl / tetrahydrofuran / 60 °C
  • 26
  • [ 16846-24-5 ]
  • [ 77418-02-1 ]
YieldReaction ConditionsOperation in experiment
Multi-step reaction with 2 steps 1: 92 percent / LiAl(O-t-Bu)3H / tetrahydrofuran / 0 °C 2: 1.) m-chloroperbenzoic acid, 2.) (CF3CO)2O, pyridine, 3.) K2CO3, CH3OH / 1) CH2Cl2, 0 deg C; 2) CH2Cl2, 0 - 25 deg C; 3) -10 deg C, 10 min
  • 27
  • [ 16846-24-5 ]
  • [ 77405-58-4 ]
YieldReaction ConditionsOperation in experiment
Multi-step reaction with 4 steps 1: 92 percent / LiAl(O-t-Bu)3H / tetrahydrofuran / 0 °C 2: 1.) m-chloroperbenzoic acid, 2.) (CF3CO)2O, pyridine, 3.) K2CO3, CH3OH / 1) CH2Cl2, 0 deg C; 2) CH2Cl2, 0 - 25 deg C; 3) -10 deg C, 10 min 3: 80 percent / DDQ / benzene / 25 °C 4: 89 percent Turnov. / p-TsOH / tetrahydrofuran / 60 °C
  • 28
  • [ 16846-24-5 ]
  • Acetic acid (7E,9E)-(3aR,5R,12R,16R,17S,17aS)-2,6-dihydroxy-17-methoxy-5,12-dimethyl-14-oxo-2,3,3a,5,6,11,12,14,15,16,17,17a-dodecahydro-4H-1,13-dioxa-cyclopentacyclohexadecen-16-yl ester [ No CAS ]
YieldReaction ConditionsOperation in experiment
Multi-step reaction with 7 steps 1: 92 percent / LiAl(O-t-Bu)3H / tetrahydrofuran / 0 °C 2: 1.) m-chloroperbenzoic acid, 2.) (CF3CO)2O, pyridine, 3.) K2CO3, CH3OH / 1) CH2Cl2, 0 deg C; 2) CH2Cl2, 0 - 25 deg C; 3) -10 deg C, 10 min 3: 80 percent / DDQ / benzene / 25 °C 4: 89 percent Turnov. / p-TsOH / tetrahydrofuran / 60 °C 5: 70 percent / K2CO3, CH3OH / 5 h / 0 °C 6: 100 percent / O2 / Pt / 25 °C 7: 50 percent Turnov. / LiAl(O-t-Bu)3H / tetrahydrofuran / 25 °C
Multi-step reaction with 13 steps 1: 92 percent / LiAl(O-t-Bu)3H / tetrahydrofuran / 0 °C 2: 1.) m-chloroperbenzoic acid, 2.) (CF3CO)2O, pyridine, 3.) K2CO3, CH3OH / 1) CH2Cl2, 0 deg C; 2) CH2Cl2, 0 - 25 deg C; 3) -10 deg C, 10 min 3: 80 percent / DDQ / benzene / 25 °C 4: 89 percent Turnov. / p-TsOH / tetrahydrofuran / 60 °C 5: 70 percent / K2CO3, CH3OH / 5 h / 0 °C 6: 90 percent / Et3N, 4-(dimethylamino)pyridine / CH2Cl2 / 25 °C 7: 95 percent / camphorsulfonic acid / acetone / 25 °C 8: 70 percent / HF-pyridine / tetrahydrofuran / 25 °C 9: 95 percent / Jones reagent / acetone / 0 °C 11: 70 percent / aq. HCl / tetrahydrofuran / 60 °C 12: 85 percent / pyridine, 4-(dimethylamino)pyridine / CH2Cl2 / 25 °C 13: 50 percent Turnov. / LiAl(O-t-Bu)3H / tetrahydrofuran / 25 °C
Multi-step reaction with 12 steps 1: 92 percent / LiAl(O-t-Bu)3H / tetrahydrofuran / 0 °C 2: 1.) m-chloroperbenzoic acid, 2.) (CF3CO)2O, pyridine, 3.) K2CO3, CH3OH / 1) CH2Cl2, 0 deg C; 2) CH2Cl2, 0 - 25 deg C; 3) -10 deg C, 10 min 3: 80 percent / DDQ / benzene / 25 °C 4: 89 percent Turnov. / p-TsOH / tetrahydrofuran / 60 °C 5: 70 percent / K2CO3, CH3OH / 5 h / 0 °C 6: 90 percent / Et3N, 4-(dimethylamino)pyridine / CH2Cl2 / 25 °C 7: 95 percent / camphorsulfonic acid / acetone / 25 °C 8: 70 percent / HF-pyridine / tetrahydrofuran / 25 °C 9: 95 percent / Jones reagent / acetone / 0 °C 10: 70 percent / aq. HCl / tetrahydrofuran / 60 °C 11: 85 percent / pyridine, 4-(dimethylamino)pyridine / CH2Cl2 / 25 °C 12: 50 percent Turnov. / LiAl(O-t-Bu)3H / tetrahydrofuran / 25 °C
  • 29
  • [ 16846-24-5 ]
  • [ 77405-57-3 ]
YieldReaction ConditionsOperation in experiment
Multi-step reaction with 4 steps 1: 92 percent / LiAl(O-t-Bu)3H / tetrahydrofuran / 0 °C 2: 1.) m-chloroperbenzoic acid, 2.) (CF3CO)2O, pyridine, 3.) K2CO3, CH3OH / 1) CH2Cl2, 0 deg C; 2) CH2Cl2, 0 - 25 deg C; 3) -10 deg C, 10 min 3: 80 percent / DDQ / benzene / 25 °C 4: 90 percent / NaSH / ethanol / 0 °C
  • 30
  • [ 16846-24-5 ]
  • [ 63838-05-1 ]
YieldReaction ConditionsOperation in experiment
Multi-step reaction with 6 steps 1: 92 percent / LiAl(O-t-Bu)3H / tetrahydrofuran / 0 °C 2: 1.) m-chloroperbenzoic acid, 2.) (CF3CO)2O, pyridine, 3.) K2CO3, CH3OH / 1) CH2Cl2, 0 deg C; 2) CH2Cl2, 0 - 25 deg C; 3) -10 deg C, 10 min 3: 80 percent / DDQ / benzene / 25 °C 4: 89 percent Turnov. / p-TsOH / tetrahydrofuran / 60 °C 5: 70 percent / K2CO3, CH3OH / 5 h / 0 °C 6: 100 percent / O2 / Pt / 25 °C
Multi-step reaction with 12 steps 1: 92 percent / LiAl(O-t-Bu)3H / tetrahydrofuran / 0 °C 2: 1.) m-chloroperbenzoic acid, 2.) (CF3CO)2O, pyridine, 3.) K2CO3, CH3OH / 1) CH2Cl2, 0 deg C; 2) CH2Cl2, 0 - 25 deg C; 3) -10 deg C, 10 min 3: 80 percent / DDQ / benzene / 25 °C 4: 89 percent Turnov. / p-TsOH / tetrahydrofuran / 60 °C 5: 70 percent / K2CO3, CH3OH / 5 h / 0 °C 6: 90 percent / Et3N, 4-(dimethylamino)pyridine / CH2Cl2 / 25 °C 7: 95 percent / camphorsulfonic acid / acetone / 25 °C 8: 70 percent / HF-pyridine / tetrahydrofuran / 25 °C 9: 95 percent / Jones reagent / acetone / 0 °C 11: 70 percent / aq. HCl / tetrahydrofuran / 60 °C 12: 85 percent / pyridine, 4-(dimethylamino)pyridine / CH2Cl2 / 25 °C
Multi-step reaction with 11 steps 1: 92 percent / LiAl(O-t-Bu)3H / tetrahydrofuran / 0 °C 2: 1.) m-chloroperbenzoic acid, 2.) (CF3CO)2O, pyridine, 3.) K2CO3, CH3OH / 1) CH2Cl2, 0 deg C; 2) CH2Cl2, 0 - 25 deg C; 3) -10 deg C, 10 min 3: 80 percent / DDQ / benzene / 25 °C 4: 89 percent Turnov. / p-TsOH / tetrahydrofuran / 60 °C 5: 70 percent / K2CO3, CH3OH / 5 h / 0 °C 6: 90 percent / Et3N, 4-(dimethylamino)pyridine / CH2Cl2 / 25 °C 7: 95 percent / camphorsulfonic acid / acetone / 25 °C 8: 70 percent / HF-pyridine / tetrahydrofuran / 25 °C 9: 95 percent / Jones reagent / acetone / 0 °C 10: 70 percent / aq. HCl / tetrahydrofuran / 60 °C 11: 85 percent / pyridine, 4-(dimethylamino)pyridine / CH2Cl2 / 25 °C
  • 31
  • [ 16846-24-5 ]
  • [ 77405-62-0 ]
YieldReaction ConditionsOperation in experiment
Multi-step reaction with 9 steps 1: 92 percent / LiAl(O-t-Bu)3H / tetrahydrofuran / 0 °C 2: 1.) m-chloroperbenzoic acid, 2.) (CF3CO)2O, pyridine, 3.) K2CO3, CH3OH / 1) CH2Cl2, 0 deg C; 2) CH2Cl2, 0 - 25 deg C; 3) -10 deg C, 10 min 3: 80 percent / DDQ / benzene / 25 °C 4: 89 percent Turnov. / p-TsOH / tetrahydrofuran / 60 °C 5: 70 percent / K2CO3, CH3OH / 5 h / 0 °C 6: 90 percent / Et3N, 4-(dimethylamino)pyridine / CH2Cl2 / 25 °C 7: 95 percent / camphorsulfonic acid / acetone / 25 °C 8: 70 percent / HF-pyridine / tetrahydrofuran / 25 °C 9: 95 percent / Jones reagent / acetone / 0 °C
  • 32
  • [ 16846-24-5 ]
  • ((7E,9E)-(1R,5R,12R,14R,15S,19S)-19-Methoxy-5,12,17,17-tetramethyl-3,11-dioxo-4,16,18-trioxa-bicyclo[13.3.1]nonadeca-7,9-dien-14-yl)-acetic acid methyl ester [ No CAS ]
YieldReaction ConditionsOperation in experiment
Multi-step reaction with 10 steps 1: 92 percent / LiAl(O-t-Bu)3H / tetrahydrofuran / 0 °C 2: 1.) m-chloroperbenzoic acid, 2.) (CF3CO)2O, pyridine, 3.) K2CO3, CH3OH / 1) CH2Cl2, 0 deg C; 2) CH2Cl2, 0 - 25 deg C; 3) -10 deg C, 10 min 3: 80 percent / DDQ / benzene / 25 °C 4: 89 percent Turnov. / p-TsOH / tetrahydrofuran / 60 °C 5: 70 percent / K2CO3, CH3OH / 5 h / 0 °C 6: 90 percent / Et3N, 4-(dimethylamino)pyridine / CH2Cl2 / 25 °C 7: 95 percent / camphorsulfonic acid / acetone / 25 °C 8: 70 percent / HF-pyridine / tetrahydrofuran / 25 °C 9: 95 percent / Jones reagent / acetone / 0 °C
  • 33
  • [ 16846-24-5 ]
  • (7E,9E)-(1R,5R,12R,14R,15S,19S)-14-[2-(tert-Butyl-diphenyl-silanyloxy)-ethyl]-19-methoxy-5,12,17,17-tetramethyl-4,16,18-trioxa-bicyclo[13.3.1]nonadeca-7,9-diene-3,11-dione [ No CAS ]
YieldReaction ConditionsOperation in experiment
Multi-step reaction with 7 steps 1: 92 percent / LiAl(O-t-Bu)3H / tetrahydrofuran / 0 °C 2: 1.) m-chloroperbenzoic acid, 2.) (CF3CO)2O, pyridine, 3.) K2CO3, CH3OH / 1) CH2Cl2, 0 deg C; 2) CH2Cl2, 0 - 25 deg C; 3) -10 deg C, 10 min 3: 80 percent / DDQ / benzene / 25 °C 4: 89 percent Turnov. / p-TsOH / tetrahydrofuran / 60 °C 5: 70 percent / K2CO3, CH3OH / 5 h / 0 °C 6: 90 percent / Et3N, 4-(dimethylamino)pyridine / CH2Cl2 / 25 °C 7: 95 percent / camphorsulfonic acid / acetone / 25 °C
  • 34
  • [ 6338-53-0 ]
  • [ 16846-24-5 ]
  • [ 1196808-61-3 ]
YieldReaction ConditionsOperation in experiment
In diethyl ether at 20℃; for 0.5h; Inert atmosphere;
  • 35
  • [ 13325-10-5 ]
  • [ 16846-24-5 ]
  • [ 1225385-68-1 ]
YieldReaction ConditionsOperation in experiment
82% Stage #1: 4-Aminobutanol; josamycin In diethyl ether at 20℃; for 0.5h; Inert atmosphere; Stage #2: With sodium tetrahydroborate In diethyl ether; ethanol for 120h; Inert atmosphere;
  • 36
  • [ 4048-33-3 ]
  • [ 16846-24-5 ]
  • [ 1225385-69-2 ]
YieldReaction ConditionsOperation in experiment
74% Stage #1: 6-amino-1-hexanol; josamycin In diethyl ether; ethanol at 20℃; for 0.5h; Inert atmosphere; Stage #2: With sodium tetrahydroborate In diethyl ether; ethanol for 120h; Inert atmosphere;
  • 37
  • [ 141-43-5 ]
  • [ 16846-24-5 ]
  • [ 1225385-66-9 ]
YieldReaction ConditionsOperation in experiment
75% Stage #1: ethanolamine; josamycin In diethyl ether at 20℃; for 0.5h; Inert atmosphere; Stage #2: With sodium tetrahydroborate In diethyl ether; ethanol for 120h; Inert atmosphere;
  • 38
  • [ 16846-24-5 ]
  • [ 156-87-6 ]
  • [ 1225385-67-0 ]
YieldReaction ConditionsOperation in experiment
62% Stage #1: josamycin; propan-1-ol-3-amine In diethyl ether at 20℃; for 0.5h; Inert atmosphere; Stage #2: With sodium tetrahydroborate In diethyl ether; ethanol for 120h; Inert atmosphere;
  • 39
  • [ 16846-24-5 ]
  • [ 71156-87-1 ]
YieldReaction ConditionsOperation in experiment
97% Stage #1: josamycin With potassium hydroxide In diethyl ether; ethanol at -20℃; for 0.5h; Stage #2: With hydrogenchloride In ethanol at -20℃; (2E)-3-deacetyl-josamycin (2) Josamycin (100 mg, 0.12 mmol) dissolved in ether was cooled down to -20°C and treated with KOH/EtOH solution (0.15 mmol KOH/3mL) and stirred for 0.5h. To avoid the formation of 3a and 3b bicyclic products on heating to room temperature, HCl/EtOH (0.05 mmol HCl/0.3mL EtOH) was added. Next the mixture was evaporated to dryness and twice extracted with CH2Cl2/H2O (30mL/20mL). Organic layer was washed with brine and evaporated. 2 josamycin derivative was obtained as a white solid. Yield: 90 mg (97%), m.p. 115-118°C: MS (HR-MALDI-TOF) Found: 768.4535 [M+H]+ for C40H66NO13, calculated: 768.4529; Elemental analysis C40H65NO13: found C=62.51% H=8.49% N=1.80%, calculated C=62.56% H=8.53% N=1.82%; FT-IR: (KBr disc): 3493 cm-1 ν(O9-H), 3438 cm-1 ν(O2’-H) and 3280 cm-1 ν(O3’’-H), 2727 cm-1 ν(C18-H) of formyl group, 1722 cm-1 ν(C=O) of formyl group, 1736 cm-1 ν(C=O) at C-8’’, 1718 cm-1 ν(C=O) at C-1, 1658 cm-1 ν(C=C) of diene and C(2)=C(3) double bond, 1165, 1119, 1080, 1053 and 1017 cm-1 ν(C-O); 1H NMR (600 MHz, CDCl3): 9.75 (s, 1H, H18), 6.53 (dd, 1H, 3JH2,H3=15.5 Hz, 3JH3,H4=9.2 Hz, H3), 6.16 (dd, 1H, 3JH10,H11=14.9 Hz, 3JH11,H12=10.7 Hz, H11), 5.98 (dd, 1H, 3JH12,H13=15.0 Hz, H12), 5.88 (d, 1H, H2), 5.61 (dd, 1H, 3JH9,H10=9.5 Hz, H10), 5.56 (ddd, 1H, 3JH13,H14a=4.4 Hz, 3JH13,H14b=10.9 Hz, H13), 5.25 (m, 1H, H15), 5.07 (d, 1H, 3JH1``,H2b``=3.8 Hz, H1``), 4.62 (d, 1H, 3JH4``,H5``=10.2 Hz, H4``), 4.47 (m, 1H, H5``), 4.33 (d, 1H, 3JH1`,H2`=7.6 Hz, H1`), 4.29 (bs, 1H, 3``-OH), 3.94 (dd, 1H, 3JH8,H9=4.1 Hz, H9), 3.82 (dd, 1H, 3JH4,H5=9.2 Hz, 3JH5,H6=1.9 Hz, H5), 3.72 (t, 1H, H4), 3.60 (dd, 1H, 3JH2`,H3`=10.1 Hz, H2`), 3.59 (bs, 1H, 2`-OH), 3.26* (m, 1H, H4`), 3.26* (m, 1H, H5`), 3.22 (s, 3H, -OCH3), 3.03 (dd, 1H, 2J =18.6 Hz, 3JH20a,H6=11.2 Hz, H17a), 2.50 (s, 6H, H7`+H8`), 2.47 (m, 1H, H17b), 2.46 (m, 1H, H3`), 2.30 (d, 2H, 3JH9`,H10``=7.2 Hz, H9``), 2.14 (m, 1H, H10``), 2.08 (m, 1H, H14a), 2.00 (d, 1H, 2J =14.3 Hz, H2a``), 2.02 (m, 1H, H6), 1.84 (m, H14b), 1.83 (dd, 1H, H2b``), 1.90* (m, 1H, H8), 1.90* (bs, 1H, 9-OH), 1.49 (ddd, 1H, 3JH6,H7a=3.4 Hz, 3JH7a,H8=13.5 Hz, 2J =13.8 Hz, H7a), 1.34 (d, 3H, 3JH15,H16=6.3 Hz, H16), 1.25 (d, 3H, 3JH5`,H6`=5.7 Hz, H6`), 1.13 (d, 3H, 3JH5``,H6``=6.2 Hz, H6``), 1.11 (s, 3H, H7``), 0.99 (d, 3H, 3JH8,H19=6.6 Hz, H19), 0.98 (d, 6H, 3J H10``,H11``+H12``=6.6 Hz, H11``+H12``), 0.92 (m, 1H, H7b), *-overlapped signals; 13C NMR (151 MHz, CDCl3): 201.6 (C18), 173.0 (C8``), 165.2 (C1), 140.5 (C3), 134.9 (C11), 133.6 (C12), 131.3 (C13), 128.6 (C10), 127.1 (C2), 105.8 (C1`), 96.8 (C1``), 82.9 (C5), 82.1 (C4), 77.1 (C4``), 75.1 (C4`), 73.1 (C5`), 72.9 (C9), 71.5 (C2`), 69.3 (C15), 69.2 (C3`), 69.1 (C3``), 63.4 (C5’’), 56.0 (-OCH3), 43.3 (C9``), 42.3 (C17), 42.0 (C7`+C8`), 41.8 (C14), 41.7 (C2``), 33.6 (C8), 29.9 (C6), 29.7 (C7), 25.5 (C10``), 25.3 (C7``), 22.4 (C11``), 22.3 (C12``), 20.2 (C16), 18.9 (C6`), 17.9 (C6’’), 14.5 (C19).
95% With potassium hydroxide In diethyl ether; ethanol at -10℃; for 1h; (2S,3S,4R,6S)-6-(((2R,3S,4R,5R,6S)-4-(dimethylamino)-5-hydroxy-6-(((3E,5S,6S,7R, 9R,10R,11E,13E,16R)-10-hydroxy-5-methoxy-9,16-dimethyl-2-oxo-7-(2-oxoethyl)oxacyclohexadeca-3,11,13-trien-6-yl)oxy)-2-methyltetrahydro-2H-pyran-3-yl)oxy)-4-hydroxy-2,4-dimethyltetrahydro-2H-pyran-3-yl 3-methylbutanoate (compound 2): josamycin 1 (100 mg, 0.12 mmol) dissolved in diethyl ether was cooled down to -10°C and treated with KOH/EtOH solution (0.15 mmol KOH/3 ml) and stirred. After 1 hour HCl/EtOH (0.05 mmol HCl/0.3 ml EtOH) was added. Next the mixture was evaporated to dryness and twice extracted with Et2O/H2O. Organic layer was washed with brine and evaporated. 88 mg of 2 josamycin derivative was obtained. Yield: 95%, mp 115-118 °C, HPLC Rt=11.471 min. Anal. Calcd for C40H65NO13: C, 62.56; H, 8.53; N, 1.82; O, 27.08. Found C, 62.58; H, 8.51; N, 1.79; O, 27.11; HRMS (ESI-TOF) m/z: [M + H]+ Calcd for C40H65NO13 768.4529; Found 768.4510. 1H NMR (600 MHz, CDCl3, 25°C): 9.75 (s, 1H, H21), 6.53 (dd, 1H, 3JH2,H3=15.5 Hz, 3JH3,H4=9.2 Hz, H3), 6.16 (dd, 1H, 3JH10,H11=14.9 Hz, 3JH11,H12=10.7 Hz, H11), 5.98 (dd, 1H, 3JH11,H12=10.6 Hz, 3JH12,H13=15.0 Hz, H12), 5.88 (d, 1H, 3JH2,H3=15.5 Hz, H2), 5.61 (dd, 1H, 3JH9,H10=9.5 Hz, 3JH10,H11=15.0 Hz, H10), 5.56 (ddd, 1H, 3JH12,H13=15.2 Hz, 3JH13,H14a=4.4 Hz, 3JH13,H14b=10.9 Hz, H13), 5.25 (m, 1H, H15), 5.07 (d, 1H, 3JH1’’,H2b’’=3.8 Hz, H1’’), 4.62 (d, 1H, 3JH4’’,H5’’=10.2 Hz, H4’’), 4.47 (m, 1H, H5’’), 4.33 (d, 1H, 3JH1’,H2’=7.6 Hz, H1’), 4.29 (bs, 1H, 3’’-OH), 3.94 (dd, 1H, 3JH8,H9=4.1 Hz, 3JH9,H10=9.5 Hz, H9), 3.82 (dd, 1H, 3JH4,H5=9.2 Hz, 3JH5,H6=1.9 Hz, H5), 3.72 (t, 3JH4,H5=9.2 Hz, 1H, H4), 3.60 (dd, 1H, 3JH1’,H2’=7.7 Hz, 3JH2’,H3’=10.1 Hz, H2’), 3.59 (bs, 1H, 2’-OH), 3.26* (m, 1H, H4’), 3.26* (m, 1H, H5’), 3.22 (s, 3H, H19), 3.03 (dd, 1H, 2J =18.6 Hz, 3JH20a,H6=11.2 Hz, H20a), 2.50 (s, 6H, H7’+H8’), 2.47 (m, 1H, H20b), 2.46 (m, 1H, H3’), 2.30 (d, 2H, 3JH9’,H10’’=7.2 Hz, H9’’), 2.14 (m, 1H, H10’’), 2.08 (m, 1H, H14a), 2.00 (d, 1H, 2J =14.3 Hz, H2a’’), 2.02 (m, 1H, H6), 1.90* (m, 1H, H8), 1.90* (bs, 1H, 9-OH), 1.84 (m, 1H H14b), 1.83 (dd, 2J =14.3 Hz, 3JH1’’,H2b’’=3.9 Hz, 1H, H2b’’), 1.49 (ddd, 1H, 3JH6,H7a=3.4 Hz, 3JH7a,H8=13.5 Hz, 2J =13.8 Hz, H7a), 1.34 (d, 3H, 3JH15,H16=6.3 Hz, H16), 1.25 (d, 3H, 3JH5’,H6’=5.7 Hz, H6’), 1.13 (d, 3H, 3JH5’’,H6’’=6.2 Hz, H6’’), 1.11 (s, 3H, H7’’), 0.99 (d, 3H, 3JH8,H22=6.6 Hz, H22), 0.98 (d, 6H, 3J H10’’,H11’’+H12’’=6.6 Hz, H11’’+H12’’), 0.92 (m, 1H, H7b); 13C NMR (600 MHz, CDCl3, 25°C): 201.6 (C21), 173.0 (C8’’), 165.2 (C1), 140.5 (C3), 134.9 (C11), 133.6 (C12), 131.3 (C13), 128.6 (C10), 127.1 (C2), 105.8 (C1’), 96.8 (C1’’), 82.9 (C5), 82.1 (C4), 77.1 (C4’’), 75.1 (C4’), 73.1 (C5’), 72.9 (C9), 71.5 (C2’), 69.3 (C15), 69.2 (C3’), 69.1 (C3’’), 63.4 (C5’’), 56.0 (C19), 43.3 (C9’’), 42.3 (C20), 42.0 (C7’+C8’), 41.8 (C14), 41.7 (C2’’), 33.6 (C8), 29.9 (C6), 29.7 (C7), 25.5 (C10’’), 25.3 (C7’’), 22.4 (C11’’), 22.3 (C12’’), 20.2 (C16), 18.9 (C6’), 17.9 (C6’’), 14.5 (C22), *-overlapped signals.
  • 40
  • [ 16846-24-5 ]
  • [ 71156-87-1 ]
  • [ 1346163-09-4 ]
  • [ 1346163-11-8 ]
YieldReaction ConditionsOperation in experiment
With potassium hydroxide In diethyl ether; ethanol at 20℃; for 1h; optical yield given as %de;
  • 41
  • [ 16846-24-5 ]
  • [ 1346163-09-4 ]
  • [ 1346163-11-8 ]
YieldReaction ConditionsOperation in experiment
1: 50.7% 2: 21.6% With potassium hydroxide In diethyl ether; ethanol at 20℃; for 0.5h; optical yield given as %de; (3R,20S)-(3a) and (3R,20R)-(3b) bicyclic derivatives Josamycin (100 mg, 0.12 mmol) dissolved in ether at 20°C and treated with KOH/EtOH solution (0.15 mmol KOH/3mL) and stirred for 0.5h. Next the mixture was evaporated to dryness and twice extracted with CH2Cl2/H2O (30mL/20mL). Organic layer was washed with brine and evaporated. Next the mixture of 3a with 3b diastereomers was separated by HPLC method. Yield: 3a 47 mg (50.7 %) and 3b 20 mg (21.6 %). (3R,17S)-3a - m.p. 110-113°C; HPLC: Rt= 2.18 min.; MS (HR-MALDI-TOF) Found: 768.4533 [M+H]+ for C40H66NO13, calculated: 768.4529; Elemental analysis C40H65NO13: found C=62.50% H=8.50% N=1.78%, calculated C=62.56% H=8.53% N=1.82%; FT-IR: (KBr disc): 3492 cm-1 ν(O9-H), 3442 cm-1 ν(O2’-H) and 3274 cm-1 ν(O3’’-H), 2750 cm-1 ν(C18-H) of formyl group, 1739 cm-1 ν(C=O) at C-8’’, 1729 cm-1 ν(C=O) at C-1, 1725 cm-1 ν(C=O) at C-18, 1654 cm-1 ν(C=C) of diene, 1164, 1119, 1082, 1054 and 1019 cm-1 ν(C-O); 1H NMR (600 MHz, CDCl3): 9.82 (d, 1H, 3JH17,H18=2.2 Hz, H18), 6.09 (dd, 1H, 3JH10,H11=15.8 Hz, 3JH11,H12=10.4 Hz, H11), 5.91 (dd, 1H, 3JH12,H13=15.0 Hz, H12), 5.78 (dd, 1H, 3JH9,H10=6.0 Hz, H10), 5.58 (ddd, 1H, 3JH13,H14a=10.3 Hz, 3JH13,H14b=5.2 Hz, H13), 5.13 (m, 1H, H15), 5.08 (d, 1H, 3JH1``,H2``=3.1 Hz, H1``), 4.63 (d, 1H, 3JH4``,H5``=10.1 Hz, H4``), 4.48 (m, 1H, H5``), 4.38 (d, 1H, 3JH1`,H2`=7.6 Hz, H1`), 4.31 (bs, 1H, 3``-OH), 4.29 (m, 1H, H9), 3.86 (dd, 1H, 3JH4,H5=5.3 Hz, 3JH5,H6=10.5 Hz, H5), 3.60 (bs, 1H, 2`-OH), 3.57 (dd, 1H, 3JH2`,H3`=10.1 Hz, H2`), 3.34* (m, 1H, H4), 3.34* (m, 1H, H5`), 3.33 (s, 3H, -OCH3), 3.31 (m, 1H, H4`), 2.62 (dd, 1H, 2J =18.0 Hz, 3JH2a,H3=3.1 Hz, H2a), 2.58 (m, 1H, H17), 2.55 (m, 1H, H3), 2.51* (m, 1H, H3`), 2.51* (s, 6H, H7`+H8`), 2.26 (dd, 1H, 3JH2a,H3=13.3 Hz, H2b), 2.33 (m, 1H, H14a), 2.31 (m, 2H, H9``), 2.16 (m, 1H, H6), 2.15 (m, 1H, H10``), 2.06 (m, 1H, H14b), 1.99 (m, 1H, H2a``), 1.86* (m, 1H, H8), 1.86* (m, 1H, H2b``), 1.84 (bs, 1H, 9-OH), 1.29 (d, 3H, 3JH5`,H6`=6.7 Hz, H6`), 1.25 (d, 3H, 3JH15,H16=6.4 Hz, H16), 1.24 (m, 1H, H7a), 1.14 (d, 3H, 3JH5``,H6``=6.1 Hz, H6``), 1.12* (m, 1H, H7b), 1.12* (s, 3H, H7’’), 1.02 (d, 3H, 3JH8,H19=6.9 Hz, H19), 0.98 (d, 6H, 3JH10``,H11``+H12``=6.5 Hz, H11``+H12``), *-overlapped signals; 13C NMR (151 MHz, CDCl3): 202.8 (C18), 173.0 (C8’’), 170.9 (C1), 137.2 (C10), 132.8 (C12), 129.6 (C13), 128.6 (C11), 102.9 (C1`), 97.0 (C1``), 91.6 (C4), 87.9 (C5), 77.1 (C4``), 75.9 (C4`), 75.4 (C9), 73.2 (C5`), 71.1 (C2`), 69.4 (C3``), 68.8 (C15), 68.7 (C3`), 63.5 (C5``), 57.3 (-OCH3), 53.8 (C20), 43.3 (C9``), 41.9* (C6), 41.9* (C7`+C8`), 41.7 (C2``), 41.0 (C14), 39.4 (C8), 38.9 (C2), 37.0 (C3), 25.6 (C10``), 25.5 (C7’’), 25.3 (C7), 22.5 (C12``), 22.4 (C11``), 20.4* (C16), 20.4* (C19), 19.0 (C6`), 17.9 (C6``), *-overlapped signals. (3R,17R)-3b - m.p. 117-121°C; HPLC: Rt=1.36 min.; MS (HR-MALDI-TOF) Found: 768.4531 [M+H]+ for C40H66NO13, calculated: 768.4529; Elemental analysis C40H65NO13: found C=62.51% H=8.49% N=1.79%, calculated C=62.56% H=8.53% N=1.82%; FT-IR: (KBr disc): 3494 cm-1 ν(O9-H), 3440 cm-1 ν(O2’-H) and 3271 cm-1 ν(O3’’-H), 2758cm-1 ν(C18-H) of formyl group, 1737 cm-1 ν(C=O) at C-8’’, 1731 cm-1 ν(C=O) at C-1, 1727 cm-1 ν(C=O) at C-18, 1652 cm-1 ν(C=C) of diene, 1162, 1120, 1081, 1052 and 1021 cm-1 ν(C-O); 1H NMR (600 MHz, CDCl3): 9.80 (d, 1H, 3JH17,H18=4.2, H18), 6.08 (dd, 1H, 3JH10,H11=14.9 Hz, 3JH11,H12=10.5 Hz, H11), 5.97 (dd, 1H, , 3JH12,H13=14.9 Hz, H12), 5.77 (dd, 2H, 3JH9,H10=6.4 Hz, H10), 5.59 (ddd, 1H, 3JH13,H14a=10.2 Hz, 3JH13,H14b=5.3 Hz, H13), 5.14 (m, 1H, H15), 5.09 (d, 1H, 3JH1``,H2``=3.1 Hz, H1``), 4.64 (d, 1H, 3JH4``,H5``=10.1 Hz, H4``), 4.48 (m, 1H, H5``), 4.37 (d, 1H, 3JH1`,H2`=7.6 Hz, H1`), 4.30 (m, 1H, H9), 4.28 (bs, 1H, 3``-OH), 3.92 (dd, 1H, 3JH4,H5=5.3 Hz, 3JH5,H6=10.5 Hz, H5), 3.58* (bs, 1H, 2`-OH), 3.58* (dd, 1H, 3JH2`,H3`=10.3 Hz, H2`), 3.38 (m, 1H, H4), 3.35 (m, 1H, H5`), 3.31 (s, 3H, -OCH3), 3.30 (m, 1H, H4`), 2.65 (dd, 1H, 2J =18.0 Hz, 3JH2a,H3=3.1 Hz, H2a), 2.59 (m, 1H, H3), 2.52 (m, 1H, H3`), 2.51 (s, 6H, H7`+H8`), 2.42 (m, 1H, H14a), 2.31 (m, 2H, H9``), 2.23 (dd, 1H, 3JH2a,H3=13.3 Hz, H2b), 2.20 (m, 1H, H14b), 2.15 (m, 1H, H10``), 2.09 (m, 1H, H6), 2.08 (m, 1H, H17), 1.99 (m, 1H, H2a``), 1.86* (m, 1H, H2b``), 1.86* (m, 1H, H8), 1.83 (bs, 1H, 9-OH), 1.30 (d, 3H, 3JH5`,H6`=6.7 Hz, H6`), 1.25 (d, 3H, 3JH15,H16=6.4 Hz, H16), 1.24 (m, 1H, H7a), 1.15 (d, 3H, 3JH5``,H6``=6.1 Hz, H6``), 1.12* (m, 1H, H7b), 1.12* (s, 3H, H7’’), 1.02 (d, 3H, 3JH8,H19=6.9 Hz, H19), 0.98 (d, 6H, 3JH10``,H11``+H12``=6.5 Hz, H11``+H12``), *-overlapped signals; 13C NMR (151 MHz, CDCl3): 204.8 (C18), 173.0 (C8’’), 171.0 (C1), 137.3 (C10), 132.0 (C12), 129.7 (C13), 127.5 (C11), 103.0 (C1`), 97.2 (C1``), 91.6 (C4), 88.1 (C5), 77.1 (C4``), 75.9 (C4`), 75.4 (C9), 73.3 (C5`), 71.2 (C2`), 69.5 (C3``), 68.7* (C15), 68.7* (C3`), 63.5 (C5``), 56.8 (-OCH3), 48.0 (C17), 43.3 (C9``), 41.9 (C7`+C8`), 41.8 (C6), 41.7 (C2``), 40.6 (C14), 39.4 (C8), 39.0 (C2), 36.9 (C3), 25.6 (C10``), 25.5 (C7’’), 25.4 (C7), 22.5 (C12``), 22.4 (C11``), 20.4* (C16), 20.4* (C19), 19.2 (C6`), 17.9 (C6``), *-overlapped signals.
  • 42
  • [ 16846-24-5 ]
  • [ 1346163-09-4 ]
YieldReaction ConditionsOperation in experiment
With potassium hydroxide In diethyl ether; ethanol at 20℃; for 1h;
  • 43
  • [ 16846-24-5 ]
  • (2S,3S,4R,6S)-6-(((2R,3S,4R,5R,6S)-4-(dimethylamino)-5-hydroxy-6-(((3E,5S,6S,7R,9R,10R,11E,13E,16R)-10-hydroxy-7-(2-hydroxyethyl)-5-methoxy-9,16-dimethyl-2-oxo-oxacyclohexadeca-3,11,13-trien-6-yl)oxy)-2-methyltetrahydro-2H-pyran-3-yl)oxy)-4-hydroxy-2,4-dimethyltetrahydro-2H-pyran-3-yl 3-methylbutanoate [ No CAS ]
YieldReaction ConditionsOperation in experiment
97% Stage #1: josamycin With sodium tetrahydroborate In methanol at 20℃; for 2h; Stage #2: With potassium hydroxide In diethyl ether; ethanol at 20℃; for 2h;
Multi-step reaction with 2 steps 1: sodium tetrahydroborate / methanol / 2 h / 20 °C 2: potassium hydroxide / diethyl ether / 2 h / 20 °C
  • 44
  • [ 16846-24-5 ]
  • (3E,5S,6S,7R,9R,10E,12E,14S,16R)-6-(((2S,3R,4S,5S,6R)-4-(dimethylamino)-3,5-dihydroxy-6-methyltetrahydro-2H-pyran-2-yl)oxy)-7-(2-hydroxyethyl)-5-methoxy-9,16-dimethyl-14-(prop-2-yn-1-yloxy)oxacyclohexadeca-3,10,12-trien-2-one [ No CAS ]
YieldReaction ConditionsOperation in experiment
Multi-step reaction with 3 steps 1: sodium tetrahydroborate / methanol / 2 h / 20 °C 2: potassium hydroxide / diethyl ether / 2 h / 20 °C 3: toluene-4-sulfonic acid / 4 h / 0 °C
Multi-step reaction with 2 steps 1.1: sodium tetrahydroborate / methanol / 2 h / 20 °C 1.2: 2 h / 20 °C 2.1: toluene-4-sulfonic acid / 4 h / 20 °C
  • 45
  • [ 16846-24-5 ]
  • (3E,5S,6S,7R,9R,10E,12E,14S,16R)-14-((1-benzyl-1H-1,2,3-triazol-4-yl)methoxy)-6-(((2S,3R,4S,5S,6R)-4-(dimethylamino)-3,5-dihydroxy-6-methyltetrahydro-2H-pyran-2-yl)oxy)-7-(2-hydroxyethyl)-5-methoxy-9,16-dimethyloxacyclohexadeca-3,10,12-trien-2-one [ No CAS ]
YieldReaction ConditionsOperation in experiment
Multi-step reaction with 4 steps 1: sodium tetrahydroborate / methanol / 2 h / 20 °C 2: potassium hydroxide / diethyl ether / 2 h / 20 °C 3: toluene-4-sulfonic acid / 4 h / 0 °C 4: ascorbic acid; copper (I) acetate / methanol; tetrahydrofuran / 24 h / 60 °C
Multi-step reaction with 3 steps 1.1: sodium tetrahydroborate / methanol / 2 h / 20 °C 1.2: 2 h / 20 °C 2.1: toluene-4-sulfonic acid / 4 h / 20 °C 3.1: ascorbic acid; copper (I) acetate / methanol; tetrahydrofuran / 24 h / 60 °C
  • 46
  • [ 16846-24-5 ]
  • (3E,5S,6S,7R,9R,10E,12E,14S,16R)-14-((1-(4-chlorobenzyl)-1H-1,2,3-triazol-4-yl)methoxy)-6-(((2S,3R,4S,5S,6R)-4-(dimethylamino)-3,5-dihydroxy-6-methyltetrahydro-2H-pyran-2-yl)oxy)-7-(2-hydroxyethyl)-5-methoxy-9,16-dimethyloxacyclohexadeca-3,10,12-trien-2-one [ No CAS ]
YieldReaction ConditionsOperation in experiment
Multi-step reaction with 4 steps 1: sodium tetrahydroborate / methanol / 2 h / 20 °C 2: potassium hydroxide / diethyl ether / 2 h / 20 °C 3: toluene-4-sulfonic acid / 4 h / 0 °C 4: ascorbic acid; copper (I) acetate / methanol; tetrahydrofuran / 4 h / 60 °C
Multi-step reaction with 3 steps 1.1: sodium tetrahydroborate / methanol / 2 h / 20 °C 1.2: 2 h / 20 °C 2.1: toluene-4-sulfonic acid / 4 h / 20 °C 3.1: ascorbic acid; copper (I) acetate / methanol; tetrahydrofuran / 4 h / 60 °C
  • 47
  • [ 16846-24-5 ]
  • (3E,5S,6S,7R,9R,10E,12E,14S,16R)-14-((1-(4-bromobenzyl)-1H-1,2,3-triazol-4-yl)methoxy)-6-(((2S,3R,4S,5S,6R)-4-(dimethylamino)-3,5-dihydroxy-6-methyltetrahydro-2H-pyran-2-yl)oxy)-7-(2-hydroxyethyl)-5-methoxy-9,16-dimethyloxacyclohexadeca-3,10,12-trien-2-one [ No CAS ]
YieldReaction ConditionsOperation in experiment
Multi-step reaction with 4 steps 1: sodium tetrahydroborate / methanol / 2 h / 20 °C 2: potassium hydroxide / diethyl ether / 2 h / 20 °C 3: toluene-4-sulfonic acid / 4 h / 0 °C 4: ascorbic acid; copper (I) acetate / methanol; tetrahydrofuran / 4 h / 60 °C
Multi-step reaction with 3 steps 1.1: sodium tetrahydroborate / methanol / 2 h / 20 °C 1.2: 2 h / 20 °C 2.1: toluene-4-sulfonic acid / 4 h / 20 °C 3.1: ascorbic acid; copper (I) acetate / methanol; tetrahydrofuran / 4 h / 60 °C
  • 48
  • [ 16846-24-5 ]
  • 2-(3-(4-((((2R,4S,5E,7E,9R,11R,12S,13S,14E)-12-(((2S,3R,4S,5S,6R)-4-(dimethylamino)-3,5-dihydroxy-6-methyltetrahydro-2H-pyran-2-yl)oxy)-11-(2-hydroxyethyl)-13-methoxy-2,9-dimethyl-16-oxo-oxacyclohexadeca-5,7,14-trien-4-yl)oxy)methyl)-1H-1,2,3-triazol-1-yl)propyl)isoindoline-1,3-dione [ No CAS ]
YieldReaction ConditionsOperation in experiment
Multi-step reaction with 4 steps 1: sodium tetrahydroborate / methanol / 2 h / 20 °C 2: potassium hydroxide / diethyl ether / 2 h / 20 °C 3: toluene-4-sulfonic acid / 4 h / 0 °C 4: ascorbic acid; copper (I) acetate / methanol; tetrahydrofuran / 24 h / 60 °C
Multi-step reaction with 3 steps 1.1: sodium tetrahydroborate / methanol / 2 h / 20 °C 1.2: 2 h / 20 °C 2.1: toluene-4-sulfonic acid / 4 h / 20 °C 3.1: ascorbic acid; copper (I) acetate / methanol; tetrahydrofuran / 24 h / 60 °C
  • 49
  • [ 16846-24-5 ]
  • C12H22O5 [ No CAS ]
  • C12H22O5 [ No CAS ]
YieldReaction ConditionsOperation in experiment
33.333 % de Stage #1: josamycin With hydrogenchloride; water at 20℃; Stage #2: With sodium hydroxide In water Overall yield = 94.5 %; Overall yield = 1.41 g; Synthesis of L-mycarose To 65 mL of HCl ( 0.35 N ) was added josamycin ( 6.90 g, 6.03 mmol ) at room temperature. The mixture was stirred at room temperature overnight. The reaction solution was adjusted pH to 4 with NaOH ( 1N ), extracted with DCM ( 3×150 mL ). The combined organic layers was dried with Na2SO4, filtered and concentrated in vacuo to give L-mycarose ( 1.41 g, 94.5 %), as a colorless oil. lH NMR ( 600 MHz, CDCl3+D2O ) δ 5.17 ( d, J=3.6 Hz, 1H ), 5.14 ( dd, J=9.6, 1.8 Hz, 0.47H ), 4.65 ( d, J=9.6 Hz, 1H ), 4.62 ( d, J=9.6, 0.41H ), 4.17 ( m, 1H ), 3.90 ( m, 0.40H ), 2.28-2.25 ( m, 2H ), 2.14-2.03 ( m, 3H ), 1.84 ( dd, J=14.4, 3.6 Hz, 1H ), 1.59 ( dd, J=13.2, 9.6 Hz, 0.47H ), 1.16-1.14 ( m, 9H ), 0.98-0.97 ( m, 9H ).
  • 50
  • [ 108-24-7 ]
  • [ 16846-24-5 ]
  • 2',9-O-diacetyl josamycin [ No CAS ]
YieldReaction ConditionsOperation in experiment
98.2% With pyridine at 0 - 20℃; Synthesis of compound 6 To a solution of josamycin ( 20.7 g, 25.0 mmol ) in 100 mL of pyridine was added acetic anhydride ( 16.9 g, 165 mmol ) dropwise at 0 °C over 0.5 h. The mixture was stirred at 0 °C for 1 h and allowed to warm to room temperature and stirred at room temperature overnight. The mixture was concentrated in vacuo. The residue was poured into 250 mL of ethyl acetate, washed with brine ( 3×150 mL ), dried with Na2SO4, filtered, concentrated in vacuo to give 1 ( 2′,9-O-diacetyl josamycin ) as a white solid ( 22.39 g, 98.2 % ). lH NMR ( 500 MHz, CDCl3 ) δ 9.63 ( s, 1H, 18-H ) , 6.68 ( dd, J=15.0, 10.5 Hz, 1H, 11-H ), 6.05 ( dd, J=15.0, 10.5 Hz, 1H,12-H ), 5.85 ( td, J=11.0, 3.5 Hz, 1H, 13-H ), 5.55 ( dd, J=15.5, 10.0 Hz, 1H, 10-H ), 5.08 ( d, J=11.5 Hz, 1H, 9-H ), 5.05 ( d, J=3.0 Hz, 1H, 1′′-H ), 5.03 ( d, J=4.0 Hz, 1H, 3-H ), 4.98( m, 1H, 15-H ), 4.95 ( dd, 1H, 2′-H ), 4.61 ( d, J=10.5 Hz, 1H, 4′′-H ), 4.59 ( d, J=8.0 Hz, 1H, 1′-H ), 4.37 ( m, 1H, 4′′-H ), 4.21 ( br, 1H, 3′′-OH ), 3.95 ( d, J=9.0 Hz, 1H, 5-H ), 3.47 ( s, 3H, 4-OCH3 ), 3.29 ( m, 1H, 5′-H ), 3.27 ( m, 1H, 4′-H ), 3.15 ( m, 1H, 4-H ), 2.79 ( dd, 1H, 17-H ), 2.67 ( dd, 1H, 2-H ), 2.41 ( s, 6H, 3′-N(CH3)2 ), 2.30 ( s, 3H, 3-OCOCH3 ), 2.29 ( d, 2H, 4′′- OCOCH2 ), 2.24 ( d, J=12.5 Hz, 1H, 2-H ), 2.16 ( m, 1H, 14-H ), 2.13 ( m, 1H, 4′′-CH(CH3)2 ), 2.01 ( s, 3H, 9-OCOCH3 ), 2.00 ( s, 3H, 2′- OCOCH3 ), 1.99 ( m, 1H, 8-H ), 1.84 ( dd, J=14.0, 4.0 Hz, 1H, 2′′-Hax ), 1.60 ( s, OH, 4′′ ), 1.45 ( m, 1H, 7-H ), 1.25 ( d, J=6.0 Hz, 3H, 16-H ), 1.17 ( d, J=5.0 Hz, 3H, 6′-H ), 1.13 ( d, J=6.0 Hz, 3H, 6′′-H ), 1.11 ( s, 3H, 3′′- CH3 ), 0.97 ( s, 3H, 8-CH3 ), 0.96 ( d, 6H, 4′′- OCOCH2CH(CH3)2 ), 0.95 ( d, 3H, 19-H ) 0.85 ( m, 1H, 7-H ).13C NMR ( 125 MHz, CDCl3 ) δ 201.1 ( 18-C ), 172.9 ( 8′′-C ), 170.6 ( 19-C ), 170.2 ( 23-C ), 169.8 ( 1-C ), 168.7 ( 9′-C ),138.1 ( 11-C ), 133.9 ( 13-C ), 131.6 ( 12-C ), 122.3 ( 10-C ), 100.7 ( 1′-C ), 97.0 ( 1′′-C ), 85.4 ( 4-C ), 77.2 ( 5-C ), 76.3 ( 4′′-C ), 75.9 ( 9-C ), 75.5 ( 4′-C ), 72.6 ( 5′-C ), 71.0 ( 2′-C ), 69.4 ( 15-C ), 69.3 ( 3-C ), 69.0 ( 3′′-C ), 67.9 ( 3′-C ), 63.5 ( 5′′-C ), 62.1 ( 21-C ), 43.3 ( 9′′-C ), 42.0 ( 17-C ), 41.6 ( 7′, 8′-C ), 41.6 ( 2′′-C ), 40.8 ( 14-C ), 37.2 ( 2-C ), 31.2 ( 8-C ), 29.7 ( 7-C ), 28.4 ( 6-C ), 25.5 ( 10′′-C ), 25.3 ( 7′′-C ), 22.6 ( 24-C ), 22.4 ( 12′′-C ), 22.4 ( 11′′-C ), 21.3 ( 10′-C ), 21.2 ( 20-C ), 20.4 ( 16-C ), 18.6 ( 6′-C ), 18.0 ( 6′′-C ), 15.0 ( 22-C ).
  • 51
  • [ 16846-24-5 ]
  • C20H32O7 [ No CAS ]
YieldReaction ConditionsOperation in experiment
With hydrogenchloride In dichloromethane; water at 50℃; for 24h; 5 Example 5: Synthesis of DY-0005 macrolide compound 2.5 g of josamycin is dissolved in 100 ml of dichloro and 200 ml of (6 M) hydrochloric acid.Add to a 500ml single-mouth round bottom bottle, heat the oil bath at 50 ° C, stir the reaction for 24 hours, react for 24 hours, separate the liquid, discard the organic layer, and adjust the PH value to about 10 with the 10% sodium hydroxide in the water phase. After the mixture was extracted with dichlorobenzene for 2 to 3 times, the organic phase was collected, dried over anhydrous sodium sulfate, and dichlorobenzene was evaporated under reduced pressure and dried in vacuo to give a white solid as a macrolide derivative (DY-0005).
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