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[ CAS No. 3842-86-2 ] {[proInfo.proName]}

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Chemical Structure| 3842-86-2
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Product Details of [ 3842-86-2 ]

CAS No. :3842-86-2 MDL No. :MFCD30474919
Formula : C8H18NO4P Boiling Point : -
Linear Structure Formula :- InChI Key :SPNSSEKVTXYNNH-UHFFFAOYSA-N
M.W :223.21 Pubchem ID :11127903
Synonyms :

Safety of [ 3842-86-2 ]

Signal Word:Warning Class:
Precautionary Statements:P261-P264-P270-P271-P280-P301+P312-P302+P352-P304+P340-P305+P351+P338-P330-P332+P313-P337+P313-P362-P403+P233-P405-P501 UN#:
Hazard Statements:H302-H315-H319-H335 Packing Group:
GHS Pictogram:

Application In Synthesis of [ 3842-86-2 ]

* 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 [ 3842-86-2 ]

[ 3842-86-2 ] Synthesis Path-Downstream   1~47

  • 1
  • [ 122-52-1 ]
  • [ 2675-89-0 ]
  • [ 3842-86-2 ]
YieldReaction ConditionsOperation in experiment
78% at 165℃; for 5.5h;
76% at 110 - 115℃; Inert atmosphere; 7 Example 7: Diethyl f2-fdimethylamino)-2-oxoethyl)phosphonate To a 500-ml 3-neck RB flask was charged triethylphosphite (284.0 g, 1674 mmol), heated to 110°C - 115°C with N2 swept through head space. 2-Chloro-N,N- dimethylacetamide was added dropwise over 3 h to 4 h at 110-115°C. The reaction mixture was aged 2 h at this temperature then concentrated under vacuum to yield desired product (313.4 g, AY=76%) as yellow oil.
20% at 150℃; 8.1 8.1 Synthesis of Intermediate 21 8.1 Synthesis of Intermediate 21A mixture of 2-chloro-N,N-dimethylacetamide (300 mg, 2.47 mmol) and triethyl phosphite (820 mg, 4.94 mmol) was stirred at 150° C. overnight. The reaction mixture was cooled to room temperature and was purified by Prep HPLC to give intermediate 21 (105 mg, 20%).
at 140 - 190℃;
4.5 g at 160℃; for 8h; Inert atmosphere; A mixture of 2-chloro-N,N-dimethylacetamide (5.0 g, 41.1 mmol) and triethyl phosphite (6.83 g, 41.1 mmol) was degassed and purged with N2 for 3 times. The mixture was stirred at 160 °C for 8 h under N2atmosphere. The mixture was concentrated and purified by column chromatography to provide diethyl (2-(dimethylamino)-2- oxoethyl)phosphonate (I-35) (4.5 g) as a yellow oil. LCMS m/z 224.3 (M+1)+.1H NMR (400 MHz, CDCl3) ^ 4.20-4.12 (m, 4H), 3.11 (s, 3H), 3.07-3.01 (d, J = 22 Hz, 2H), 2.97 (s, 3H), 1.35-1.31 (t, J = 7.2 Hz, 6H).

  • 2
  • [ 3842-86-2 ]
  • [ 135159-24-9 ]
  • Acetic acid (S)-4-((E)-2-dimethylcarbamoyl-vinyl)-1-(2-nitro-benzoyl)-2,3-dihydro-1H-pyrrol-2-ylmethyl ester [ No CAS ]
  • 3
  • [ 3842-86-2 ]
  • [ 148680-22-2 ]
  • [ 148680-23-3 ]
  • 4
  • [ 127-19-5 ]
  • [ 814-49-3 ]
  • [ 3842-86-2 ]
YieldReaction ConditionsOperation in experiment
With lithium diisopropyl amide 1.) THF, hexane, 12-15 deg C, 2.) THF, hexane, RT,; Yield given. Multistep reaction;
  • 5
  • [ 3842-86-2 ]
  • [ 4637-24-5 ]
  • [ 98934-36-2 ]
YieldReaction ConditionsOperation in experiment
95% With calcium chloride for 2h; Heating;
  • 6
  • [ 3842-86-2 ]
  • [ 190974-29-9 ]
  • [ 190974-49-3 ]
YieldReaction ConditionsOperation in experiment
67% With lithium diisopropyl amide In tetrahydrofuran at -78 - 20℃;
  • 7
  • [ 683-08-9 ]
  • [ 3842-86-2 ]
YieldReaction ConditionsOperation in experiment
68% With n-butyllithium; lithium diisopropyl amide In tetrahydrofuran; hexane at -60℃;
  • 8
  • [ 3842-86-2 ]
  • [ 116777-68-5 ]
  • [ 116777-68-5 ]
  • [ 116777-68-5 ]
YieldReaction ConditionsOperation in experiment
With n-butyllithium In tetrahydrofuran
  • 9
  • [ 3842-86-2 ]
  • [ 183872-18-6 ]
  • [(Z)-3-((E)-3-tert-butyldimethylsilyloxy-7-phenyl-1-hepten-1-yl)cyclohexylidene]-N,N-dimethyl-acetamide [ No CAS ]
  • [(E)-3-((E)-3-tert-butyldimethylsilyloxy-7-phenyl-1-hepten-1-yl)cyclohexylidene]-N,N-dimethyl-acetamide [ No CAS ]
YieldReaction ConditionsOperation in experiment
1: 33.5% 2: 52.5% Stage #1: diethyl N,N-dimethylcarbamoylmethylphosphonate With sodium hydride In tetrahydrofuran at 20℃; for 0.5h; Stage #2: 3-[(E)-3-tert-butyldimethylsilyloxy-7-phenyl-1-hepten-1-yl]cyclohexanone In tetrahydrofuran at 60℃; for 1h;
  • 10
  • [ 89424-83-9 ]
  • [ 3842-86-2 ]
  • 3-(1,3-dihydro-isobenzofuran-5-yl)-<i>N</i>,<i>N</i>-dimethyl-acrylamide [ No CAS ]
  • 11
  • [ 3842-86-2 ]
  • [ 86-81-7 ]
  • (E)-N,N-dimethyl-3-(3,4,5-trimethoxyphenyl)acrylamide [ No CAS ]
YieldReaction ConditionsOperation in experiment
85% With potassium hydroxide In tetrahydrofuran at 20℃; for 1h;
  • 12
  • [ 3842-86-2 ]
  • [ 378787-86-1 ]
  • [ 378787-87-2 ]
YieldReaction ConditionsOperation in experiment
Stage #1: diethyl N,N-dimethylcarbamoylmethylphosphonate With n-butyllithium In tetrahydrofuran; hexane at 0℃; for 0.5h; Stage #2: (S)-5-acetoxymethyl-3-formyl-1-(4,5-methylenedioxy-2-nitrobenzoyl)-2-pyrroline In tetrahydrofuran; hexane
  • 13
  • [ 62142-34-1 ]
  • [ 3842-86-2 ]
  • [ 853928-53-7 ]
YieldReaction ConditionsOperation in experiment
48% Stage #1: diethyl N,N-dimethylcarbamoylmethylphosphonate With sodium hydride In diethyl ether for 0.0833333h; Stage #2: 1-vinylcyclohexanecarboxaldehyde In diethyl ether at 20℃; for 15h;
  • 14
  • [ 3842-86-2 ]
  • [ 117954-70-8 ]
  • [ 897921-28-7 ]
YieldReaction ConditionsOperation in experiment
82% Stage #1: diethyl N,N-dimethylcarbamoylmethylphosphonate With sodium hydride In tetrahydrofuran at -40 - 0℃; Stage #2: 3-formyl-1-<(4-methylphenyl)sulfonyl>pyrrole In tetrahydrofuran at 0 - 5℃; for 0.5h;
  • 15
  • [ 3842-86-2 ]
  • [ 96-22-0 ]
  • 3-ethyl-N,N-dimethyl-2-pentenamide [ No CAS ]
YieldReaction ConditionsOperation in experiment
46% Stage #1: diethyl N,N-dimethylcarbamoylmethylphosphonate With sodium hydride In benzene for 0.75h; Stage #2: pentan-3-one In benzene for 21h; Heating;
  • 16
  • [ 3842-86-2 ]
  • [ 98934-39-5 ]
YieldReaction ConditionsOperation in experiment
Multi-step reaction with 2 steps 1: 95 percent / CaCl2 / 2 h / Heating 2: 71 percent Spectr. / 3M HCl / H2O; diethyl ether / 20 °C
  • 17
  • [ 3842-86-2 ]
  • [ 98934-59-9 ]
YieldReaction ConditionsOperation in experiment
Multi-step reaction with 2 steps 1: 95 percent / CaCl2 / 2 h / Heating 2: 29 percent Spectr. / 3M HCl / H2O; diethyl ether / 20 °C
  • 18
  • [ 79-37-8 ]
  • [ 3842-86-2 ]
  • [ 133995-30-9 ]
  • (E)-3-[(2S,4S)-N-allyloxycarbonyl-4-tritylthiopyrrolidin-2-yl]-N,N-dimethylacrylamide [ No CAS ]
YieldReaction ConditionsOperation in experiment
88.1% With dimethyl sulfoxide; triethylamine R.6.1 (E)-3-[(2S,4S)-N-Allyloxycarbonyl-4-tritylthiopyrrolidin-2-yl]-N,N-dimethylacrylamide STR371 REFERENCE EXAMPLE 6-1) (E)-3-[(2S,4S)-N-Allyloxycarbonyl-4-tritylthiopyrrolidin-2-yl]-N,N-dimethylacrylamide STR371 The same operation as in Reference Example 4-1) was carried out by using (2S,4S)-N-allyloxycarbonyl-2-hydroxymethyl-4-tritylthiopyrrolidine (the compound obtained in Reference Example 3-1); 2.00 g, 4.35 mmol), dimethyl sulfoxide (0.87 ml, 12.2 mmol), oxalyl chloride (0.56 ml, 6.5 mmol), triethylamine (3.03 ml, 21 8 mmol), 2-(diethylphosphono)-N,N-dimethylacetamide (1.17 g, 5.22 mmol) and 60% sodium hydride (174 mg, 4.35 mmol), followed by flash column chromatographic purification on silica gel (Wakogel C-300, 40 ml, elution with hexane-ethyl acetate 1 1) to give the title compound (2.02 g, 88.1% yield) NMR(CDCl3) δ: 1.6(1H,m), 2.1(1H,m), 2.7-3.4(3H,m), 2.96(3H,s), 3.0(3H,s), 4.18(1H,q,J=7 Hz), 4.46(2H,m), 5.1-5.3(2H,m), 5.82(1H,m), 6.28(1H,m), 6.6(1H,m), 7.1-7.5(15H,m)
  • 19
  • [ 1117-52-8 ]
  • [ 3842-86-2 ]
  • N,N-dimethyl-3,7,11,15-tetramethyl-2,6,10,14-hexadecatetraenamide [ No CAS ]
YieldReaction ConditionsOperation in experiment
In tetrahydrofuran; water 60 EXAMPLE 60 EXAMPLE 60 This Example illustrates the synthesis of N,N-dimethyl-3,7,11,15-tetramethyl-2,6,10,14-hexadecatetraenamide (compound K). To a suspension of 5 g of 55% sodium hydride in anhydrous tetrahydrofuran was added 28.5 g of N,N-dimethyldiethylphosphonoacetamide, and 16.8 g of farnesylacetone was further added and the mixture was stirred at 50° C. for 2 hours. To the liquid reaction mixture was added 100 ml of water, and the mixture was extracted with n-hexane. The extract was washed with water and dried. The solvent was removed by distillation and the residue was purified by column chromatography using silica gel to obtain 16 g of the intended compound in the form of an oil. Infrared absorption spectrum (cm-1, neat): 1650 Mass spectrum: 331 (M+) Elementary analysis values as C22 H37 ON: Calculated: C=79.70%, H=11.25%, N=4.23% Found: C=79.61%, H=11.31%, N=4.35% NMR spectrum (δ, CDCl3): 1.64 (9H, s), 1.72 (3H, s), 1.92 (3H, s) 2.0-2.2 (12H, m), 2.98 (3H, s), 3.02 (3H,s), 5.0-5.2 (3H,m), 5.8 (1H, s)
  • 20
  • [ 39482-50-3 ]
  • [ 3842-86-2 ]
  • [ 1006584-66-2 ]
YieldReaction ConditionsOperation in experiment
29% Stage #1: diethyl N,N-dimethylcarbamoylmethylphosphonate With sodium hydride In tetrahydrofuran for 0.0833333h; Stage #2: 2,2,4-trimethylpent-4-enal In tetrahydrofuran at 20℃; for 16h; Further stages.;
  • 21
  • [ 993-67-9 ]
  • [ 3842-86-2 ]
  • [ 1006584-77-5 ]
YieldReaction ConditionsOperation in experiment
27% Stage #1: diethyl N,N-dimethylcarbamoylmethylphosphonate With sodium hydride In tetrahydrofuran for 0.0833333h; Stage #2: 2,2,3,3-tetramethylpent-4-enal In tetrahydrofuran at 20℃; for 16h; Further stages.;
  • 22
  • [ 3842-86-2 ]
  • [ 13637-68-8 ]
  • diethyl ester of 2-dimethylamino-2-oxoethylphosphonic acid molybdenum dioxodichloride [ No CAS ]
YieldReaction ConditionsOperation in experiment
71% In ethanol soln. (EtO)2POCH2CON(CH3)2 (EtOH) added to MoO2Cl2; stirring for 60 min at 25°C; liaving for 20 h at 25°C;; ppt. filtered; washed with cold EtOH/Et2O (1:4); dried for 2 h at 60°C; elem. anal.;
  • 23
  • ammonium hexafluorophosphate [ No CAS ]
  • hydrated ammonium tetrachlorouranate(III) [ No CAS ]
  • [ 3842-86-2 ]
  • [U(diethyl-N,N-dimethylcarbamoylmethylenephosphonate)4][PF6]3 [ No CAS ]
YieldReaction ConditionsOperation in experiment
In ethanol N2-atmosphere; dissoln. of NH4UCl4 in soln. of ligand, addn. of NH4PF6 soln.;
  • 24
  • hydrated ammonium tetrachlorouranate(III) [ No CAS ]
  • [ 3842-86-2 ]
  • [ 143-66-8 ]
  • [U(diethyl-N,N-dimethylcarbamoylmethylenephosphonate)4][B(C6H5)4]3 [ No CAS ]
YieldReaction ConditionsOperation in experiment
In ethanol N2-atmosphere; dissoln. of NH4UCl4 in soln. of ligand, addn. of NaBPh4 soln.;
  • 25
  • [ 3842-86-2 ]
  • [ 667419-29-6 ]
  • C19H29NO3 [ No CAS ]
YieldReaction ConditionsOperation in experiment
91% With sodium hydride In tetrahydrofuran at 0 - 20℃;
  • 26
  • 3-dimethylamino-butyraldehyde [ No CAS ]
  • [ 3842-86-2 ]
  • C10H20N2O [ No CAS ]
  • [ 1119825-11-4 ]
YieldReaction ConditionsOperation in experiment
493 mg Stage #1: diethyl N,N-dimethylcarbamoylmethylphosphonate With sodium hexamethyldisilazane In tetrahydrofuran at 0℃; for 1.16667h; Stage #2: 3-dimethylamino-butyraldehyde In tetrahydrofuran at 20℃; for 0.833333h;
  • 27
  • [ 1191029-17-0 ]
  • [ 3842-86-2 ]
  • [ 1191029-24-9 ]
YieldReaction ConditionsOperation in experiment
63% With sodium hydride In tetrahydrofuran at 0 - 20℃; for 24h;
  • 28
  • [ 1191029-18-1 ]
  • [ 3842-86-2 ]
  • [ 1191029-25-0 ]
YieldReaction ConditionsOperation in experiment
64% With sodium hydride In tetrahydrofuran at 0 - 20℃; for 24h;
  • 29
  • [ 1191029-19-2 ]
  • [ 3842-86-2 ]
  • [ 1191029-27-2 ]
YieldReaction ConditionsOperation in experiment
69% With sodium hydride In tetrahydrofuran at 0 - 20℃; for 24h;
  • 30
  • [ 1191029-21-6 ]
  • [ 3842-86-2 ]
  • [ 1191029-29-4 ]
YieldReaction ConditionsOperation in experiment
64% With sodium hydride In tetrahydrofuran at 0 - 20℃; for 24h;
  • 31
  • [ 36884-29-4 ]
  • [ 3842-86-2 ]
  • [ 1203792-16-8 ]
YieldReaction ConditionsOperation in experiment
40% Stage #1: diethyl N,N-dimethylcarbamoylmethylphosphonate With sodium hydride In tetrahydrofuran; mineral oil Inert atmosphere; Stage #2: 4-bromo-pent-4-enal In tetrahydrofuran; mineral oil at 20℃; for 16h; Inert atmosphere;
  • 32
  • [ 3973-43-1 ]
  • [ 3842-86-2 ]
  • [ 1203792-15-7 ]
YieldReaction ConditionsOperation in experiment
80% Stage #1: diethyl N,N-dimethylcarbamoylmethylphosphonate With sodium hydride In tetrahydrofuran; mineral oil Inert atmosphere; Stage #2: 4-methylpent-4-enal In tetrahydrofuran; mineral oil at 20℃; for 16h; Inert atmosphere;
  • 33
  • [ 3842-86-2 ]
  • [ 145100-62-5 ]
  • [ 1203792-21-5 ]
YieldReaction ConditionsOperation in experiment
55% Stage #1: diethyl N,N-dimethylcarbamoylmethylphosphonate With sodium hydride In tetrahydrofuran; mineral oil Inert atmosphere; Stage #2: 4-cyclohexyl-4-pentenal In tetrahydrofuran; mineral oil at 20℃; for 16h; Inert atmosphere;
  • 34
  • [ 3842-86-2 ]
  • [ 1191029-24-9 ]
YieldReaction ConditionsOperation in experiment
63% Stage #1: diethyl N,N-dimethylcarbamoylmethylphosphonate With sodium hydride In tetrahydrofuran; mineral oil at 20℃; for 2h; Stage #2: diethyl N,N-dimethylcarbamoylmethylphosphonate In tetrahydrofuran; mineral oil at 0 - 20℃; 18A Diethyl Λ/,Λ/-dimethylcarbamoylmethylphosphonate (prepared by the method of Paul A. Bartlett, Nicholas I. Carruthers, Beat M. Winter, and Karen P. Long. J.Org.Chem. 47, 1284-1291 , 1982) (4.1 g, 18 mmol) in THF (10 mL) is added in portions to a stirred suspension of NaH (0.45 g, 18 mmol) in THF (80 mL) at rt and the reaction mixture is stirred for 2 h, then cooled to 00C. A solution of 2,2-bis(octyloxymethyl)propanedial (1.6 g, 4.5 mmol) in THF (10 ml_) is added and the reaction mixture is stirred for 24 h at rt. A saturated aqueous ammonium chloride solution (20 mL) is added to the reaction mixture and then the volatile organic components are removed by concentration. The resulting solution is extracted with ethyl acetate (3 x 30 mL). The combined organic layers are washed with water (2 x 20 mL), brine (20 mL), dried (Na2SO4), filtered and concentrated. The residue is purified by flash column chromatography using a gradient of 80 to 90% EtOAc in hexanes as eluent, yielding compound 18a as a viscous liquid: yield 1.4g (63%); RF 0.35 (dichloromethane: methanol 94:6); 1H NMR δ 0.88 (t, 6H, J = 7 Hz, 2 x Me), 1.26-1.34 (br s, 2OH, 1O x CH2), 1.53 (pentet, 4H, J = 7 Hz, 2 OCH2CH2), 2.99 (s, 3H, NCH3), 3.05 (s, 3H, NCH3), 3.39 (t, 4H, J = 6.5 Hz, decyl OCH2), 3.49 (s, 4H, OCH2C), 6.36 (d, 2H, J = 16 Hz, COCHCH), 6.86 (d, 2H, J = 16 Hz, COCHCH); 13C NMR δ 166.8 (C=O), 145.3 (CH=CHC), 121.9 (COCH=), 72.9 (CH2CH2OC), 71.9 (OCH2C), 48.9 (q C), 37.5 (NCH3), 35.8 (NCH3), 32.0 (CH2CH2CH3), 29.77, 29.61 , 29.45 (3 octyl CH2), 26.4 (CH2CH2CH2O), 22.8 (CH2CH3), 14.2 (Me); HR ESI MS m/z calcd for C29H54N2O4Na (M+Na) 517.3976, found 517.3971.
  • 35
  • [ 1248555-92-1 ]
  • [ 3842-86-2 ]
  • [ 1248555-93-2 ]
YieldReaction ConditionsOperation in experiment
95% Stage #1: diethyl N,N-dimethylcarbamoylmethylphosphonate With sodium hydride In dichloromethane; mineral oil at 0℃; for 0.166667h; Stage #2: 2-(trimethylsilyl)ethyl 4-(4-formylphenyl)isoquinoline-6-carboxylate In dichloromethane; mineral oil for 1h; 13b (13b) 2-(Trimethylsilyl)ethyl 4-{4-[(1E)-3-(dimethylamino)-3-oxopropen-1-yl]phenyl}isoquinoline-5-carboxylate Diethyl [2-(dimethylamino)-2-oxoethyl]phosphonate (133 mg, 0.597 mmol) was dissolved in dichloromethane (4 mL), to which 55% sodium hydride (21 mg, 0.48 mmol) was added at 0°C, followed by stirring for 10 minutes. To this solution, 2-(trimethylsilyl)ethyl 4-(4-formylphenyl)isoquinoline-6-carboxylate (150 mg, 0.40 mmol) synthesized in Example 13 (13a) was added, followed by stirring for one hour. To the resulting reaction liquid, a saturated aqueous solution of ammonium chloride was added, followed by extraction with ethyl acetate. The resulting organic layer was washed with saturated brine and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure. The residue thus obtained was purified by silica gel column chromatography (hexane : ethyl acetate, 100 : 0 - 35 : 65, V/V) to give the desired title compound (168 mg, yield 95%). 1H-NMR (CDCl3) δ: 0.05 (9H, s), 1.09-1.16 (2H, m), 3.11 (3H, s), 3.23 (3H, s), 4.40-4.52 (2H, m), 7.01 (1H, d, J = 15.4 Hz), 7.55 (2H, d, J = 8.3 Hz), 7.72 (2H, d, J = 8.3 Hz), 7.78 (1H, d, J = 15.4 Hz), 8.11 (1H, d, J = 8.5 Hz), 8.22 (1H, d, J = 8.5 Hz), 8.58 (1H, s), 8.64 (1H, s), 9.33 (1H, s). MS (FAB) m/z: 447 (M+H)+.
  • 36
  • [ 1224174-07-5 ]
  • [ 3842-86-2 ]
  • (1R,2R)-N,N-dimethyl-2-(pent-4-en-1-yl)cyclopropane-1-carboxamide [ No CAS ]
YieldReaction ConditionsOperation in experiment
82% With sodium t-butanolate In 2-methyltetrahydrofuran at 0 - 78℃; for 20h; Inert atmosphere; 2 Example 2: Preparation of Cvclopropyl Amide A 2-L 3-neck round-bottom flask equipped with a condenser, an overhead stirrer under N2 was charged with 2-methyl-THF (600 mL, KF To a 2-MeTHF solution of chlorohydrin from Step 1 (36.9 g assay, 0.248 mol, KF = 220) from Example 1 was added diethyl[2-(dimethylamino)-2-oxoethyl] phosphonate (80.2 g, 86 wt%, 0.309 mol). This mixed solution (-230 mL) was transferred via cannula to the above sodium tert-butoxide solution over 10 min with the temperature rising to 18°C. The reaction solution was heated to 78°C and aged for 20 h. The reaction solution was cooled to RT (20°C), and water (375 mL) was added dropwise, while the internal temperature was maintained at For epoxide intermediate: XH NMR (500 MHz, CDC13) δ 5.82 (m, 1 H), 5.04 (d, J = 17.3 Hz, 1 H), 4.98 (d, J = 10.2 Hz, 1 H), 2.93 (m, 1 H), 2.76 (m, 1 H), 2.48 (m, 1 H), 2.13 (m, 2 H), 1.57 (m, 4 H). 1 C NMR (125 MHz, CDC13) δ 138.5, 115.0, 52.4, 47.3, 33.6, 32.1, 25.4. For N,N-dimethyl amide product: XH NMR (500 MHz, J^-MeOH) δ 5.81 (m, 1 H), 5.00 (m, 1 H), 4.93 (m, 1 H), 3.20 (s, 3 H), 2.94 (s, 3 H), 2.09 (m, 2 H), 1.67 (m, 1 H), 1.52 (m, 2 H), 1.37 (m, 1 H), 1.25 (m, 1 H), 1.07 (m, 1 H), 0.67 (m, 1 H). 13C NMR (125 MHz, < 4-MeOH) δ 175.8, 140.0, 115.2, 38.0, 36.4, 34.6, 33.7, 29.9, 23.2, 19.7, 15.5.
39 g With sodium t-butanolate In 2-methyltetrahydrofuran at 78℃; for 20h; diastereoselective reaction;
  • 37
  • [ 1026660-51-4 ]
  • [ 3842-86-2 ]
  • (1R,2S)-N,N-dimethyl-2-(pent-2-yn-1-yl)cyclopropane-carboxamide [ No CAS ]
YieldReaction ConditionsOperation in experiment
67% With n-butyllithium In 2-methyltetrahydrofuran at -35 - 72℃; for 17.5h; 8 Example 8: Cyclopropanation To the solution of (s)-l-chlorohept-yn-2-ol (100.0 g, 76 wt%, 518 mmol) and diethyl (2-(dimethylamino)-2-oxoethyl)phosphonate (140 g, 82 wt%, 518 mmol) in 2-Me-THF (1700 ml) at -35°C was added n-BuLi solution dropwise over 30 min maintaining temperature < -20°C. The reaction was allowed to warm up to RT then heated to reflux at 72°C for 17 h. The reaction was cooled to 10°C and quenched with 10 wt% brine (1000 ml). The organic layer was separated, dried over MgSC^, filtered and concentrated to yield 112.0 g red oil, which was purified by silica gel chromatography (30% EtO Ac/Hex) to yield desired product as a red oil (76.7g, IY= 67%) 1H NMR 5 (500 MHz, CDC13): 0.79-0.83 (m, 1H), 1.10 (q, J=7.45 Hz, 3H), 1.16- 1.20 (m, 1H), 1.46-1.52 (m, 1H), 1.69-1.73 (m, 1H), 2.12-2.17 (m, 2H), 2.25-2.3 l(m, 1H), 2.45- 2.49 (m, 1H), 2.96 (s, 3H), 3.18(s, 3H)
  • 38
  • [ 3842-86-2 ]
  • [ 953047-22-8 ]
  • (1R,2R)-2-allyl-N,N-dimethylcyclopropanecarboxamide [ No CAS ]
YieldReaction ConditionsOperation in experiment
77% With n-butyllithium In tetrahydrofuran; 2-methyltetrahydrofuran at -40℃; Reflux; 17 Example 1 -2-allyl-N \-dimethylcvclopropanecarboxamide To a RB flask was charged (S)-l-chloropent-4-en-2-ol (11.3 g, 68.2 mmol) from Example 16, and the material was further dried by concentrating with 2-MeTHF. Diethyl (2- (dimethylamino)-2-oxoethyl)phosphonate (21.3 g, 82 mmol) and THF (250mL) were then charged, and the mixture was then cooled to an internal temperature of -40°C. n-BuLi (66 mL, 165 mmol, 2.5M) was then slowly charged via syringe over 25 min, keeping the internal temperature below -28°C. The reaction was then allowed to warm to RT over approximately 20 min and then heated to an internal temperature of 55°C overnight. The mixture was then refluxed (4 h); the reaction was deemed complete by HPLC analysis and then cooled to 10°C, where it was quenched with half-saturated NH4C1 (160 mL). The layers were then separated, and the organic layer was washed 10% NaCl (2 x 50 mL) and then concentrated. The combined aqueous layers were then combined and back-extracted with EtOAc (50 mL). The layers were separated, and the organic layer was washed with 10% NaCl (20 mL). The final organic layers were combined and concentrated to yield a crude oil. The crude product was further purified via silica gel chromatographed (eluted with hexanes: EtOAc 1st 70: 30 then 50:50) to yield the desired product (8.01 g, 77% yield) upon concentration and flushing with THF.
  • 39
  • [ 3842-86-2 ]
  • C39H54N4O10 [ No CAS ]
  • C43H61N5O10 [ No CAS ]
YieldReaction ConditionsOperation in experiment
28% With sodium hydride In tetrahydrofuran at 0 - 20℃; for 1h; 8.2 8.2 Synthesis of 22 8.2 Synthesis of 22To a solution of 21 (50 mg, 0.224 mmol) in THF (1.0 mL) was added NaH (1.6 mg, 0.068 mmol) in anhydrous THF (0.2 mL) at 0° C. with stirring. The solution was then stirred at room temperature until it became clear. Then 8 (40 mg, 0.054 mmol) was added to the clear solution and the mixture stirred at room temperature for 1 h. The mixture was quenched with water (10 mL) and extracted with EA (3×20 mL). The organic layer was washed with brine and dried over Na2SO4, filtered, evaporated. The residue was purified by Prep HPLC [Column: Spring C18(25*250 mm, 10 μm), Mobile phase: A:H2O B:Acetonitrile, Gradient: B from 30% to 40% over 10 min] to obtained 22 as a white solid (12.4 mg, 28%). LC-MS: 808 [M+1]+. See FIG. 6 for 1H NMR.
  • 40
  • [ 3842-86-2 ]
  • 4-(1-cyclohexyl-1,6-dihydroimidazo[4,5-d]pyrrolo[2,3-b]pyridin-2-yl)benzaldehyde [ No CAS ]
  • (E)-3-(4-(1-cyclohexyl-1,6-dihydroimidazo[4,5-d]pyrrolo[2,3-b]pyridin-2-yl)phenyl)-N,N-dimethylacrylamide [ No CAS ]
YieldReaction ConditionsOperation in experiment
70% With 1,8-diazabicyclo[5.4.0]undec-7-ene; lithium chloride In chloroform; acetonitrile at 20℃; for 4h;
  • 41
  • [ 3842-86-2 ]
  • 3-(1-cyclohexyl-1,6-dihydroimidazo[4,5-d]pyrrolo[2,3-b]pyridin-2-yl)benzaldehyde [ No CAS ]
  • (E)-3-(3-(1-cyclohexyl-1,6-dihydroimidazo[4,5-d]pyrrolo[2,3-b]pyridin-2-yl)phenyl)-N,N-dimethylacrylamide [ No CAS ]
YieldReaction ConditionsOperation in experiment
74% With 1,8-diazabicyclo[5.4.0]undec-7-ene; lithium chloride In chloroform; acetonitrile at 20℃; for 2h;
  • 42
  • [ 3842-86-2 ]
  • 5-(1-cyclohexyl-1,6-dihydroimidazo[4,5-d]pyrrolo[2,3-b]pyridin-2-yl)furan-2-carbaldehyde [ No CAS ]
  • (E)-3-(5-(1-cyclohexyl-1,6-dihydroimidazo[4,5-d]pyrrolo[2,3-b]pyridin-2-yl)furan-2-yl)-N,N-dimethylacrylamide [ No CAS ]
YieldReaction ConditionsOperation in experiment
88% With 1,8-diazabicyclo[5.4.0]undec-7-ene; lithium chloride In chloroform; acetonitrile at 20℃; for 2h;
  • 43
  • [ 3842-86-2 ]
  • [ 129241-89-0 ]
  • (E,2S)-2-[bis(tert-butoxycarbonyl)amino]-7-(dimethylamino)-7-oxohept-5-enoate [ No CAS ]
YieldReaction ConditionsOperation in experiment
1.1 g Stage #1: diethyl N,N-dimethylcarbamoylmethylphosphonate With lithium hexamethyldisilazane In 1,2-dimethoxyethane at 0℃; for 0.5h; Stage #2: tert-butyl (2S)-2-{bis[(tert-butoxy)carbonyl]amino}-5-oxopentanoate In 1,2-dimethoxyethane at 0℃; for 1h; 3 To a solution of 2-diethoxyphosphoryl-N,N-dimethyl-acetamide (633 mg, 2.84 mmol) in DME (10 mL) was added LiHMDS (1 M, 2.84 mL) at 0 °C. The mixture was stirred at °C for 0.5 h. Then tert-butyl (2S)-2-[bis(tert-butoxycarbonyl)amino]-5-oxo- pentanoate (1 g, 2.58 mmol) in DME (5 mL) was added , the mixture was stirred at 0 °C for 1 h. The mixture was added H2O (50 mL), and extracted with EtOAc (30 mL × 3). The combined organic layers were washed with brine (30 mL × 3), dried over anhydrous Na2SO4, filtered and concentrated under reduced pressure to give a residue. The residue was purified by column chromatography to give (E,2S)-2-[bis(tert-butoxycarbonyl)amino]-7- (dimethylamino)-7-oxo-hept-5-enoate (I-85) (1.1 g) as a yellow oil.1H NMR (400 MHz, CDCl3) d 6.93-6.78 (m, 1H), 6.27 (d, J = 15.2 Hz, 1H), 4.80-4.64 (m, 1H), 3.09-2.94 (m, 6H), 2.30-2.16 (m, 3H), 2.03-1.95 (m, 1H), 1.49 (s, 18H), 1.43 (s, 9H).
  • 44
  • [ 3842-86-2 ]
  • (2S)-tert-butyl-2-[tert-butoxycarbonyl-[2-[tert-butyl(diphenyl)silyl]oxyethoxycarbonyl]amino]-5-oxopentanoate [ No CAS ]
  • tert-butyl (E,2S)-2-[tert-butoxycarbonyl-[2-[tert-butyl(diphenyl)silyl]oxyethoxycarbonyl]amino]-7-(dimethylamino)-7-oxohept-5-enoate [ No CAS ]
YieldReaction ConditionsOperation in experiment
23% Stage #1: diethyl N,N-dimethylcarbamoylmethylphosphonate With sodium hydride In tetrahydrofuran at -5 - 20℃; for 0.5h; Stage #2: (2S)-tert-butyl-2-[tert-butoxycarbonyl-[2-[tert-butyl(diphenyl)silyl]oxyethoxycarbonyl]amino]-5-oxopentanoate In tetrahydrofuran at -5℃; for 0.5h; 39 Example 39: To a stirring solution of diethyl (2-(dimethylamino)-2-oxoethyl)phosphonate (2.18 g, 9.77 mmol) in THF (50 mL) was added NaH (391 mg, 9.77 mmol) at -5 °C. The resulting suspension was stirred at 20 °C for 0.5 h. A solution of tert-butyl(2S)-2-[tert-butoxycarbonyl- [2-[tert-butyl(diphenyl)silyl]oxyethoxycarbonyl]amino]-5-oxo-pentanoate (5 g, 8.15 mmol) in THF (20 mL) was then added dropwise at -5 °C over 0.5 h. The reaction mixture(combined with the other four bateches) was poured into saturated NH4Cl solution (200 mL) and extracted with EtOAc (200 mL × 2). The combined organic layers were washed with brine (500 mL) and dried over anhydrous Na2SO4, filtered and concentrated in vacuum to give a residue. The residue was purified by silica gel chromatography to give tert- butyl(E,2S)-2-[tert-butoxycarbonyl-[2-[tert-butyl(diphenyl)silyl]oxyethoxycarbonyl]amino]- 7-(dimethylamino)-7-oxo-hept-5-enoate (I-352) (6.3 g, 23% yield) as a colorless oil.1H NMR (400 MHz, CDCl3) d 7.69-7.64 (m, 4H), 7.45-7.36 (m, 6H), 6.88-6.79 (m, 1H), 6.24 (d, J = 14.8 Hz, 1H), 4.86-4.78 (m, 1H), 4.39-4.21 (m, 2H), 3.88 (t, J = 5.2 Hz, 2H), 3.49 (s, 3H), 3.02 (s, 3H), 2.99 (s, 3H), 2.30-2.19 (m, 3H), 2.14-1.97 (m, 1H), 1.49 (s, 9H), 1.43 (s, 9H), 1.05 (s, 9H).
  • 45
  • [ 3842-86-2 ]
  • (S)-tert-butyl 2-((dimethylcarbamoyl)oxy)-5-oxopentanoate [ No CAS ]
  • (S,E)-tert-butyl 7-(dimethylamino)-2-((dimethylcarbamoyl)oxy)-7-oxohept-5-enoate [ No CAS ]
YieldReaction ConditionsOperation in experiment
78% Stage #1: diethyl N,N-dimethylcarbamoylmethylphosphonate With potassium <i>tert</i>-butylate In tetrahydrofuran at 0℃; for 0.5h; Stage #2: (S)-tert-butyl 2-((dimethylcarbamoyl)oxy)-5-oxopentanoate In tetrahydrofuran at 0℃; for 0.5h; To a mixture of diethyl (2-(dimethylamino)-2-oxoethyl)phosphonate (I-35) (310 mg, 1.39 mmol) in THF (10 mL) was added t-BuOK (156 mg, 1.39 mmol) at 0 °C. The mixture was stirred at 0 °C for 0.5 h. (S)-tert-butyl 2-((dimethylcarbamoyl)oxy)-5- oxopentanoate (I-34) (0.3 g, 1.16 mmol) in THF (5 mL) was added to the above solution. The mixture was stirred at 0 °C for 0.5 h. The resulting solution was diluted with water (10 mL) and extracted with ethyl acetate (20 mL × 2). The combined organic layers were washed with brine (30 mL), dried over anhydrous Na2SO4, filtered and concentrated in vacuum to give a residue. The residue was purified by silica gel chromatography to afford (S,E)-tert-butyl 7- (dimethylamino)-2-((dimethylcarbamoyl)oxy)-7-oxohept-5-enoate (I-36) (0.3 g, 78% yield) as a colorless oil.
  • 46
  • [ 3842-86-2 ]
  • tert-butyl 3,3-dideuterio-2-(dimethylcarbamoyloxy)-5-oxopentanoate [ No CAS ]
  • tert-butyl (E)-3,3-dideuterio-7-(dimethylamino)-2-(dimethylcarbamoyloxy)-7-oxohept-5-enoate [ No CAS ]
YieldReaction ConditionsOperation in experiment
3 g Stage #1: diethyl N,N-dimethylcarbamoylmethylphosphonate With sodium hydride In tetrahydrofuran at -10℃; for 0.166667h; Stage #2: tert-butyl 3,3-dideuterio-2-(dimethylcarbamoyloxy)-5-oxopentanoate In tetrahydrofuran at -10℃; for 1h; To a solution of diethyl (2-(dimethylamino)-2-oxoethyl)phosphonate (I-35) (2.77 g, 12.4 mmol) in THF (20 mL) was added NaH (496 mg, 12.4 mmol, 60% purity) at -10 °C, The mixture was stirred for 10 min. Then the solution of tert-butyl 3,3-dideuterio-2- (dimethylcarbamoyloxy)-5-oxo-pentanoate (I-52) (2.7 g, 10.3 mmol) in THF (10 mL) was add dropwise to the reaction at -10 °C. After stirred at -10 °C for 1 h, the mixture was poured into H2O (100 mL). The resultant was extracted with EtOAc (50 mL × 3). The combined organic layers were dried over Na2SO4, filtered and concentrated to give tert-butyl (E)-3,3- dideuterio-7-(dimethylamino)-2-(dimethylcarbamoyloxy)-7-oxo-hept-5-enoate (I-53) (3.0 g, 8.72 mmol) as a light yellow oil. LCMS m/z 331.1 (M+1)+.
  • 47
  • [ 590-14-7 ]
  • [ 3842-86-2 ]
  • C11H22NO4P [ No CAS ]
YieldReaction ConditionsOperation in experiment
Stage #1: diethyl N,N-dimethylcarbamoylmethylphosphonate With sodium hydride In tetrahydrofuran at 0℃; for 0.5h; Inert atmosphere; Stage #2: 1-bromo-1-propene at 0 - 20℃;
Same Skeleton Products
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