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Product Details of [ 76-09-5 ]

CAS No. :76-09-5 MDL No. :MFCD00004462
Formula : C6H14O2 Boiling Point : -
Linear Structure Formula :- InChI Key :IVDFJHOHABJVEH-UHFFFAOYSA-N
M.W : 118.17 Pubchem ID :6425
Synonyms :

Calculated chemistry of [ 76-09-5 ]

Physicochemical Properties

Num. heavy atoms : 8
Num. arom. heavy atoms : 0
Fraction Csp3 : 1.0
Num. rotatable bonds : 1
Num. H-bond acceptors : 2.0
Num. H-bond donors : 2.0
Molar Refractivity : 33.36
TPSA : 40.46 Ų

Pharmacokinetics

GI absorption : High
BBB permeant : Yes
P-gp substrate : No
CYP1A2 inhibitor : No
CYP2C19 inhibitor : No
CYP2C9 inhibitor : No
CYP2D6 inhibitor : No
CYP3A4 inhibitor : No
Log Kp (skin permeation) : -6.96 cm/s

Lipophilicity

Log Po/w (iLOGP) : 1.64
Log Po/w (XLOGP3) : 0.09
Log Po/w (WLOGP) : 0.53
Log Po/w (MLOGP) : 0.61
Log Po/w (SILICOS-IT) : 0.13
Consensus Log Po/w : 0.6

Druglikeness

Lipinski : 0.0
Ghose : None
Veber : 0.0
Egan : 0.0
Muegge : 1.0
Bioavailability Score : 0.55

Water Solubility

Log S (ESOL) : -0.56
Solubility : 32.3 mg/ml ; 0.273 mol/l
Class : Very soluble
Log S (Ali) : -0.49
Solubility : 37.9 mg/ml ; 0.32 mol/l
Class : Very soluble
Log S (SILICOS-IT) : -0.33
Solubility : 55.9 mg/ml ; 0.473 mol/l
Class : Soluble

Medicinal Chemistry

PAINS : 0.0 alert
Brenk : 0.0 alert
Leadlikeness : 1.0
Synthetic accessibility : 1.0

Safety of [ 76-09-5 ]

Signal Word:Warning Class:N/A
Precautionary Statements:P501-P270-P264-P280-P302+P352-P337+P313-P305+P351+P338-P362+P364-P332+P313-P301+P312+P330 UN#:N/A
Hazard Statements:H302-H315-H319 Packing Group:N/A
GHS Pictogram:

Application In Synthesis of [ 76-09-5 ]

* 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.

  • Upstream synthesis route of [ 76-09-5 ]
  • Downstream synthetic route of [ 76-09-5 ]

[ 76-09-5 ] Synthesis Path-Upstream   1~152

  • 1
  • [ 76-09-5 ]
  • [ 6361-22-4 ]
  • [ 4964-69-6 ]
Reference: [1] Advanced Synthesis and Catalysis, 2018, vol. 360, # 11, p. 2216 - 2220
  • 2
  • [ 13311-84-7 ]
  • [ 67-63-0 ]
  • [ 76-09-5 ]
  • [ 1939-27-1 ]
Reference: [1] Journal of Photochemistry and Photobiology A: Chemistry, 2015, vol. 298, p. 55 - 61
  • 3
  • [ 76-09-5 ]
  • [ 121-43-7 ]
  • [ 1195-66-0 ]
YieldReaction ConditionsOperation in experiment
90% for 6 h; Inert atmosphere; Reflux Synthesis of 2-methoxy-4,4,5,5-tetramethyl[1,3,2]dioxaborolane
A flask equipped with a reflux condenser, stirrer, an inert gas inlet and a thermocouple set in heating mantle was charged with trimethyl borate and pinacol under positive pressure of nitrogen.
The resulting mixture was heated at reflux for 6 hours.
The mixture was cooled to ambient temperatures and transferred to a flask with a Vigreux column.
The mixture was distilled at atmospheric pressure to afford 2-methoxy-4,4,5,5-tetramethyl[1,3,2]dioxaborolane (bp 159° C.) in high yield (90percent).
1H NMR (400 MHz, CDCl3): δ.box. 3.41 (m, 3H), 1.11 (m, 12H).
11B NMR (128.3 MHz, CDCl3): δ 22.2. 13C NMR (100.6 MHz, CDCl3): δ.box. 82.7, 52.6, 24.6.
Reference: [1] Patent: US2012/289733, 2012, A1, . Location in patent: Page/Page column 4
[2] Angewandte Chemie - International Edition, 2005, vol. 44, # 20, p. 3133 - 3135
  • 4
  • [ 76-09-5 ]
  • [ 870-63-3 ]
  • [ 141550-13-2 ]
Reference: [1] European Journal of Organic Chemistry, 2009, # 23, p. 3964 - 3972
  • 5
  • [ 76-09-5 ]
  • [ 1714-29-0 ]
  • [ 164461-18-1 ]
  • [ 349666-24-6 ]
Reference: [1] European Journal of Organic Chemistry, 2001, # 20, p. 3819 - 3829
  • 6
  • [ 76-09-5 ]
  • [ 166329-94-8 ]
  • [ 185990-03-8 ]
Reference: [1] Tetrahedron, 1999, vol. 55, # 29, p. 8787 - 8800
[2] Chemical Communications, 1996, # 24, p. 2777 - 2778
  • 7
  • [ 76-09-5 ]
  • [ 87199-17-5 ]
  • [ 128376-64-7 ]
YieldReaction ConditionsOperation in experiment
91% at 20℃; for 2 h; To a solution of 4-formylphenylboronic acid (1 g) in anhydrous THF (10 ml_) was added 2,3-dimethyl-butane-2,3-diol (0.867 mg) and the mixture was EPO <DP n="15"/>stirred at room temperature for 2 hours. The solvent was evaporated to dryness. The residue was dissolved in dichloromethane (40 ml_), washed with water (25 ml_ x 3), dried and evaporated under vacuum to obtain 4-(4,4,5,5- tetramethyl-[1 ,3,2]dioxaborolan-2-yl)-benzaldehyde (1.41 g, 91percent yield). 1H- NMR (400 MHz, CDCI3): δ 1.34 (s, 12 H, 4 CH3), 7.86 (d, J = 8.4 Hz, 2 H, H- Ar), 7.96 (d, J = 8 Hz, 2 H, H-Ar), 10.05 (s, 1 H, CHO) ppm.
91% at 20℃; for 2 h; Example 2: Preparation of 4-(4A5,5-tetramethyl-H ,3,21dioxaborolan-2-yl)- benzaldehvde; To a solution of 4-formylphenylboronic acid (1 g) in anhydrous THF (10 mL) was added 2,3-dimethyl-butane-2,3-diol (0.867 mg) and the mixture was stirred at room temperature for 2 hours. The solvent was evaporated to dryness. The residue was dissolved in dichloromethane (40 mL), washed with water (25 mL x 3), dried and evaporated under vacuum to obtain 4-(4, 4,5,5- tetramethyl-[1 ,3,2]dioxaborolan-2-yl)-benzaldehyde (1.41 g, 91 percent yield). 1H- NMR (400 MHz, CDCI3): δ 1.34 (s, 12 H, 4 CH3), 7.86 (d, J = 8.4 Hz, 2 H, H- Ar), 7.96 (d, J = 8 Hz, 2 H, H-Ar), 10.05 (s, 1 H, CHO) ppm.
Reference: [1] Synthetic Communications, 2002, vol. 32, # 17, p. 2669 - 2676
[2] European Journal of Organic Chemistry, 2000, # 9, p. 1703 - 1710
[3] Israel Journal of Chemistry, 2009, vol. 49, # 1, p. 1 - 8
[4] Journal of Organic Chemistry, 2007, vol. 72, # 12, p. 4328 - 4339
[5] Journal of Physical Chemistry A, 2017, vol. 121, # 40, p. 7550 - 7564
[6] Journal of the American Chemical Society, 2003, vol. 125, # 32, p. 9668 - 9681
[7] Journal of the American Chemical Society, 2003, vol. 125, # 32, p. 9668 - 9681
[8] Applied Organometallic Chemistry, 2019, vol. 33, # 1,
[9] Organic Letters, 2003, vol. 5, # 23, p. 4389 - 4392
[10] Patent: WO2006/67216, 2006, A2, . Location in patent: Page/Page column 13-14
[11] Patent: WO2007/71750, 2007, A1, . Location in patent: Page/Page column 17
[12] Tetrahedron, 2001, vol. 57, # 45, p. 9285 - 9298
[13] Organic Letters, 2010, vol. 12, # 14, p. 3216 - 3218
[14] Journal of Materials Chemistry B, 2018, vol. 6, # 16, p. 2489 - 2496
[15] Chem, 2017, vol. 3, # 3, p. 437 - 460
[16] Canadian Journal of Chemistry, 2001, vol. 79, # 7, p. 1115 - 1123
[17] Canadian Journal of Chemistry, 2001, vol. 79, # 7, p. 1115 - 1123
[18] Journal of the American Chemical Society, 2010, vol. 132, # 21, p. 7268 - 7269
[19] Acta Crystallographica Section C: Crystal Structure Communications, 2012, vol. 68, # 6, p. o213-o215
[20] Journal of the American Chemical Society, 2013, vol. 135, # 7, p. 2552 - 2559
[21] Organic Letters, 2013, vol. 15, # 18, p. 4850 - 4853
[22] Molecules, 2013, vol. 18, # 10, p. 12346 - 12367
[23] Journal of Organic Chemistry, 2015, vol. 80, # 6, p. 3036 - 3049
[24] Organic Letters, 2015, vol. 17, # 12, p. 3086 - 3089
[25] Arkivoc, 2016, vol. 2017, # 2, p. 107 - 117
[26] Journal of Organic Chemistry, 2018, vol. 83, # 4, p. 1842 - 1851
[27] Inorganic Chemistry, 2018, vol. 57, # 9, p. 4877 - 4890
[28] Patent: US6576789, 2003, B1,
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Reference: [1] European Journal of Organic Chemistry, 2009, # 23, p. 3964 - 3972
  • 9
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  • [ 190788-58-0 ]
Reference: [1] Chemical Communications, 2007, # 35, p. 3667 - 3669
[2] Tetrahedron Letters, 2013, vol. 54, # 2, p. 166 - 169
  • 10
  • [ 76-09-5 ]
  • [ 104-95-0 ]
  • [ 51901-85-0 ]
  • [ 7440-66-6 ]
  • [ 190788-58-0 ]
Reference: [1] Chemical Communications, 2007, # 35, p. 3667 - 3669
  • 11
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  • [ 98546-51-1 ]
  • [ 190788-58-0 ]
Reference: [1] Journal of Organic Chemistry, 2011, vol. 76, # 13, p. 5240 - 5246
[2] Chemical Communications, 2015, vol. 51, # 21, p. 4406 - 4409
  • 12
  • [ 76-09-5 ]
  • [ 22092-92-8 ]
  • [ 456-27-9 ]
  • [ 171364-83-3 ]
YieldReaction ConditionsOperation in experiment
71%
Stage #1: With ferrocene In acetonitrile at 20℃; for 2.5 h;
Stage #2: With methanol In acetonitrile at 0 - 20℃; for 1 h;
Stage #3: at 20℃; for 4 h;
Example 3: General procedure D for the synthesis of the arylpinacolboronates by arylation of diisopropylaminoborane, catalysed by ferrocene (1percent), followed by methanolysis and transesterification In a dried tube reactor under argon as described in example 2, the arenediazonium salt (1 mmol) and the ferrocene (ΙΟμιηοΙ, 1.8mg) were dissolved in 2mL of anhydrous CH3CN. Diisopropylaminoborane (2mmol, 226mg) was then added to the solution and the mixture was stirred for 2h30 at room temperature. The reaction mixture was quenched by a slow addition of anhydrous MeOH at 0°C (2mL) and stirred for an additional hour at room temperature. After removal of all the volatiles, 1.3eq of pinacol was added in Et20 (2mL), the mixture was stirred 4h at room temperature. The crude mixture was washed with a 50g/L CuCl2 solution (2 x 5mL). The organic layer were separated, dried over Na2S04, filtered and concentrated to dryness. The resulted oil was dissolved with CH2C12 and filtered of a pad of silica gel, eluting with CH2C12 to afford the corresponding boronate. Example 9: synthesis of 2-(4-nitrophenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane [CAS 171364-83-3], compound VI6. 176 mg of 2-(3-iodophenyl)-4,4,5,5-tetramethyl-l,3,2-dioxaborolane were obtained following the general procedure D according to example 3, using 237 mg of 4-nitrobenzenediazonium tetrafluoroborate as a pale yellow oil, with an isolated yield of 71percent. 1H NMR (300 MHz, CDC13) δ 8.19 (d, J = 8.7 Hz, 2H) 7.96 (d, J = 8.7 Hz, 2H) 1.37 (s, 12H) 11Β NMR (100 MHz, CDC13) δ 30.87 13C NMR (75 MHz, CDC13) δ 135.80; 122.56; 84.78; 25.02 MS (EI) tR = 10.31 min; m/z: 249 (Μ+', 100percent)
Reference: [1] Patent: WO2014/9169, 2014, A1, . Location in patent: Page/Page column 56-57
  • 13
  • [ 76-09-5 ]
  • [ 24067-17-2 ]
  • [ 171364-83-3 ]
Reference: [1] Journal of Organic Chemistry, 2009, vol. 74, # 9, p. 3316 - 3322
[2] Chemical Communications, 2015, vol. 51, # 21, p. 4406 - 4409
[3] Organic Letters, 2010, vol. 12, # 14, p. 3216 - 3218
[4] Organic Letters, 2015, vol. 17, # 12, p. 3086 - 3089
  • 14
  • [ 76-09-5 ]
  • [ 92203-81-1 ]
  • [ 171364-83-3 ]
Reference: [1] Tetrahedron Letters, 2014, vol. 55, # 10, p. 1702 - 1705
  • 15
  • [ 76-09-5 ]
  • [ 171364-83-3 ]
Reference: [1] Advanced Synthesis and Catalysis, 2013, vol. 355, # 6, p. 1083 - 1088
  • 16
  • [ 76-09-5 ]
  • [ 14047-29-1 ]
  • [ 180516-87-4 ]
YieldReaction ConditionsOperation in experiment
81% for 2 h; Heating / reflux 4-Carboxyphenylboronic acid (10.0 g, 60.3 mmol) was suspended in 100 mL of toluene and pinnacol added (7.1 g, 60.3 mmol). The reaction was heated to reflux with a Dean-Stark trap attached. The reaction became homogenous upon heating. After 2 h reflux the reaction was allowed to stand overnight and white needles were collected by filtration, rinsed with toluene, and vacuum dried to 4-(4,4,5,5-tetramethyl-[1,3,2]dioxaborolan-2-yl)-benzoic acid 12.2 g (81percent). MS (FD MS): M=248. Analysis calculated for C13H17BO4: C, 62.94; H, 6.91 Found: C, 62.71; H, 6.91.
81% for 2 h; Heating / reflux 4-Carboxyphenylboronic acid (10.0 g, 60.3 mmol) was suspended in 100 mL of toluene and pinnacol added (7.1 g, 60.3 mmol). The reaction was heated to reflux with a Dean-Stark trap attached. The reaction became homogenous upon heating. After 2 h reflux the reaction was allowed to stand overnight and white needles were collected by filtration and rinsed with toluene. The title compound was vacuum dried to 12.2 g (81percent).[0153] Mass Spectrum (FD MS): M=248. Analysis calculated for C13H17BO4: percent C, 62.94; percent H, 6.91; Found: percent C, 62.71; percent H, 6.91.
Reference: [1] Synthetic Communications, 2002, vol. 32, # 17, p. 2669 - 2676
[2] Journal of Organic Chemistry, 2006, vol. 71, # 20, p. 7915 - 7918
[3] Patent: US2004/6114, 2004, A1, . Location in patent: Page 64
[4] Patent: US6639107, 2003, B1, . Location in patent: Page/Page column 31
[5] Organic letters, 2001, vol. 3, # 6, p. 917 - 920
[6] Patent: US2002/55631, 2002, A1,
[7] Patent: US2002/86887, 2002, A1,
[8] Bioorganic and Medicinal Chemistry, 2012, vol. 20, # 16, p. 5012 - 5016
[9] Patent: WO2015/106292, 2015, A1, . Location in patent: Paragraph 00323; 00330; 00331
[10] Chemistry - An Asian Journal, 2017, vol. 12, # 10, p. 1087 - 1094
[11] Journal of Organic Chemistry, 2018, vol. 83, # 4, p. 1842 - 1851
  • 17
  • [ 76-09-5 ]
  • [ 494225-46-6 ]
  • [ 180516-87-4 ]
Reference: [1] Tetrahedron Letters, 2013, vol. 54, # 2, p. 166 - 169
  • 18
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  • [ 557-93-7 ]
  • [ 28049-80-1 ]
  • [ 126726-62-3 ]
YieldReaction ConditionsOperation in experiment
66%
Stage #1: With lithium In tetrahydrofuran at -10 - 25℃; for 6 h;
Stage #2: With 2,6-di-tert-butyl-4-methyl-phenol In tetrahydrofuranReflux
Dissolve isopropenyl bromide (89.58, 0.7411101) in 75011 ^ tetrahydrofuran, dropwise add bis (diisopropylAmine) boron chloride (183 g, 0.74 mol), lithium metal (10.4 g, 1.5 ml), and 110 mL of tetrahydrofuran were added dropwise a process controlThe reaction temperature was -10 ° C to 0 ° C. After completion of the dropwise addition, the temperature was maintained for 1 hour,The reaction was then continued for 5 hours at 25 ° C.After the completion of the reaction, pinacol (988, 0.83111 01), 2,6-di-tert-butyl-4-methylphenol (4.58) and 1201 tetrahydrofuran were added and the temperature was raised to reflux.Distillation under reduced pressure afforded the colorless transparent liquid isopropenylboronic acid pinacol ester 82.lg, yield 66percent, GC: 99.7percent2,6-di-tert-butyl-4-methylphenol (0.45 g) was added for long-term storage.
Reference: [1] Patent: CN105503923, 2016, A, . Location in patent: Paragraph 0018
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  • [ 126726-62-3 ]
Reference: [1] Organic Letters, 2004, vol. 6, # 22, p. 4037 - 4039
[2] Journal of the American Chemical Society, 2006, vol. 128, # 50, p. 16384 - 16393
  • 20
  • [ 76-09-5 ]
  • [ 1692-15-5 ]
  • [ 181219-01-2 ]
Reference: [1] Journal of Alloys and Compounds, 2013, vol. 555, p. 22 - 27
  • 21
  • [ 76-09-5 ]
  • [ 15854-87-2 ]
  • [ 181219-01-2 ]
Reference: [1] Tetrahedron Letters, 2005, vol. 46, # 28, p. 4737 - 4740
  • 22
  • [ 76-09-5 ]
  • [ 181219-01-2 ]
Reference: [1] Angewandte Chemie (International Edition in English), 2000, vol. 39, # 21, p. X3843-3845
  • 23
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  • [ 138500-85-3 ]
Reference: [1] Synlett, 2006, # 3, p. 475 - 477
[2] Patent: WO2017/8743, 2017, A1,
[3] Angewandte Chemie - International Edition, 2018, vol. 57, # 21, p. 6324 - 6328[4] Angew. Chem., 2018, vol. 130, p. 6432 - 6436,5
[5] Patent: US6335451, 2002, B1,
  • 24
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  • [ 68162-47-0 ]
  • [ 138500-85-3 ]
Reference: [1] Organic Preparations and Procedures International, 1991, vol. 23, # 6, p. 729 - 734
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  • [ 5720-05-8 ]
  • [ 138500-85-3 ]
Reference: [1] Patent: CN107417714, 2017, A,
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  • [ 76-09-5 ]
  • [ 1765-93-1 ]
  • [ 18107-18-1 ]
  • [ 243145-83-7 ]
YieldReaction ConditionsOperation in experiment
77%
Stage #1: at 50℃; for 1 h;
Stage #2: With tetrabutyl ammonium fluoride In tetrahydrofuran; 1,4-dioxane; hexane; water at 50℃; for 1 h;
To a 10 mL reaction tube equipped with a magnet was added 0.4 mg (0.8 mmol) of 4-fluorophenylboronic acid (56 mmol), trimethylsilyl diazomethane (2M n-hexane solution), 1 mL of 1, 4-dioxane, plug the rubber stopper and react for 1 hour at 50 ° C on an electromagnetic heating stirrer.(0.4 mmol) of tetramethylammonium fluoride (1 M tetrahydrofuran solution) and 200 uL of water were added to an electromagnetic heating stirrer at 50 ° C, respectively, followed by the addition of 40 mg of pinacol (dissolved in 1 mL of 1,4-dioxane) To continue for 1 hour.After completion of the reaction, the organic solvent was removed by a rotary evaporator and purified by column chromatography4-fluorobenzyl boronic acid pinacol ester, its structure is as follows:The compound was a colorless liquid in a yield of 77percent with the following NMR data:
Reference: [1] Patent: CN105884808, 2016, A, . Location in patent: Paragraph 0070; 0071; 0072; 0073; 0074; 0075
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  • [ 159087-45-3 ]
Reference: [1] Organic Letters, 2018, vol. 20, # 16, p. 4719 - 4722
  • 28
  • [ 76-09-5 ]
  • [ 150255-96-2 ]
  • [ 214360-46-0 ]
YieldReaction ConditionsOperation in experiment
4.72 g With sodium sulfate In tetrahydrofuran at 25℃; for 12 h; Inert atmosphere To a solution of 3-cyanophenyl boronic acid (2.5 g, CAS: 150255-96-2) in anhydrous THF (150 ml) under an atmosphere of nitrogen were added pinacol (2.95 g) and Na2SO4 (10 g) at 25°C.The reaction mixture was stirred for 12 h at 25°C under an atmosphere of nitrogen. Then, Na2SO4was filtered off and all volatiles were evaporated. The residue was partitioned between ethylacetate and water. The organic layer was then separated, dried over Na2SO4 and concentrated to afford the title compound (4.72 g) as off white solid which was directly used in the next reaction step without further characterization.
Reference: [1] Journal of the American Chemical Society, 2013, vol. 135, # 7, p. 2552 - 2559
[2] Patent: WO2017/37146, 2017, A1, . Location in patent: Page/Page column 195; 196
[3] Journal of Organic Chemistry, 2018, vol. 83, # 4, p. 1842 - 1851
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  • [ 6952-59-6 ]
  • [ 214360-46-0 ]
Reference: [1] Helvetica Chimica Acta, 2000, vol. 83, # 1, p. 93 - 113
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  • [ 121-43-7 ]
  • [ 6952-59-6 ]
  • [ 214360-46-0 ]
Reference: [1] Helvetica Chimica Acta, 2000, vol. 83, # 1, p. 93 - 113
  • 31
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  • [ 214360-60-8 ]
Reference: [1] Tetrahedron Letters, 2013, vol. 54, # 2, p. 166 - 169
  • 32
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  • [ 121-43-7 ]
  • [ 24265-23-4 ]
  • [ 287944-16-5 ]
YieldReaction ConditionsOperation in experiment
63% With hydrogenchloride; magnesium; methyl iodide In tetrahydrofuran; water; ethyl acetate at 20℃; Reflux Step two: adding magnesium metal (1.9 g, 78mmol) and 10 ml of tetrahydrofuran, add 2-3 drop iodine methane initiating the dropwise 11.9 g 3,6-dihydro -2H-pyran-4-polybromide dissolved in 60 ml tetrahydrofuran solution, reagent cheng Geshi preparing reflux reaction is omitted, then drop by adding trimethoxy-in (9.1 g, 87mmol), after the reaction is complete, by adding 15percent hydrochloric acid solution to adjust PH= 3-4, organic layer by adding 90 ml of ethyl acetate and pinacone (10.3 g, 87mmol), stirring at room temperature until the reaction is complete. After laminating, an organic layer saturated salt water washing, solvent after evaporation to dryness, by adding normal heptane, cooling to -10 °C, filtering to obtain 9.7 g of white solid: 3,6-dihydro -2H-pyran-4-boronic acid pinacone ester, GC: 99.2percent, HNMR > 98percent, the yield is 63percent.
Reference: [1] Patent: CN105503927, 2016, A, . Location in patent: Paragraph 0013
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  • [ 141091-37-4 ]
Reference: [1] Angewandte Chemie - International Edition, 2018, vol. 57, # 51, p. 16832 - 16836[2] Angew. Chem., 2018, vol. 130, p. 17074 - 17078,5
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  • [ 103989-84-0 ]
  • [ 312303-48-3 ]
Reference: [1] Tetrahedron, 2004, vol. 60, # 20, p. 4377 - 4386
  • 35
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  • [ 160688-99-3 ]
  • [ 329214-79-1 ]
Reference: [1] Journal of Organic Chemistry, 2002, vol. 67, # 15, p. 5394 - 5397
[2] Organic Syntheses, 2005, vol. 81, p. 89 - 97
  • 36
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  • [ 121-43-7 ]
  • [ 329214-79-1 ]
Reference: [1] Angewandte Chemie - International Edition, 2016, vol. 55, # 35, p. 10396 - 10400[2] Angew. Chem., 2016, vol. 128, # 35, p. 10552 - 10556,5
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  • [ 1692-25-7 ]
  • [ 329214-79-1 ]
Reference: [1] Journal of the American Chemical Society, 2011, vol. 133, # 30, p. 11438 - 11441
  • 38
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  • [ 329214-79-1 ]
Reference: [1] Journal of Organometallic Chemistry, 2006, vol. 691, # 6, p. 1301 - 1306
  • 39
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  • [ 16419-60-6 ]
  • [ 377780-72-8 ]
YieldReaction ConditionsOperation in experiment
80%
Stage #1: for 2 h; Dean-Stark; Reflux; Inert atmosphere
Stage #2: With N-Bromosuccinimide; 2,2'-azobis(isobutyronitrile) In acetonitrile at 90℃; for 2 h; Inert atmosphere
To a three-necked flask equipped with a Dean-Stark trap was added 30 mL of toluene,Then 2-methylbenzeneboronic acid (0.21 g, 1.55 mmol) was added,Pinacol-H2O (0.22 g, 1.86 mmol),The resulting mixture was heated to reflux for two hours.After the reaction,The mixture was washed with water (30 mL x 3)Unreacted pinacol and phenylboronic acid were removed,The separated organic phase was then evaporated under reduced pressure to remove the toluene solvent.The resulting crude product was dissolved with dichloromethane (50 mL)After washing again (30 mL)To the resulting organic phase, anhydrous sodium sulfate was added for drying,The dried solution was evaporated under reduced pressure to give 0.32 g of crude product.The resulting crude product (0.32 g, 1.47 mmol)NBS (N-bromosuccinimide, 0.39 g, 2.2 mmol),AIBN (azobisisobutyronitrile, 0.003 g, 0.018 mmol) dissolved in acetonitrile (10 mL).The resulting reaction solution was refluxed at 90 ° C for two hours.After cooling at room temperature,The solvent was distilled off under reduced pressure,Crude product.The resulting crude product was purified by silica gel column chromatography,With petroleum ether (60 ~ 90 ) / ethyl acetate (v / v) = 1: 1 as eluent,The product was obtained as a white solid (0.53 g, 80percent yield).
Reference: [1] Patent: CN107383078, 2017, A, . Location in patent: Paragraph 0058; 0063; 0064; 0065; 0066; 0067; 0068
  • 40
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  • [ 377780-72-8 ]
Reference: [1] Chemistry - A European Journal, 2013, vol. 19, # 27, p. 9050 - 9058
[2] Chemical Communications, 2017, vol. 53, # 14, p. 2218 - 2221
  • 41
  • [ 76-09-5 ]
  • [ 365564-07-4 ]
YieldReaction ConditionsOperation in experiment
254 mg
Stage #1: at -5 - 20℃; for 1 h;
Stage #2: at 20℃; for 4 h;
In a reaction flask charged with Pd(OAc)2 (4.5 mg, 0.02 mmol), potassium iodide (83 mg, 0.5 mmol), and XPhos (28 mg, 0.06 mmol) under argon atmosphere was added, in this following order: anhydrous solvent (2 mL), Et3N (0.4 mL, 3 mmol), l-chloro-3,5- dimethoxybenzene (0.17 mL, 1 mmol) and diisopropylammoborane (0.3 mL, 2 mmol). The reaction was then heated at 50 °C. After total consumption of either starting material, the reaction was cooled at -5 °C, quenched with anhydrous MeOH (2 mL) and stirred for 1 h at room temperature. All volatiles were removed under vacuum before adding pinacol (153 mg, 1.3 mmol) in Et20 (2 mL), and the mixture was stirred for 4 h at room temperature. The reaction mixture was diluted with Et20 (10 mL), and the organic phase was washed first with a solution of HC1 (0.1 N, 2x10 mL), followed by an aqueous solution of CuCl2 (50g/L, 3x10 mL), dried over anhydrous Na2S04, filtered and concentrated under vacuum. The crude oil was passed through a pad of silica gel, eluting with Et20. The resulting filtrate was concentrated under vacuum to afford 2-(3,5- dimethoxyphenyl)-4,4,5,5-tetramethyl-l ,3,2-dioxaborolane (254 mg, 95percent). 1H NMR (300 MHz, CDC13) δ 7.35 (dd, IH, J 7.4, 0.9 Hz), 7.17 (t, IH, J 7.8 Hz), 6.96 (dd, IH, J 7.5, 1.0 Hz), 3.82 (s, 3H), 2.44 (s, 3H), 1.36 (s, 12H); 13C NMR (100 MHz, CDC13) δ 160.50, 1 1 1.72, 104.59, 83.96, 55.47, 24.94; nB NMR (96 MHz, CDC13) δ +30.29; MS (EI) tR = 10.527 min; m/z: 264 (M+, 100percent).
254 mg at 20℃; for 4 h; Inert atmosphere In a reaction flask charged with Pd(OAc)2 (4.5 mg, 0.02 mmol), potassium iodide (83 mg, 0.5 mmol), and XPhos (28 mg, 0.06 mmol) under argon atmosphere was added, in this following order: anhydrous solvent (2 mL), Et3N (0.4 mL, 3 mmol), 1-chloro-3,5-dimethoxybenzene (0.17 mL, 1 mmol) and diisopropylaminoborane (0.3 mL, 2 mmol).
The reaction was then heated at 50 °C.
After total consumption of either starting material, the reaction was cooled at -5 °C, quenched with anhydrous MeOH (2 mL) and stirred for 1 h at room temperature.
All volatiles were removed under vacuum before adding pinacol (153 mg, 1.3 mmol) in Et2O (2 mL), and the mixture was stirred for 4 h at room temperature.
The reaction mixture was diluted with Et2O (10 mL), and the organic phase was washed first with a solution of HCl (0.1 N, 2x10 mL), followed by an aqueous solution of CuCl2 (50g/L, 3x10 mL), dried over anhydrous Na2SO4, filtered and concentrated under vacuum.
The crude oil was passed through a pad of silica gel, eluting with Et2O.
The resulting filtrate was concentrated under vacuum to afford 2-(3,5-dimethoxyphenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (254 mg, 95percent).
1H NMR (300 MHz, CDCl3) δ 7.35 (dd, 1H, J 7.4, 0.9 Hz), 7.17 (t, 1H, J 7.8 Hz), 6.96 (dd, 1H, J 7.5, 1.0 Hz), 3.82 (s, 3H), 2.44 (s, 3H), 1.36 (s, 12H); 13C NMR (100 MHz, CDCl3) δ 160.50, 111.72, 104.59, 83.96, 55.47, 24.94; 11B NMR (96 MHz, CDCl3) δ +30.29; MS (EI) tR = 10.527 min; m/z: 264 (M+, 100percent).
Reference: [1] Chemistry - A European Journal, 2014, vol. 20, # 19, p. 5573 - 5579
[2] Patent: WO2015/82592, 2015, A2, . Location in patent: Page/Page column 92
[3] Patent: EP2881398, 2015, A1, . Location in patent: Paragraph 0281
  • 42
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  • [ 192182-54-0 ]
  • [ 365564-07-4 ]
Reference: [1] Journal of Organic Chemistry, 2018, vol. 83, # 4, p. 1842 - 1851
  • 43
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  • [ 122775-35-3 ]
  • [ 365564-10-9 ]
Reference: [1] Australian Journal of Chemistry, 2004, vol. 57, # 6, p. 537 - 548
  • 44
  • [ 76-09-5 ]
  • [ 365564-11-0 ]
YieldReaction ConditionsOperation in experiment
90% With triethylamine In dichloromethane for 3 h; Step 2: On completion of borylation Et3N (0.1 ml) and pinacol (38 mg, 3.2x10"4 mol) in CH2CI2 (0.1 ml) were added to the reaction mixture and stirred for 3 h. Volatiles were removed under vacuum and the product extracted with 3x10 ml of hexane. Removal of the solvent yielded the desired product as a colourless oil (101 mg, 90percent).1 H NMR (CDCI3) δ: 7.24 (t, J = 1 .5 Hz, 1 H), 6.82 (dd, J= 2.0, 2.5 Hz, 1 H), 6.63 (dd, J = 1 .3, 2.5 Hz, 1 H), 1 .46 (t, J = 7.6 Hz, 3 H), 1 .33 (s, 12 H), 1 .09 (d, J = 7.6 Hz, 18 H).13C NMR (CDCI3) δ: 133.7, 125.0, 1 15.6, 82.7, 24.8, 17.8, 1 1 .6. 11 B NMR δ: 30.1 (br)
Reference: [1] Patent: WO2012/25760, 2012, A1, . Location in patent: Page/Page column 35
[2] Angewandte Chemie - International Edition, 2017, vol. 56, # 13, p. 3712 - 3717[3] Angew. Chem., 2017, vol. 129, p. 3766 - 3771,6
[4] Angewandte Chemie - International Edition, 2011, vol. 50, # 9, p. 2102 - 2106
[5] Journal of the American Chemical Society, 2013, vol. 135, # 1, p. 474 - 487
[6] Heterocycles, 2017, vol. 95, # 1, p. 158 - 166
  • 45
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  • [ 87630-35-1 ]
  • [ 365564-11-0 ]
YieldReaction ConditionsOperation in experiment
90%
Stage #1: With 2,6-dimethylpyridine; aluminum (III) chloride; boron trichloride In n-heptane; dichloromethane at 20℃; for 14 h; Inert atmosphere
Stage #2: With triethylamine In n-heptane; dichloromethane at 20℃; for 0.5 h; Inert atmosphere
Example 33 - Borylation of A/-TIPS pyrrole1 equiv. BCI30.95 equiv,20 °C, 30 min[00142] An oven dried 1 L 3-necked round-bottomed flask cooled under N2, was charged with AICI3 (10.6 g, 79.3 mmol, 1 .1 equiv.). This was then suspended in CH2CI2 (288 ml_) and 2,6-lutidine (8.79 ml_, 75.7 mmol, 1 .05 equiv.) was added. To the resulting suspension was then added a solution of BCI3 (1 .0 M in heptanes, 72.1 ml_, 72.1 mmol, 1 equiv.). After 30 minutes a homogeneous yellow solution was obtained to which was added A/-TIPS pyrrole (15.3 g, 68.5 mmol, 0.95 equiv.). The reaction was stirred for 14 hours before being transferred over 45 minutes via a cannula under a positive pressure of N2 to a solution of pinacol (17 g, 144 mmol, 2.1 equiv.) in triethylamine (143 ml_, 1 .03 mol, 15 equiv.) contained in an oven dried 2 L round-bottomed flask, cooled under N2, with care taken not to allow any significant rise in reaction temperature. After washing the flask with CH2CI2 (2 x 20 ml_) the volatiles were removed in vacuo. The resulting beige solid was suspended in pentane (100 ml_) and the solids removed by filtration, upon washing with further pentane (5 χ 50 ml_) the extracts were combined and the volatiles removed in vacuo to give the crude product which was purified by chromatography on silica gel eluting with petroleum ether 40/60 then 5percent EtOAc in petroleum ether 40/60 to give, 3-(4,4,5,5- tetramethyl-1 ,3,2-dioxaborolan-2-yl)-1 -[triisopropylsilyl]-pyrrole (21 .7 g, 62.1 mmol, 90percent) as pale yellow solid (M.p. 67 - 69 <.euro.).1 H NMR (CDCI3) δ: 7.24 (t, J = 1 .5 Hz, 1 H), 6.82 (dd, J = 2.0, 2.5 Hz, 1 H), 6.63 (dd, J = 1 .3, 2.5 Hz, 1 H), 1 .46 (t, J = 7.6 Hz, 3 H), 1 .33 (s, 12 H), 1 .09 (d, J = 7.6 Hz, 18 H).13C NMR (CDCI3) δ: 133.7, 125.0, 1 15.6, 82.7, 24.8, 17.8, 1 1 .6. 11 B NMR δ: 30.1 (br)
Reference: [1] Patent: WO2012/25760, 2012, A1, . Location in patent: Page/Page column 57
  • 46
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  • [ 365564-11-0 ]
Reference: [1] Chemical Communications, 2011, vol. 47, # 46, p. 12459 - 12461
  • 47
  • [ 76-09-5 ]
  • [ 87630-35-1 ]
  • [ 365564-11-0 ]
Reference: [1] Angewandte Chemie - International Edition, 2011, vol. 50, # 9, p. 2102 - 2106
  • 48
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  • [ 87630-35-1 ]
  • [ 365564-11-0 ]
Reference: [1] Angewandte Chemie - International Edition, 2011, vol. 50, # 9, p. 2102 - 2106
  • 49
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  • [ 10294-34-5 ]
  • [ 365564-11-0 ]
Reference: [1] Chemical Communications, 2011, vol. 47, # 46, p. 12459 - 12461
  • 50
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  • [ 55718-76-8 ]
  • [ 87630-35-1 ]
  • [ 365564-11-0 ]
Reference: [1] Patent: WO2012/25760, 2012, A1, . Location in patent: Page/Page column 62-63
  • 51
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  • [ 365564-11-0 ]
Reference: [1] Angewandte Chemie - International Edition, 2011, vol. 50, # 9, p. 2102 - 2106
  • 52
  • [ 76-09-5 ]
  • [ 402503-13-3 ]
YieldReaction ConditionsOperation in experiment
79 mg at 20℃; for 1.5 h; Inert atmosphere General procedure: In a glovebox filled with nitrogen, [Ir(OMe)(cod)]2 (33.1 mg, 0.050 mmol, 0.10 equiv), ICy·HCl(26.2 mg, 0.10 mmol, 0.20 equiv), NaOt-Bu (19.2 mg, 0.20 mmol, 0.40 equiv) andmethylcyclohexane (1.0 mL) were added to a 10 mL-sample vial with a Teflon-sealed screwcap, andstirred for 5 min at room temperature. A heteroarene (0.50 mmol, 1.0 equiv) and 1g (113.1 mg, 2.0equiv) were added, and then the cap was screwed on seal the vial. The vial was stirred at 110 °C for4 h. The reaction mixture was cooled to room temperature. Pinacol (236 mg, 2.0 mmol) in THF (2.0mL) was added and the reaction mixture was stirred under N2 at room temperature for 1.5 h. Thecrude mixture was filtered through a pad of Celite and eluted with EtOAc. The filtrate wasconcentrated in vacuo and sampled for analysis by 1HNMR spectroscopy using 1,2-dichloroethaneas an internal standard. The residue was purified by flash column chromatography over silica geleluting with hexane/EtOAc. Product-containing fractions were concentrated in vacuo to give a pureborylated product.
Reference: [1] Beilstein Journal of Organic Chemistry, 2016, vol. 12, p. 654 - 661
  • 53
  • [ 76-09-5 ]
  • [ 6091-64-1 ]
  • [ 51901-85-0 ]
  • [ 7440-66-6 ]
  • [ 269409-99-6 ]
Reference: [1] Chemical Communications, 2007, # 35, p. 3667 - 3669
  • 54
  • [ 380430-53-5 ]
  • [ 76-09-5 ]
  • [ 269409-99-6 ]
Reference: [1] Chemistry - A European Journal, 2015, vol. 21, # 19, p. 7030 - 7034
[2] Chemical Communications, 2015, vol. 51, # 21, p. 4406 - 4409
  • 55
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  • [ 269409-99-6 ]
Reference: [1] Chemical Communications, 2007, # 35, p. 3667 - 3669
  • 56
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  • [ 374790-93-9 ]
Reference: [1] Journal of the American Chemical Society, 2016, vol. 138, # 30, p. 9521 - 9532
  • 57
  • [ 76-09-5 ]
  • [ 87199-16-4 ]
  • [ 380151-86-0 ]
YieldReaction ConditionsOperation in experiment
100% at 20℃; for 18 h; Inert atmosphere Stage 1. 3-(4,4, 5, 5-Tetramethyl- 1, 3,2-dioxaborolan-2-yl)benzaldehyde To a solution of 3-formyl phenylboronic acid (5 g, 33 mmol) in anhydrous THF (50 mL) was added pinacol (4.34 g, 37 mmol). The reaction mixture was allowed to stir at RT under nitrogen for 18 hrs before concentration in vacuo. The crude residue was dissolved in DCM (150 mL) and washed with water (3 x 100 mL). The organic layer was dried over MgSO4 and evaporated in vacuo to give the title compound as a yellow oil (7.73 g, 100percent).1H NMR (300 MHz, ODd3) ö ppm: 10.06 (1H, 5), 8.31 (1H, 5), 8.07 (1H, d, J=7.4 Hz),7.99 (1H, dt, J=1.5, 7.4 Hz), 7.54 (1H, t, J=7.4 Hz), 1.38 (12H, 5).
Reference: [1] Patent: WO2014/1802, 2014, A1, . Location in patent: Page/Page column 39; 40
[2] Chemical Biology and Drug Design, 2010, vol. 76, # 1, p. 17 - 24
[3] Canadian Journal of Chemistry, 2001, vol. 79, # 7, p. 1115 - 1123
[4] Canadian Journal of Chemistry, 2001, vol. 79, # 7, p. 1115 - 1123
[5] Molecules, 2013, vol. 18, # 10, p. 12346 - 12367
[6] Organic Letters, 2015, vol. 17, # 12, p. 3086 - 3089
  • 58
  • [ 53939-30-3 ]
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  • [ 444120-94-9 ]
Reference: [1] Tetrahedron, 2002, vol. 58, # 14, p. 2885 - 2890
  • 59
  • [ 76-09-5 ]
  • [ 444120-91-6 ]
  • [ 444120-94-9 ]
Reference: [1] Organic Letters, 2013, vol. 15, # 6, p. 1346 - 1349
  • 60
  • [ 16110-09-1 ]
  • [ 76-09-5 ]
  • [ 444120-94-9 ]
Reference: [1] Tetrahedron, 2002, vol. 58, # 14, p. 2885 - 2890
  • 61
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Reference: [1] Tetrahedron, 2002, vol. 58, # 14, p. 2885 - 2890
  • 62
  • [ 73583-37-6 ]
  • [ 76-09-5 ]
  • [ 458532-84-8 ]
Reference: [1] Tetrahedron, 2002, vol. 58, # 22, p. 4369 - 4373
  • 63
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  • [ 458532-96-2 ]
  • [ 458532-84-8 ]
Reference: [1] Organic Letters, 2013, vol. 15, # 6, p. 1346 - 1349
  • 64
  • [ 109-09-1 ]
  • [ 76-09-5 ]
  • [ 452972-11-1 ]
Reference: [1] Tetrahedron, 2002, vol. 58, # 17, p. 3323 - 3328
  • 65
  • [ 52200-48-3 ]
  • [ 76-09-5 ]
  • [ 452972-11-1 ]
Reference: [1] Tetrahedron, 2002, vol. 58, # 17, p. 3323 - 3328
  • 66
  • [ 76-09-5 ]
  • [ 78607-36-0 ]
  • [ 452972-11-1 ]
Reference: [1] Tetrahedron, 2002, vol. 58, # 17, p. 3323 - 3328
  • 67
  • [ 76-09-5 ]
  • [ 381248-04-0 ]
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Reference: [1] Organic Letters, 2013, vol. 15, # 6, p. 1346 - 1349
  • 68
  • [ 76-09-5 ]
  • [ 372-48-5 ]
  • [ 5419-55-6 ]
  • [ 452972-14-4 ]
YieldReaction ConditionsOperation in experiment
34%
Stage #1: With n-butyllithium; diisopropylamine In tetrahydrofuran; diethyl ether at -60℃; for 1 h; Inert atmosphere
Stage #2: at -60 - 20℃; Inert atmosphere
Stage #3: With acetic acid In tetrahydrofuran; diethyl ether at 20℃; Inert atmosphere
Step 8 : 2-fluoro-3-(4,4,5,5-tetramethyl-l ,3,2-dioxaborolan-2-yl)pyridineTo a solution of diisopropylamine (42.5 g, 0.42 mol) in THF (200 mL) was added n-BuLi (2.5 M, 175 mL) at 0°C under N2 atmosphere and the mixture was stirred for 30 hrs. 2-fluoropyridine (34.0 g, 0.35 mol) in ether (50 mL) was added under -60°C. After stirring for 1 hrs at -60°C, triisopropyl borate (82.4 g, 0.44 mol) was drop-wised and the mixture was warmed to room temperature and stirred for 2 hrs. Then pinacol (55.6 g, 0.47 mol) was added, followed by HO Ac (22.1 g, 0.37 mol) and the resulting reaction mixture was stirred at room temperature for overnight. The mixture was filtered, the filtrate was extracted with aqueous NaOH (5percent), the aqueous was neutralized with HCl (3N) to pH=6-7 and extracted with EtOAc, washed with brine, dried over Na2S04, filtered and concentrated in vacuo to afford the desired product (27.0 g, 34percent) .1H NMR (CDCI3): ? 8.31-8.29 (1H, m), 5.19-8.15 (1H, m), 7.27-7.16 (1H, m), 1.37 (12H, s)
Reference: [1] Patent: WO2013/71865, 2013, A1, . Location in patent: Page/Page column 27
  • 69
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  • [ 452972-14-4 ]
Reference: [1] Tetrahedron, 2002, vol. 58, # 17, p. 3323 - 3328
  • 70
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  • [ 174669-73-9 ]
  • [ 452972-14-4 ]
Reference: [1] Organic Letters, 2013, vol. 15, # 6, p. 1346 - 1349
  • 71
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  • [ 452972-14-4 ]
Reference: [1] Journal of Organic Chemistry, 2007, vol. 72, # 5, p. 1588 - 1594
  • 72
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  • [ 214360-62-0 ]
Reference: [1] Tetrahedron, 2002, vol. 58, # 14, p. 2885 - 2890
  • 73
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Reference: [1] Organic Letters, 2013, vol. 15, # 6, p. 1346 - 1349
  • 74
  • [ 73290-22-9 ]
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Reference: [1] Tetrahedron, 2002, vol. 58, # 14, p. 2885 - 2890
  • 75
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Reference: [1] Tetrahedron, 2002, vol. 58, # 14, p. 2885 - 2890
  • 76
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  • [ 171197-80-1 ]
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Reference: [1] Tetrahedron, 2002, vol. 58, # 14, p. 2885 - 2890
  • 77
  • [ 625-92-3 ]
  • [ 76-09-5 ]
  • [ 452972-13-3 ]
Reference: [1] Tetrahedron, 2002, vol. 58, # 17, p. 3323 - 3328
[2] Patent: WO2006/51270, 2006, A1, . Location in patent: Page/Page column 140
  • 78
  • [ 76-09-5 ]
  • [ 452972-13-3 ]
Reference: [1] Chemistry - A European Journal, 2013, vol. 19, # 7, p. 2450 - 2456
  • 79
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  • [ 459409-74-6 ]
Reference: [1] Organic Letters, 2013, vol. 15, # 18, p. 4666 - 4669
  • 80
  • [ 76-09-5 ]
  • [ 306934-95-2 ]
  • [ 459409-74-6 ]
Reference: [1] Chemistry - A European Journal, 2002, vol. 8, # 10, p. 2384 - 2396
  • 81
  • [ 76-09-5 ]
  • [ 55552-70-0 ]
  • [ 248924-59-6 ]
Reference: [1] Journal of the American Chemical Society, 2015, vol. 137, # 3, p. 1330 - 1340
  • 82
  • [ 76-09-5 ]
  • [ 476004-80-5 ]
YieldReaction ConditionsOperation in experiment
108 mg at 20℃; for 1.5 h; Inert atmosphere General procedure: In a glovebox filled with nitrogen, [Ir(OMe)(cod)]2 (33.1 mg, 0.050 mmol, 0.10 equiv), ICy·HCl(26.2 mg, 0.10 mmol, 0.20 equiv), NaOt-Bu (19.2 mg, 0.20 mmol, 0.40 equiv) andmethylcyclohexane (1.0 mL) were added to a 10 mL-sample vial with a Teflon-sealed screwcap, andstirred for 5 min at room temperature. A heteroarene (0.50 mmol, 1.0 equiv) and 1g (113.1 mg, 2.0equiv) were added, and then the cap was screwed on seal the vial. The vial was stirred at 110 °C for4 h. The reaction mixture was cooled to room temperature. Pinacol (236 mg, 2.0 mmol) in THF (2.0mL) was added and the reaction mixture was stirred under N2 at room temperature for 1.5 h. Thecrude mixture was filtered through a pad of Celite and eluted with EtOAc. The filtrate wasconcentrated in vacuo and sampled for analysis by 1HNMR spectroscopy using 1,2-dichloroethaneas an internal standard. The residue was purified by flash column chromatography over silica geleluting with hexane/EtOAc. Product-containing fractions were concentrated in vacuo to give a pureborylated product.
Reference: [1] Beilstein Journal of Organic Chemistry, 2016, vol. 12, p. 654 - 661
  • 83
  • [ 76-09-5 ]
  • [ 476004-80-5 ]
Reference: [1] Organic Letters, 2018, vol. 20, # 7, p. 1828 - 1831
  • 84
  • [ 76-09-5 ]
  • [ 162607-20-7 ]
  • [ 476004-80-5 ]
Reference: [1] Journal of Heterocyclic Chemistry, 2013, vol. 50, # 4, p. 891 - 898
  • 85
  • [ 554-14-3 ]
  • [ 76-09-5 ]
  • [ 476004-80-5 ]
Reference: [1] Angewandte Chemie - International Edition, 2011, vol. 50, # 9, p. 2102 - 2106
  • 86
  • [ 76-09-5 ]
  • [ 476004-80-5 ]
Reference: [1] Angewandte Chemie - International Edition, 2011, vol. 50, # 9, p. 2102 - 2106
  • 87
  • [ 76-09-5 ]
  • [ 59016-93-2 ]
  • [ 302348-51-2 ]
YieldReaction ConditionsOperation in experiment
92% for 22 h; Reflux A suspension of 4-(hydroxymethyl)phenylboronic acid (1.00 g, 6.6. mmol) and pinacol (0.79 g, 6.7 mmol) in tetrahydrofurane (40 mL) was refluxed over 22 h.
During this time the starting materials were completely dissolved.
The solvent was removed in vacuum (10 mbar), the residue redissolved in CH2Cl2 / EtOAc and purified by column chromatography on silica gel using the mixture of CH2Cl2 / EtOAc (9/1, v/v) as eluent.
Yield 1.4 g (92percent). Rf= 0.3 (silica, eluent - CH2Cl2 / EtOAc, 9/1, v/v).
1H NMR (200 MHz, CDCl3), δ in ppm: 1.35 (s, 12H), 4.71 (s, 2H), 7.37 (d, 2H, 3J = 8.2 Hz), 7.81 (d, 2H, 3J = 8.2 Hz).
92% for 22 h; Reflux Synthesis4-(Hvdroxymethyl)phenylboronic acid pinacol ester:A suspension of 4-(hydroxymethyl)phenylboronic acid (1.00 g, 6.6 mmol) and pinacol (0.79 g, 6.7 mmol) in tetrahydrofurane (40 ml_) was refluxed over 22 h. During this time the starting materials were completely dissolved. The solvent was removed in vacuum (10 mbar), the residue redissolved in CH2CI2 / EtOAc and purified by column chromatography on silica gel using the mixture of CH2CI2 / EtOAc (9/1 , v/v) as eluent. Yield 1.4 g (92percent). Rf= 0.3 (silica, eluent - CH2CI2 / EtOAc, 9/1 , v/v). H NMR (200 MHz, CDCI3), δ in ppm: 1.35 (s, 12H), 4.71 (s, 2H), 7.37 (d, 2H, 3J = 8.2 Hz), 7.81 (d, 2H, 3J = 8.2 Hz).
Reference: [1] Journal of the American Chemical Society, 2011, vol. 133, # 4, p. 756 - 758
[2] Journal of Medicinal Chemistry, 2012, vol. 55, # 2, p. 924 - 934
[3] Patent: EP2497775, 2012, A1, . Location in patent: Page/Page column 11
[4] Patent: WO2012/123076, 2012, A1, . Location in patent: Page/Page column 21-22
[5] Angewandte Chemie - International Edition, 2017, vol. 56, # 45, p. 14025 - 14030[6] Angew. Chem., 2017, vol. 129, p. 14213 - 14218,6
[7] Organic Letters, 2013, vol. 15, # 18, p. 4850 - 4853
[8] Angewandte Chemie - International Edition, 2017, vol. 56, # 12, p. 3206 - 3210[9] Angew. Chem., 2017, vol. 129, # 12, p. 3254 - 3258,5
[10] Angewandte Chemie - International Edition, 2017, vol. 56, # 31, p. 9155 - 9159[11] Angew. Chem., 2017, vol. 129, # 31, p. 9283 - 9287,5
[12] Organic and Biomolecular Chemistry, 2017, vol. 15, # 11, p. 2459 - 2466
[13] Analytical Chemistry, 2016, vol. 88, # 21, p. 10728 - 10735
[14] Patent: WO2017/33163, 2017, A1, . Location in patent: Page/Page column 33; 34
  • 88
  • [ 76-09-5 ]
  • [ 302348-51-2 ]
Reference: [1] Molecules, 2013, vol. 18, # 10, p. 12346 - 12367
  • 89
  • [ 76-09-5 ]
  • [ 116491-57-7 ]
  • [ 476004-81-6 ]
Reference: [1] Organic Letters, 2005, vol. 7, # 13, p. 2523 - 2526
  • 90
  • [ 3141-27-3 ]
  • [ 76-09-5 ]
  • [ 688-74-4 ]
  • [ 175361-81-6 ]
YieldReaction ConditionsOperation in experiment
75%
Stage #1: With n-butyllithium In tetrahydrofuran; hexane at -78℃; for 1 h;
Stage #2: at -78 - 20℃; for 2 h;
Stage #3: With acetic acid In tetrahydrofuran; hexane at 20℃; for 14 h;
To a solution of 2,5-dibromothiophene (2.0 g, 8.3 mmol) in dry THF (40) was addedn-BuLi (15 mL, 1.6 M solution in hexane, 25 mmol) dropwise at -78 °C and the mixturewas stirred for 1 h at the same temperature. Tributylborate (6.4 mL, 25 mmol) wasadded to the reaction mixture at -78 °C and the mixture was gradually warmed to roomtemperature. After stirred for additional 2 h, pinacol (3.8 g, 33 mmol) and acetic acid(1.4 mL, 25 mmol) were added to the mixture and the resulting mixture was stirred atambient temperature for 14 h. The solution was filtered through a celite pad and thefiltrate was evaporated in vacuo. The residue (a brown soild) was purified byrecrystallization from ethyl acetate and hexane solution to give the titled compound (2.0g, 75percent) as a white solid
Reference: [1] Chem, 2016, vol. 1, # 1, p. 91 - 101
  • 91
  • [ 188290-36-0 ]
  • [ 76-09-5 ]
  • [ 22092-92-8 ]
  • [ 193978-23-3 ]
  • [ 175361-81-6 ]
YieldReaction ConditionsOperation in experiment
39%
Stage #1: With (1,5-cyclooctadiene)(methoxy)iridium(I) dimer; 1,3-dicyclohexyl-1H-imidazol-3-ium chloride; sodium t-butanolate In methyl cyclohexane at 110℃; for 4 h; Glovebox; Inert atmosphere
Stage #2: at 20℃; for 1.5 h; Inert atmosphere
General procedure: In a glovebox filled with nitrogen, [Ir(OMe)(cod)]2 (33.1 mg, 0.050 mmol, 0.10 equiv), ICy·HCl(26.2 mg, 0.10 mmol, 0.20 equiv), NaOt-Bu (19.2 mg, 0.20 mmol, 0.40 equiv) andmethylcyclohexane (1.0 mL) were added to a 10 mL-sample vial with a Teflon-sealed screwcap, andstirred for 5 min at room temperature. A heteroarene (0.50 mmol, 1.0 equiv) and 1g (113.1 mg, 2.0equiv) were added, and then the cap was screwed on seal the vial. The vial was stirred at 110 °C for4 h. The reaction mixture was cooled to room temperature. Pinacol (236 mg, 2.0 mmol) in THF (2.0mL) was added and the reaction mixture was stirred under N2 at room temperature for 1.5 h. Thecrude mixture was filtered through a pad of Celite and eluted with EtOAc. The filtrate wasconcentrated in vacuo and sampled for analysis by 1HNMR spectroscopy using 1,2-dichloroethaneas an internal standard. The residue was purified by flash column chromatography over silica geleluting with hexane/EtOAc. Product-containing fractions were concentrated in vacuo to give a pureborylated product.
Reference: [1] Beilstein Journal of Organic Chemistry, 2016, vol. 12, p. 654 - 661
  • 92
  • [ 76-09-5 ]
  • [ 175361-81-6 ]
YieldReaction ConditionsOperation in experiment
236 mg
Stage #1: at -5 - 20℃; for 1 h;
Stage #2: at 20℃; for 4 h;
In a reaction flask charged with Pd(OAc)2 (4.5 mg, 0.02 mmol), potassium iodide (83 mg, 0.5 mmol), and XPhos (28 mg, 0.06 mmol) under argon atmosphere was added, in this following order: anhydrous solvent (2 mL), Et3N (0.4 mL, 3 mmol), 2,5-dichlorothiophene (0.11 mL, 1 mmol) and diisopropylaminoborane (0.6 mL, 4 mmol). The reaction was then heated at 50 °C. After total consumption of either starting material, the reaction was cooled at -5 °C, quenched with anhydrous MeOH (2 mL) and stirred for 1 h at room temperature. All volatiles were removed under vacuum before adding pinacol (306 mg, 2.6 mmol) in Et20 (4 mL), and the mixture was stirred for 4 h at room temperature. The reaction mixture was diluted with Et20 (10 mL), and the organic phase was washed first with a solution of HC1 (0.1 N, 2x10 mL), followed by an aqueous solution of CuCl2 (50g/L, 3x10 mL), dried over anhydrous Na2S04, filtered and concentrated under vacuum. The crude oil was passed through a pad of silica gel, eluting with Et20. The resulting filtrate was concentrated under vacuum to afford 2,5-bis(4,4,5,5-tetramethyl-l,3,2-dioxaborolan-2-yl)thiophene (236 mg, 70percent). 1H NMR (300 MHz, CDC13) δ 7.67 (s, 2H), 1.34 (s, 24H); 13C NMR (100 MHz, CDC13) δ 137.80, 84.25, 24.89; nB NMR (96 MHz, CDC13) δ +29.49; MS (EI) tR = 13.150 min; m/z: 336 (M+, 100percent).
236 mg at 20℃; for 4 h; Inert atmosphere In a reaction flask charged with Pd(OAc)2 (4.5 mg, 0.02 mmol), potassium iodide (83 mg, 0.5 mmol), and XPhos (28 mg, 0.06 mmol) under argon atmosphere was added, in this following order: anhydrous solvent (2 mL), Et3N (0.4 mL, 3 mmol), 2,5-dichlorothiophene (0.11 mL, 1 mmol) and diisopropylaminoborane (0.6 mL, 4 mmol).
The reaction was then heated at 50 °C.
After total consumption of either starting material, the reaction was cooled at -5 °C, quenched with anhydrous MeOH (2 mL) and stirred for 1 h at room temperature.
All volatiles were removed under vacuum before adding pinacol (306 mg, 2.6 mmol) in Et2O (4 mL), and the mixture was stirred for 4 h at room temperature.
The reaction mixture was diluted with Et2O (10 mL), and the organic phase was washed first with a solution of HCl (0.1 N, 2x10 mL), followed by an aqueous solution of CuCl2 (50g/L, 3x10 mL), dried over anhydrous Na2SO4, filtered and concentrated under vacuum.
The crude oil was passed through a pad of silica gel, eluting with Et2O.
The resulting filtrate was concentrated under vacuum to afford 2,5-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)thiophene (236 mg, 70percent).
1H NMR (300 MHz, CDCl3) δ 7.67 (s, 2H), 1.34 (s, 24H); 13C NMR (100 MHz, CDCl3) δ 137.80, 84.25, 24.89; 11B NMR (96 MHz, CDCl3) δ +29.49; MS (EI) tR = 13.150 min; m/z: 336 (M+, 100percent).
Reference: [1] Chemistry - A European Journal, 2014, vol. 20, # 19, p. 5573 - 5579
[2] Patent: WO2015/82592, 2015, A2, . Location in patent: Page/Page column 98; 99
[3] Patent: EP2881398, 2015, A1, . Location in patent: Paragraph 0299; 0300
  • 93
  • [ 76-09-5 ]
  • [ 26076-46-0 ]
  • [ 175361-81-6 ]
Reference: [1] Macromolecules, 2005, vol. 38, # 4, p. 1114 - 1122
  • 94
  • [ 76-09-5 ]
  • [ 364794-79-6 ]
Reference: [1] Organic Letters, 2013, vol. 15, # 18, p. 4850 - 4853
  • 95
  • [ 76-09-5 ]
  • [ 364794-80-9 ]
Reference: [1] Organic Letters, 2013, vol. 15, # 18, p. 4850 - 4853
  • 96
  • [ 76-09-5 ]
  • [ 214360-58-4 ]
YieldReaction ConditionsOperation in experiment
70% With montmorillonite K10 In tetrahydrofuran at 25℃; Molecular sieve General procedure: In a flask containing the appropriate boronic acid 1a-m (0.25 mmol) in tetrahydrofuran (THF; 3 mL) was added montmorillonite K10 (150percent m/m) followed by pinacol(30 mg, 0.25 mmol). The mixture was stirred for 15 minto homogenize the contents, and powdered 4 Å molecularsieves (150percent m/m) were added. The mixture was then stirredat room temperature for the time indicated in Scheme 2.After this period, the mixture was extracted with EtOAc(3 × 10 mL) and the organic phase was washed with water(2 × 15 mL). The organic phase was dried over anhydrousMgSO4, filtered and the solvent was removed in vacuo.
Reference: [1] Journal of the Brazilian Chemical Society, 2018, vol. 29, # 9, p. 1777 - 1785
  • 97
  • [ 76-09-5 ]
  • [ 22092-92-8 ]
  • [ 459-45-0 ]
  • [ 214360-58-4 ]
YieldReaction ConditionsOperation in experiment
61%
Stage #1: With ferrocene In acetonitrile at 20℃; for 2.5 h;
Stage #2: With methanol In acetonitrile at 0 - 20℃; for 1 h;
Stage #3: at 20℃; for 4 h;
Example 3: General procedure D for the synthesis of the arylpinacolboronates by arylation of diisopropylaminoborane, catalysed by ferrocene (1percent), followed by methanolysis and transesterification In a dried tube reactor under argon as described in example 2, the arenediazonium salt (1 mmol) and the ferrocene (ΙΟμιηοΙ, 1.8mg) were dissolved in 2mL of anhydrous CH3CN. Diisopropylaminoborane (2mmol, 226mg) was then added to the solution and the mixture was stirred for 2h30 at room temperature. The reaction mixture was quenched by a slow addition of anhydrous MeOH at 0°C (2mL) and stirred for an additional hour at room temperature. After removal of all the volatiles, 1.3eq of pinacol was added in Et20 (2mL), the mixture was stirred 4h at room temperature. The crude mixture was washed with a 50g/L CuCl2 solution (2 x 5mL). The organic layer were separated, dried over Na2S04, filtered and concentrated to dryness. The resulted oil was dissolved with CH2C12 and filtered of a pad of silica gel, eluting with CH2C12 to afford the corresponding boronate. Example 17: synthesis of 2-(4-fluorophenyr)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane [CAS 214360-58-4], compound VIA14. 135 mg of 2-(3-iodophenyl)-4,4,5,5-tetramethyl-l,3,2-dioxaborolane were obtained following the general procedure D according to example 3, using 210 mg of 4-fluorobenzenediazonium tetrafluoroborate as a pale yellow oil, with an isolated yield of 61percent. 1H NMR (300 MHz, CDC13) δ 7.80 (dd, J = 8.6, 6.3 Hz, 1H), 7.09 - 6.99 (m, 1H), 1.34 (s, 12H) nB NMR (100 MHz, CDC13) δ 30.26 13C NMR (75 MHz, CDC13) δ 166.91, 163.59, 137.18, 137.07, 115.11, 114.84, 84.05, 25.01. MS (EI) tR= 7.07min; m/z: 222 (Μ+', 100percent)
Reference: [1] Patent: WO2014/9169, 2014, A1, . Location in patent: Page/Page column 60
  • 98
  • [ 76-09-5 ]
  • [ 214360-58-4 ]
YieldReaction ConditionsOperation in experiment
219 mg
Stage #1: at -5 - 20℃; for 1 h;
Stage #2: at 20℃; for 4 h;
In a reaction flask charged with Pd(OAc)2 (4.5 mg, 0.02 mmol), potassium iodide (3.3 mg, 0.02 mmol), and XPhos (28 mg, 0.06 mmol) under argon atmosphere was added, in this following order: anhydrous solvent (2 mL), Et3N (0.4 mL, 3 mmol), l-chloro-4- fluorobenzene (0.16 mL, 1 mmol) and diisopropylaminoborane (0.3 mL, 2 mmol). The reaction was then heated at 50 °C. After total consumption of either starting material, the reaction was cooled at -5 °C, quenched with anhydrous MeOH (2 mL) and stirred for 1 h at room temperature. All volatiles were removed under vacuum before adding pinacol (153 mg, 1.3 mmol) in Et20 (2 mL), and the mixture was stirred for 4 h at room temperature. The reaction mixture was diluted with Et20 (10 mL), and the organic phase was washed first with a solution of HC1 (0.1 N, 2x10 mL), followed by an aqueous solution of CuCl2 (50g/L, 3x10 mL), dried over anhydrous Na2S04, filtered and concentrated under vacuum. The crude oil was passed through a pad of silica gel, eluting with Et20. The resulting filtrate was concentrated under vacuum to afford 2-(4- fluorophenyl)-4,4,5,5-tetramethyl-l,3,2-dioxaborolane (219 mg, 99percent). 1H NMR (300 MHz, CDCls) δ 7.85-7.82 (m, 2H), 7.10-7.06 (m, 2H), 1,39 (s, 12H); 13C NMR (100 MHz, CDCI3) 5 166.19, 164.07, 137.24, 115.33, 83.88, 25.05; nB NMR (96 MHz, CDCI3) δ +30.62; 19F NMR (96 MHz, CDC13) δ -109.65; MS (EI) tR = 7.049 min; m/z: 222 (M+, 100percent).
Reference: [1] Advanced Synthesis and Catalysis, 2013, vol. 355, # 6, p. 1083 - 1088
[2] Chemistry - A European Journal, 2014, vol. 20, # 19, p. 5573 - 5579
[3] Patent: WO2015/82592, 2015, A2, . Location in patent: Page/Page column 89; 90
  • 99
  • [ 76-09-5 ]
  • [ 1765-93-1 ]
  • [ 214360-58-4 ]
Reference: [1] Advanced Synthesis and Catalysis, 2013, vol. 355, # 18, p. 3553 - 3557
[2] Chemical Communications, 2015, vol. 51, # 21, p. 4406 - 4409
[3] Angewandte Chemie - International Edition, 2012, vol. 51, # 37, p. 9385 - 9388
[4] Journal of Organic Chemistry, 2014, vol. 79, # 21, p. 10568 - 10580
[5] Bulletin of the Chemical Society of Japan, 2009, vol. 82, # 7, p. 870 - 878
[6] Journal of the American Chemical Society, 2013, vol. 135, # 7, p. 2552 - 2559
[7] Organic Letters, 2018, vol. 20, # 20, p. 6573 - 6577
  • 100
  • [ 76-09-5 ]
  • [ 214360-58-4 ]
YieldReaction ConditionsOperation in experiment
219 mg at 20℃; for 4 h; Inert atmosphere In a reaction flask charged with Pd(OAc)2 (4.5 mg, 0.02 mmol), potassium iodide (3.3 mg, 0.02 mmol), and XPhos (28 mg, 0.06 mmol) under argon atmosphere was added, in this following order: anhydrous solvent (2 mL), Et3N (0.4 mL, 3 mmol), 1-chloro-4-fluorobenzene (0.16 mL, 1 mmol) and diisopropylaminoborane (0.3 mL, 2 mmol).
The reaction was then heated at 50 °C.
After total consumption of either starting material, the reaction was cooled at -5 °C, quenched with anhydrous MeOH (2 mL) and stirred for 1 h at room temperature.
All volatiles were removed under vacuum before adding pinacol (153 mg, 1.3 mmol) in Et2O (2 mL), and the mixture was stirred for 4 h at room temperature.
The reaction mixture was diluted with Et2O (10 mL), and the organic phase was washed first with a solution of HCl (0.1 N, 2x10 mL), followed by an aqueous solution of CuCl2 (50g/L, 3x10 mL), dried over anhydrous Na2SO4 filtered and concentrated under vacuum.
The crude oil was passed through a pad of silica gel, eluting with Et2O.
The resulting filtrate was concentrated under vacuum to afford 2-(4-fluorophenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (219 mg, 99percent).
1H NMR (300 MHz, CDCl3) δ 7.85-7.82 (m, 2H), 7.10-7.06 (m, 2H), 1,39 (s, 12H); 13C NMR (100 MHz, CDCl3) δ 166.19, 164.07, 137.24, 115.33, 83.88, 25.05; 11B NMR (96 MHz, CDCl3) δ +30.62; 19F NMR (96 MHz, CDCl3) δ -109.65; MS (EI) tR = 7.049 min; m/z: 222 (M+, 100percent).
Reference: [1] Tetrahedron Letters, 2014, vol. 55, # 10, p. 1702 - 1705
[2] Patent: EP2881398, 2015, A1, . Location in patent: Paragraph 0275
  • 101
  • [ 76-09-5 ]
  • [ 31685-21-9 ]
  • [ 214360-58-4 ]
Reference: [1] Chemical Communications, 2015, vol. 51, # 14, p. 2878 - 2881
  • 102
  • [ 76-09-5 ]
  • [ 1321604-73-2 ]
  • [ 1321604-76-5 ]
  • [ 214360-58-4 ]
Reference: [1] Chemistry - A European Journal, 2011, vol. 17, # 29, p. 8005 - 8008
  • 103
  • [ 76-09-5 ]
  • [ 448-59-9 ]
  • [ 214360-58-4 ]
Reference: [1] Journal of the American Chemical Society, 2011, vol. 133, # 7, p. 2116 - 2119
  • 104
  • [ 76-09-5 ]
  • [ 338998-93-9 ]
YieldReaction ConditionsOperation in experiment
71 mg at 20℃; for 1.5 h; Inert atmosphere General procedure: In a glovebox filled with nitrogen, [Ir(OMe)(cod)]2 (33.1 mg, 0.050 mmol, 0.10 equiv), ICy·HCl(26.2 mg, 0.10 mmol, 0.20 equiv), NaOt-Bu (19.2 mg, 0.20 mmol, 0.40 equiv) andmethylcyclohexane (1.0 mL) were added to a 10 mL-sample vial with a Teflon-sealed screwcap, andstirred for 5 min at room temperature. A heteroarene (0.50 mmol, 1.0 equiv) and 1g (113.1 mg, 2.0equiv) were added, and then the cap was screwed on seal the vial. The vial was stirred at 110 °C for4 h. The reaction mixture was cooled to room temperature. Pinacol (236 mg, 2.0 mmol) in THF (2.0mL) was added and the reaction mixture was stirred under N2 at room temperature for 1.5 h. Thecrude mixture was filtered through a pad of Celite and eluted with EtOAc. The filtrate wasconcentrated in vacuo and sampled for analysis by 1HNMR spectroscopy using 1,2-dichloroethaneas an internal standard. The residue was purified by flash column chromatography over silica geleluting with hexane/EtOAc. Product-containing fractions were concentrated in vacuo to give a pureborylated product.
Reference: [1] Beilstein Journal of Organic Chemistry, 2016, vol. 12, p. 654 - 661
  • 105
  • [ 76-09-5 ]
  • [ 89466-08-0 ]
  • [ 269409-97-4 ]
Reference: [1] Angewandte Chemie - International Edition, 2013, vol. 52, # 37, p. 9755 - 9758
[2] Organic Letters, 2013, vol. 15, # 11, p. 2806 - 2809
[3] Advanced Synthesis and Catalysis, 2015, vol. 357, # 10, p. 2287 - 2300
[4] Synthesis (Germany), 2016, vol. 48, # 19, p. 3155 - 3164
[5] Journal of Organic Chemistry, 2018, vol. 83, # 4, p. 1842 - 1851
  • 106
  • [ 76-09-5 ]
  • [ 10294-34-5 ]
  • [ 269409-97-4 ]
Reference: [1] Journal of the American Chemical Society, 2016, vol. 138, # 25, p. 7982 - 7991
  • 107
  • [ 76-09-5 ]
  • [ 408492-27-3 ]
YieldReaction ConditionsOperation in experiment
71% at 80 - 90℃; The reaction liquid was cooled to 0 ° C, filtered, and the solvent was evaporated to dryness, and then sulfolane was added, and the intermediate was rectified to obtain 2,6-dichloropyridine-4-(ditetrahydropyrrolyl)borate in a yield of 78percent.After heating and melting the pinacol (18.4 g, 0.16 mol), the temperature was 80-90 ° C, and the mixture was dropped into the above intermediate.During the dropwise addition, the tetrahydropyrrole formed was separated and completely exchanged. After cooling, the ethanol and n-heptane mixed solvent were beaten to obtain 38.9 g of a pale yellow solid, and the yield was 71percent.
Reference: [1] Patent: CN107987097, 2018, A, . Location in patent: Paragraph 0016; 0019; 0023; 0027
  • 108
  • [ 76-09-5 ]
  • [ 380430-49-9 ]
  • [ 330793-01-6 ]
YieldReaction ConditionsOperation in experiment
99% With 1H-imidazole; iron(III) chloride In water; acetonitrile at 20℃; for 0.5 h; Inert atmosphere General procedure: To a solution of aryl boronic acid (1 mmol) in MeCN (4 mL) was added, sequentially, asolution of FeCl3 (8 mg, 0.05 mmol, 5 molpercent) in H2O (1 mL), imidazole (204 mg, 3 mmol)and pinacol (118 mg, 1 mmol). The resulting cloudy orange mixture was stirred at roomtemperature for 30 min. The reaction was then diluted with H2O (5 mL) and extracted withEt2O (3 x 8 mL). The combined organic extracts were dried (Na2SO4) and concentrated invacuo. The resulting oil was then purified by a filtration through a silica gel plug (eluting withEt2O), affording the title compound.
Reference: [1] Synlett, 2014, vol. 25, # 4, p. 551 - 555
  • 109
  • [ 76-09-5 ]
  • [ 144104-59-6 ]
  • [ 269410-24-4 ]
Reference: [1] Patent: WO2015/106292, 2015, A1, . Location in patent: Paragraph 00729; 00740; 00741
  • 110
  • [ 76-09-5 ]
  • [ 87199-18-6 ]
  • [ 214360-76-6 ]
YieldReaction ConditionsOperation in experiment
94% at 20℃; for 48 h; To a 500 mL three-necked flask, 3-hydroxyphenylboronic acid (10.0 g, 72.46 mmol, 1.0 eq) and methylene chloride (300 mL) were added, and pinacol (10.0 g, 84.60 mmol, 1.2 eq) was added under stirring, followed by stirring at room temperature for 48 h. The reaction solution was poured into water (400 mL). The mixed solution was poured into a separatory funnel. The organic phase was separated and the aqueous phase was extracted twice with dichloromethane (400 mL). The combined organic phases were dried over anhydrous sodium sulfate and filtered. The crude product was purified by column chromatography (200-300 mesh silica gel, methylene chloride/methanol mixed solvent at a volume ratio of 100/1 as eluent) to obtain 15.0 g of a white solid with a yield of 94percent and a purity of 97percent.
Reference: [1] Patent: CN107188901, 2017, A, . Location in patent: Paragraph 0035; 0036
[2] Organic Letters, 2010, vol. 12, # 23, p. 5474 - 5477
  • 111
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  • [ 170230-88-3 ]
  • [ 515131-35-8 ]
Reference: [1] Angewandte Chemie - International Edition, 2016, vol. 55, # 12, p. 3909 - 3913[2] Angew. Chem., 2016, p. 3977 - 3981,5
  • 112
  • [ 76-09-5 ]
  • [ 126689-01-8 ]
YieldReaction ConditionsOperation in experiment
91% for 1 h; Inert atmosphere; Reflux Under nitrogen protection, the product obtained in the above Example 3 was dissolved in 70 ml of tetrahydrofuran. Warming up to reflux, Gradually add dropwise pinacol (0.85 mol) A solution of tetrahydrofuran. Keep the solution weakly refluxed throughout the process. During the dropwise addition, tetrahydropyrrole is gradually formed. After the addition is completed, The reaction was stirred for 1 hour under reflux conditions. The GC detected the reaction of the starting material. After the temperature was lowered, the solvent and tetrahydropyrrole were distilled off under reduced pressure, and then the mixture was subjected to temperature distillation to obtain 12.4 g of a colorless, transparent liquid, cyclopropanol boronic acid ester, yield 91percent, GC: 99.2percent, H NMR structure.
Reference: [1] Patent: CN104876956, 2018, B, . Location in patent: Paragraph 0036-0038
  • 113
  • [ 76-09-5 ]
  • [ 1065010-87-8 ]
  • [ 126689-01-8 ]
Reference: [1] Journal of Organic Chemistry, 2015, vol. 80, # 11, p. 5428 - 5435
  • 114
  • [ 76-09-5 ]
  • [ 220587-29-1 ]
  • [ 216439-76-8 ]
Reference: [1] Patent: US2011/124865, 2011, A1, . Location in patent: Page/Page column 4; 5
  • 115
  • [ 76-09-5 ]
  • [ 218301-87-2 ]
  • [ 262444-42-8 ]
YieldReaction ConditionsOperation in experiment
81% at 20℃; for 1 h; Step 3 15 g of the boronic acid from step 2 (59 mmol) and 14 g pinacol (118 mmol) were stirred in MeOH at rt for 1 h. TLC indicated complete conversion, water (45 mL) was added to the reaction mixture, and the precipitated oil started crystallizing after trituration. The precipitate was filtered, washed with 70percent MeOH, and dried (16 g, 48 mmol, yield: 81percent). 1H-NMR (DMSO, 300 MHz): 9.11 (s, 1 H); 7.73 (t, 1 H); 7.38 (d, 1 H); 7.28 (d, 1 H); 1.43 (s, 9 H); 1.25 (s, 12 H).
81% at 20℃; for 1 h; Step 3 15 g of the boronic acid from step 2 (59 mmol) and 14 g pinacol (118 mmol) were stirred in MeOH at rt for 1 h. TLC indicated complete conversion, water (45 ml_) was added to the reaction mixture, and the precipitated oil started crystallizing after trituration. The precipitate was filtered, washed with 70percent MeOH, and dried (16 g, 48 mmol, yield: 81percent).1H-NMR (DMSO, 300 MHz): 9.11 (s, 1 H); 7.73 (t, 1 H); 7.38 (d, 1 H); 7.28 (d, 1 H); 1.43 (s, 9 H); 1.25 (s, 12 H).
Reference: [1] Patent: EP1878726, 2008, A1, . Location in patent: Page/Page column 38
[2] Patent: WO2007/147574, 2007, A1, . Location in patent: Page/Page column 56
  • 116
  • [ 76-09-5 ]
  • [ 501945-71-7 ]
Reference: [1] Advanced Synthesis and Catalysis, 2015, vol. 357, # 6, p. 1167 - 1174
  • 117
  • [ 76-09-5 ]
  • [ 121-43-7 ]
  • [ 1072850-89-5 ]
  • [ 402960-38-7 ]
YieldReaction ConditionsOperation in experiment
74%
Stage #1: With n-butyllithium In tetrahydrofuran; hexane at -78℃; for 1 h;
Stage #2: at -85℃; for 1 h;
A mixture of 212.3 g (1.22 mole) 5-bromo-pyrimidin-2-ylamin, 211.8 g (1.16 mole) benzophenone and 11.1 g (58.2 mmole) p-toluenesulfonic acid in 1000 g toluene is heated to boiling for 24 h under reflux, whereby the generated water is removed. Eventually obtained solid substance is filtered, the filtrate is distillatively freed from toluene. Crystallization of the residue is initiated by slow addition of methanol in the cold. The crystals are sucked off, washed with toluene and dried under vacuum. The thereby prepared solid is the protected amine benzhydryliden-(5-bromo-pyrimidin-2-yl)-amine.Yield: 286.5 g (0.847 mole, 73percent).25.0 g (73.9 mmole) benzhydryliden-(5-bromo-pyrimidin-2-yl)-amine are dissolved in 185 g dry THF and cooled to -78° C. At this temperature 22.1 g (81.3 mmole) of 2.5 M n-butyllithium solution in hexane is slowly added. The mixture is continually stirred for 60 min and then cooled to -85° C. 9.25 g (88.7 mmole) of trimethylborate are slowly added. The mixture is again stirred for 60 min, then left to warm up to -10° C. and then poured into a prepared solution of 12.0 g of 96percent sulphuric acid in 166 g water covered with a layer of 65 g toluene. The mixture is intensively stirred for one hour. After completion of phase separation the aqueous phase is covered with a layer of 249 g of fresh toluene and 10.5 9 (88.7 mmole) pinacol are added. By adding 68.9 g of 10percent sodium hydroxide solution a pH-value of about 8.5 is set. The mixture is stirred intensely for 12 h, then again phase separation takes place. From the organic phase the bulk of the solvent is removed at 100-150 mbar. The residue is cooled to -5° C. The thereby obtained solid substance is sucked off, washed and dried under vacuum. Thus, colorless crystals of (2-aminopyrimidin-5-yl)-boronic acid pinacol ester are obtained.Yield: 12.1 g (54.7 mmole, 74percent).Yield over all steps: 54percent.
Reference: [1] Patent: US2008/269523, 2008, A1, . Location in patent: Page/Page column 7
  • 118
  • [ 76-09-5 ]
  • [ 121-43-7 ]
  • [ 226713-38-8 ]
  • [ 461699-81-0 ]
YieldReaction ConditionsOperation in experiment
69%
Stage #1: With n-butyllithium In tetrahydrofuran; hexane at -78℃; for 1 h;
Stage #2: at -85℃; for 1 h;
A mixture of 246.6 g (1.22 mole) 4-bromo-2-methoxyaniline, 211.8 g (1.16 mole) benzophenone and 11.1 g (58.2 mmole) p-toluenesulfonic acid in 1000 g toluene is heated to boiling for 24 h under reflux, whereby the generated water is removed. Eventually obtained solid substance is filtered, the filtrate is distillatively freed from toluene. The crystallization of the residue is initiated by slow addition of methanol in the cold. The crystals are sucked off, washed with toluene and dried under vacuum. The thereby prepared solid is the protected amine benzhydryliden-(4-bromo-2-methoxyphenyl)-amine.Yield: 305.9 g (0.835 mole, 72percent).25.0 g (68.3 mmole) benzhydryliden-(4-bromo-2-methoxyphenyl)-amine are dissolved in 170 g dry THE and cooled to -78° C. At this temperature 20.4 g (75.1 mmole) of 2.5 M n-butyllithium solution in hexane is slowly added. The mixture is continually stirred for 60 min and then cooled to -85° C. 8.55 g (82.0 mmole) of trimethylborate are slowly added. The mixture is again stirred for 60 min, then left to warm up to -10° C. and then poured into a prepared solution of 11.1 g of 96percent sulphuric acid in 153 g water covered with a layer of 60 g toluene. The mixture is intensely stirred for one hour. After completion of phase separation the aqueous phase is covered with a layer of 230 g of fresh toluene and 9.69 g (82.0 mmole) pinacol are added. By adding 63.7 g of 10percent sodium hydroxide solution a pH-value of about 8.5 is set. The mixture is stirred intensely for 12 h, then again phase separation takes place. From the organic phase the bulk of the solvent is removed at 100-150 mbar. The residue is cooled to -5° C. The thereby obtained solid substance is sucked off, washed and dried under vacuum. Thus, colorless crystals of 4-aminophenylboronic acid pinacol ester are obtained.Yield: 11.7 g (47.1 mmole, 69percent).Yield over all steps: 50percent.
Reference: [1] Patent: US2008/269523, 2008, A1, . Location in patent: Page/Page column 6
  • 119
  • [ 76-09-5 ]
  • [ 179117-44-3 ]
Reference: [1] Tetrahedron Letters, 2013, vol. 54, # 2, p. 166 - 169
  • 120
  • [ 76-09-5 ]
  • [ 25487-66-5 ]
  • [ 269409-73-6 ]
YieldReaction ConditionsOperation in experiment
91% for 4 h; General procedure: The boronic acids 26 and 27 (0.667 mmol) were dissolved in 6 mL of ethyl acetate and, stirring the solution, pinacol (0.667 mmol) was added. After 4 h the reaction was stopped adding anhydrous Na2SO4 (1 g) and CaCl2 (1 g). The mixture was filtered and concentrated in vacuo (Yields: 91percent of 28 and 89percent of 29).
Reference: [1] European Journal of Medicinal Chemistry, 2012, vol. 54, p. 311 - 323
[2] Journal of Organic Chemistry, 2014, vol. 79, # 21, p. 10568 - 10580
[3] Bioorganic and Medicinal Chemistry, 2012, vol. 20, # 16, p. 5012 - 5016
  • 121
  • [ 76-09-5 ]
  • [ 214360-57-3 ]
Reference: [1] Patent: US6639107, 2003, B1,
  • 122
  • [ 76-09-5 ]
  • [ 269410-26-6 ]
Reference: [1] Tetrahedron Letters, 2013, vol. 54, # 2, p. 166 - 169
  • 123
  • [ 76-09-5 ]
  • [ 51067-38-0 ]
  • [ 269410-26-6 ]
Reference: [1] Bulletin of the Chemical Society of Japan, 2009, vol. 82, # 7, p. 870 - 878
  • 124
  • [ 50720-12-2 ]
  • [ 76-09-5 ]
  • [ 445264-60-8 ]
Reference: [1] Chemical Communications, 2011, vol. 47, # 30, p. 8605 - 8607
  • 125
  • [ 76-09-5 ]
  • [ 405520-68-5 ]
  • [ 400727-57-3 ]
Reference: [1] Journal of the American Chemical Society, 2013, vol. 135, # 7, p. 2552 - 2559
[2] Organic Letters, 2015, vol. 17, # 12, p. 3086 - 3089
  • 126
  • [ 76-09-5 ]
  • [ 1003845-06-4 ]
  • [ 1003845-08-6 ]
YieldReaction ConditionsOperation in experiment
100% With magnesium sulfate In toluene at 20℃; for 15 h; 34). Synthesis of 2-chloro-5-(4,4,5,5-tetramethyl-[1,3,2]dioxaborolan-2-yl)-pyrimidine; To a solution of 5-bromo-2-chloro-pyrimidine (10 mmol, 1.93 g) and triisopropyl borate (12 mmol, 2.8 ml.) in toluene (16 ml) and THF (4 mi_) is added n-buty. lithium \\r, hexane (1.58 M, 12 mmol, 7.6 mL) dropwise at -78 0C over 45 min and stirred at -78 0C for 1 hour. The mixture is warmed to -20 0C, then added aq. hydrogen chloride (1M, 20 mL). The mixture is warmed to room temperature. The precipitate is collected and washed with hexane to give a colorless powder (808 mg, 51percent). A mixture of the powder (3.63 mmol, 575 mg), pinacol (3.81 mmol, 450 mg) and MgSO4 (18.15 mmol, 2.2 g) in toluene (10 mL) is <n="192"/>stirred at room temperature for 15 hour. The mixture is filtrated and the solution is concentrated under reduced pressure. The resultant solid is washed with water to give 2- chloro-5-(4,4,5,5-tetramethyl-[1 ,3,2]dioxaborolan-2-yl)-pyrimidine (875 mg, quant); ESI-MS m/z: 159 [M+1-pinacol]\\ Retention time 1.75 min (condition A).
100% With magnesium sulfate In toluene at 20℃; for 15 h; Example 14; 1)
Synthesis of 2-chloro-5-(4,4,5,5-tetramethyl-[1,3,2]dioxaborolan-2-yl)-pyrimidine
To a solution of 5-bromo-2-chloro-pyrimidine (10 mmol, 1.93 g) and triisopropyl borate (12 mmol, 2.8 mL) in toluene (16 mL) and THF (4 mL) is added n-butyl lithium in hexane (1.58 M, 12 mmol, 7.6 mL) dropwise at -78° C. over 45 min and stirred at -78° C. for 1 hour.
The mixture is warmed to -20° C., then added aqueous 1 M HCl (20 mL).
The mixture is warmed to room temperature.
The precipitate is collected and washed with hexane to give a colorless powder (808 mg, 51percent).
A mixture of the powder (3.63 mmol, 575 mg), pinacol (3.81 mmol, 450 mg) and MgSO4 (18.15 mmol, 2.2 g) in toluene (10 mL) is stirred at room temperature for 15 hour.
The mixture is filtrated and the solution is concentrated under reduced pressure.
The resultant solid is washed with water to give 2-chloro-5-(4,4,5,5-tetramethyl-[1,3,2]dioxaborolan-2-yl)-pyrimidine (875 mg, quant); ESI-MS m/z: 159 [M+1-pinacol]+, Retention time 1.75 min (condition A).
Reference: [1] Patent: WO2008/9435, 2008, A1, . Location in patent: Page/Page column 189-190
[2] Patent: US2009/118287, 2009, A1, . Location in patent: Page/Page column 67-68
  • 127
  • [ 76-09-5 ]
  • [ 100-63-0 ]
  • [ 1002334-12-4 ]
Reference: [1] Patent: CN105440067, 2016, A, . Location in patent: Paragraph 0018
  • 128
  • [ 76-09-5 ]
  • [ 1028092-65-0 ]
Reference: [1] Journal of Organic Chemistry, 2008, vol. 73, # 11, p. 4309 - 4312
  • 129
  • [ 76-09-5 ]
  • [ 209919-30-2 ]
  • [ 1030832-75-7 ]
YieldReaction ConditionsOperation in experiment
97%
Stage #2: With magnesium sulfate In diethyl ether at 20℃; for 24 h;
4-Chloro-2-methylphenylboronic acid (5.Og, 29 mmol) and 100 ml of Diethyl ether were placed in round-bottom flask. Then pinacol was added (3.43, 29 mmol, leq) and the resulting reaction mixture was stirred for couple of minutes until the solution became clear. Finally, MgSO,? (6.98, 58 mmol, 2eq) was added and the solution was allowed to stir at ambient temperature, under N2 balloon overnight. After 24h the reaction was worked up. MgSO4 was filtered off and <n="81"/>washed with Et2O. Organic layer was collected and the solvent was then removed. Pure product (7.2g, 97percent yield) was obtained as a white powder.Structure determination:RP-HPLC Conditions: HP 1100 HPLC chromatograph, Waters 3.9 x 150 mm NovaPak HR C18 column with guard column, 0.010 mL injection, 1.5 mL/min, 1.500 mL injection loop, 254 nm detection, A = water (0.1percent v/v TFA) and B = MeCN (0.1percent v/v TFA), gradient 10percent B 1 min, 10-80percent B over 9 min, 80-100percent B over 1 min, 100 percentB 1 min, retention time 12.6 min. 1H NMR (400 MHz, CDCl3): δ 1.33 (s, 12H), 2.50 (s, 3H), 7.14 (m, 2H) , 7.68 (d, IH) .
Reference: [1] Patent: WO2008/66921, 2008, A2, . Location in patent: Page/Page column 78-79
  • 130
  • [ 110-87-2 ]
  • [ 76-09-5 ]
  • [ 121-43-7 ]
  • [ 1025707-93-0 ]
Reference: [1] Organic Letters, 2012, vol. 14, # 19, p. 4998 - 5001,4
  • 131
  • [ 76-09-5 ]
  • [ 1040281-83-1 ]
Reference: [1] Chemistry - A European Journal, 2015, vol. 21, # 49, p. 17890 - 17896
[2] Chemistry - A European Journal, 2014, vol. 20, # 34, p. 10685 - 10694
  • 132
  • [ 76-09-5 ]
  • [ 87199-15-3 ]
  • [ 443776-76-9 ]
Reference: [1] Organic Letters, 2013, vol. 15, # 18, p. 4850 - 4853
  • 133
  • [ 76-09-5 ]
  • [ 443776-76-9 ]
Reference: [1] Molecules, 2013, vol. 18, # 10, p. 12346 - 12367
  • 134
  • [ 76-09-5 ]
  • [ 79265-30-8 ]
  • [ 1086111-09-2 ]
Reference: [1] Tetrahedron, 2009, vol. 65, # 29-30, p. 5739 - 5746
  • 135
  • [ 76-09-5 ]
  • [ 503176-50-9 ]
Reference: [1] Journal of Organometallic Chemistry, 2009, vol. 694, # 22, p. 3597 - 3607
[2] Journal of Organometallic Chemistry, 2009, vol. 694, # 22, p. 3597 - 3607
  • 136
  • [ 76-09-5 ]
  • [ 479-27-6 ]
  • [ 1214264-88-6 ]
Reference: [1] Journal of the American Chemical Society, 2010, vol. 132, p. 2548 - 2549
  • 137
  • [ 76-09-5 ]
  • [ 1630-79-1 ]
  • [ 479-27-6 ]
  • [ 1214264-88-6 ]
Reference: [1] Organic and Biomolecular Chemistry, 2015, vol. 13, # 37, p. 9659 - 9664
[2] Chemical Communications, 2015, vol. 51, # 9, p. 1693 - 1696
  • 138
  • [ 76-09-5 ]
  • [ 1073339-07-7 ]
YieldReaction ConditionsOperation in experiment
257 mg
Stage #1: at -5 - 20℃; for 1 h;
Stage #2: at 20℃; for 4 h;
In a reaction flask charged with Pd(OAc)2 (4.5 mg, 0.02 mmol), potassium iodide (83 mg, 0.5 mmol), and XPhos (28 mg, 0,06 mmol) under argon atmosphere was added, in this following order: anhydrous solvent (2 mL), Et3N (0.4 mL, 3 mmol), l-chloro-3,5- dimethoxybenzene (0.17 mL, 1 mmol) and diisopropylaminoborane (0.3 mL, 2 mmol). The reaction was then heated at 50 °C. After total consumption of either starting material, the reaction was cooled at -5 °C, quenched with anhydrous MeOH (2 mL) and stirred for 1 h at room temperature. All volatiles were removed under vacuum before adding pinacol (153 mg, 1.3 mmol) in Et20 (2 mL), and the mixture was stirred for 4 h at room temperature. The reaction mixture was diluted with Et20 (10 mL), and the organic phase was washed first with a solution of HC1 (0.1 N, 2x10 mL), followed by an aqueous solution of CuCl2 (50g/L, 3x10 mL), dried over anhydrous Na2S04, filtered and concentrated under vacuum. The crude oil was passed through a pad of silica gel, eluting with Et20. The resulting filtrate was concentrated under vacuum to afford 2-(3,5- dimethoxyphenyl)-4,4,5,5-tetramethyl-l,3,2-dioxaborolane (257 mg, 97percent). 1H NMR (300 MHz, CDCls) δ 7.21 (d, IH, J 3.2 Hz), 6.93 (dd, IH, J 8.9, 3.2 Hz), 6.83 (d, IH, J 8.9 Hz), 3.79 (s, 3H), 3.78 (s, 3H), 1.35 (s, 12H); 13C NMR (100 MHz, CDC13) δ 158.61, 153.29, 121.09, 118.04, 114.66, 83.56, 56.75, 55.82, 24.81; nB NMR (96 MHz, CDC13) δ +30.29; MS (EI) tR= 10.173 min; m/z: 264 (M+, 100percent).
257 mg at 20℃; for 4 h; Inert atmosphere In a reaction flask charged with Pd(OAc)2 (4.5 mg, 0.02 mmol), potassium iodide (83 mg, 0.5 mmol), and XPhos (28 mg, 0,06 mmol) under argon atmosphere was added, in this following order: anhydrous solvent (2 mL), Et3N (0.4 mL, 3 mmol), 1-chloro-3,5-dimethoxybenzene (0.17 mL, 1 mmol) and diisopropylaminoborane (0.3 mL, 2 mmol).
The reaction was then heated at 50 °C.
After total consumption of either starting material, the reaction was cooled at -5 °C, quenched with anhydrous MeOH (2 mL) and stirred for 1 h at room temperature.
All volatiles were removed under vacuum before adding pinacol (153 mg, 1.3 mmol) in Et2O (2 mL), and the mixture was stirred for 4 h at room temperature.
The reaction mixture was diluted with Et2O (10 mL), and the organic phase was washed first with a solution of HCl (0.1 N, 2x10 mL), followed by an aqueous solution of CuCl2 (50g/L, 3x10 mL), dried over anhydrous Na2SO4, filtered and concentrated under vacuum.
The crude oil was passed through a pad of silica gel, eluting with Et2O.
The resulting filtrate was concentrated under vacuum to afford 2-(3,5-dimethoxyphenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (257 mg, 97percent).
1H NMR (300 MHz, CDCl3) δ 7.21 (d, 1H, J 3.2 Hz), 6.93 (dd, 1H, J 8.9, 3.2 Hz), 6.83 (d, 1H, J 8.9 Hz), 3.79 (s, 3H), 3.78 (s, 3H), 1.35 (s, 12H); 13C NMR (100 MHz, CDCl3) δ 158.61, 153.29, 121.09, 118.04, 114.66, 83.56, 56.75, 55.82, 24.81; 11B NMR (96 MHz, CDCl3) δ +30.29; MS (EI) tR = 10.173 min; m/z: 264 (M+, 100percent).
Reference: [1] Chemistry - A European Journal, 2014, vol. 20, # 19, p. 5573 - 5579
[2] Patent: WO2015/82592, 2015, A2, . Location in patent: Page/Page column 92; 93
[3] Patent: EP2881398, 2015, A1, . Location in patent: Paragraph 0283
  • 139
  • [ 76-09-5 ]
  • [ 1238702-56-1 ]
  • [ 1238702-58-3 ]
YieldReaction ConditionsOperation in experiment
64% at 10 - 40℃; Reference Example 1321-Phenyl-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-pyrazole To a mixture of (1-phenyl-1H-pyrazol-5-yl)boronic acid (8.57 g, 45.6 mmol) in toluene (86 mL) was added pinacol (5.39 g, 45.6 mmol) at room temperature. The mixture was heated to 40° C. for 2 days. The mixture was concentrated in vacuo and triturated with hexane to yield the title compound (7.93 g, 64percent yield) as a pale yellow solid: 1H NMR (DMSO-d6, 300 MHz): δ ppm 1.23 (12H, s), 6.84 (1H, s), 7.34-7.59 (5H, m), 7.75 (1H, d, J=1.9 Hz)
19.8 g at 40℃; for 48 h; B)
1-phenyl-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-pyrazole
(1-Phenyl-1H-pyrazol-5-yl)boronic acid (25.0 g) was dissolved in toluene (700 mL), pinacol (18.0 g) was added thereto at room temperature, and the mixture was stirred at 40° C. for 2 days.
The reaction mixture was diluted with dichloromethane, and the mixture was washed with water and saturated brine, dried over anhydrous sodium sulfate, filtered, and concentrated.
The resulting solid was collected by filtration, and washed with hexane to give the title compound (19.8 g).
1H NMR (400 MHz, CDCl3) δ 1.27 (12H, s), 6.89 (1H, d, J=1.6 Hz), 7.33-7.43 (3H, m), 7.52-7.55 (2H, m), 7.72 (1H, d, J=1.6 Hz).
19.8 g at 20 - 40℃; for 48 h; B)
1-phenyl-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-pyrazole
(1-Phenyl-1H-pyrazol-5-yl)boronic acid (25.0 g) was dissolved in toluene (700 mL), pinacol (18.0 g) was added at room temperature, and the mixture was stirred at 40° C. for 2 days.
The reaction mixture was diluted with dichloromethane, washed successively with water and saturated brine, dried over anhydrous sodium sulfate and filtered, and the filtrate was concentrated.
The resulting solid was collected by filtration, and washed with hexane to give the title compound (19.8 g).
1H NMR (400 MHz, CDCl3) δ 1.27 (12H, s), 6.89 (1H, d, J=1.6 Hz), 7.33-7.43 (3H, m), 7.52-7.55 (2H, m), 7.72 (1H, d, J=1.6 Hz).
19.8 g at 20 - 40℃; for 48 h; E)
1-phenyl-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-pyrazole
(1-Phenyl-1H-pyrazol-5-yl)boronic acid (25.0 g) was dissolved in toluene (700 mL), pinacol (18.0 g) was added at room temperature, and the mixture was stirred at 40° C. for 2 days.
The reaction mixture was diluted with dichloromethane, washed with water and saturated brine, dried over anhydrous sodium sulfate, filtered and concentrated.
The resulting solid was collected by filtration and washed with hexane to give the title compound (19.8 g).
1H NMR (400 MHz, CDCl3) δ 1.27 (12H, s), 6.89 (1H, d, J=1.6 Hz), 7.33-7.43 (3H, m), 7.52-7.55 (2H, m), 7.72 (1H, d, J=1.6 Hz).

Reference: [1] Patent: US2010/197651, 2010, A1, . Location in patent: Page/Page column 73-74
[2] Patent: US2013/150344, 2013, A1, . Location in patent: Paragraph 0586; 0587
[3] Patent: US2013/137700, 2013, A1, . Location in patent: Paragraph 0449; 0450
[4] Patent: US2013/137675, 2013, A1, . Location in patent: Paragraph 0673; 0674
  • 140
  • [ 76-09-5 ]
  • [ 149105-19-1 ]
  • [ 1187591-17-8 ]
Reference: [1] Synthesis (Germany), 2012, vol. 44, # 14, p. 2173 - 2180
  • 141
  • [ 76-09-5 ]
  • [ 13675-18-8 ]
  • [ 1048970-17-7 ]
Reference: [1] Patent: WO2018/189157, 2018, A1, . Location in patent: Page/Page column 6-7
  • 142
  • [ 76-09-5 ]
  • [ 13675-18-8 ]
  • [ 13826-27-2 ]
  • [ 1048970-17-7 ]
Reference: [1] Patent: WO2018/189157, 2018, A1, . Location in patent: Page/Page column 6
  • 143
  • [ 76-09-5 ]
  • [ 13826-27-2 ]
  • [ 1048970-17-7 ]
Reference: [1] Journal of the American Chemical Society, 2018, vol. 140, # 34, p. 10700 - 10704
  • 144
  • [ 76-09-5 ]
  • [ 1048970-17-7 ]
Reference: [1] Science, 2017, vol. 357, # 6348, p. 283 - 286
  • 145
  • [ 76-09-5 ]
  • [ 1423-26-3 ]
  • [ 18107-18-1 ]
  • [ 1190235-39-2 ]
YieldReaction ConditionsOperation in experiment
72%
Stage #1: at 50℃; for 3 h;
Stage #2: With tetrabutyl ammonium fluoride In tetrahydrofuran; 1,4-dioxane; water at 50℃; for 3 h;
To a 10 mL reaction tube equipped with a magnet was added 76 mg (0.4 mmol) of 3-trifluoromethylphenylboronic acid, 0.4 mL (0.8 mmol) of trimethylsilyl diazomethane (2M n-hexane solution) 1 mL of toluene, stoppered with a rubber stopper and reacted on an electromagnetic heating stirrer at 50 ° C for 3 hours.Followed by addition of 71 mg (0.6 mmol) of pinacol (dissolved in 1 mL of 1,4-dioxane), 0.5 mL of tetrabutylammonium fluoride (1 M tetrahydrofuran solution) and 200 uL of water at 50 ° C in an electromagnetic heating stirrer To continue for 3 hours.After completion of the reaction, the organic solvent was removed by a rotary evaporator and purified by column chromatography3-trifluoromethylbenzyl boronic acid pinacol ester, its structure is as follows:The compound was a colorless liquid in a yield of 72percent with the following NMR data:
Reference: [1] Patent: CN105884808, 2016, A, . Location in patent: Paragraph 0136; 0137; 0138; 0139; 0140; 0141
  • 146
  • [ 25015-63-8 ]
  • [ 76-09-5 ]
  • [ 455-68-5 ]
  • [ 1293284-58-8 ]
YieldReaction ConditionsOperation in experiment
70% With triethylamine In tetrahydrofuran at 65℃; for 1 h; Inert atmosphere Step B: 5-Fluoro-2-(4,4,5,5-tetramethyl-[1 ,3,2]dioxaborolan-2-yl)-benzoic acid methyl ester. To a 1 L round-bottomed flask equipped with a reflux condenser, temperature probe, and nitrogen line, was added 5-fluoro-2-iodo- benzoic acid methyl ester (23 g, 82 mmol) in anhydrous THF (250 mL).Anhydrous triethylamine (34 mL, 246.4 mmol) was added and the resulting mixture was degassed with a nitrogen sparge for 5 minutes. Pinacol borane (17.9 mL, 123.2 mmol) was added and the reaction mixture was degassed once more for 5 minutes. Lastly, tri(o-tolyl)phosphine (1 .25 g, 4.1 mmol) and palladium acetate (461 mg, 2.053 mmol) were added. Again, the reaction mixture was degassed with a nitrogen sparge. The mixture was heated to 65 C and stirred for 1 h. After cooling to room temperature, the reaction mixture was quenched with half sat. ammonium chloride solution (250 mL), and the resulting layers were separated. The aqueous layer was extracted with additional ethyl acetate (250 mL) and the combined organics were dried over magnesium sulfate. After filtration and concentration, the crude product was obtained as a yellow oil (23 g). The crude product was then slurried in 25percent EA/hexanes (250 mL). The resulting solids were not desired product and were removed by filtration. The resulting solution was then concentrated to a yellow oil (21 g, 75 wtpercent desired, 16.1 g actual product, 70percent yield), which was used directly in the next step. By 1H-NMR, the crude product was also found to contain 14 wtpercent pinacol, 6.5 wtpercent ligand, and 4 wtpercent des-iodo starting material. 1 H NMR (400 MHz, CDCIs): 7.61 (dd, J = 9.5, 2.5 Hz, 1 H), 7.52 - 7.45 (m, 1 H), 7.21 (td, J = 8.3, 2.5 Hz, 1 H), 3.91 (s, 3H), 1 .41 (s, 12H).
Reference: [1] Patent: WO2011/50202, 2011, A1, . Location in patent: Page/Page column 77-78
  • 147
  • [ 76-09-5 ]
  • [ 1256359-15-5 ]
Reference: [1] Patent: WO2011/134971, 2011, A1,
[2] Patent: US2013/40984, 2013, A1,
  • 148
  • [ 76-09-5 ]
  • [ 1238196-66-1 ]
  • [ 1377503-12-2 ]
Reference: [1] Patent: WO2012/66442, 2012, A1, . Location in patent: Page/Page column 31
  • 149
  • [ 76-09-5 ]
  • [ 1131912-76-9 ]
Reference: [1] Science, 2017, vol. 357, # 6348, p. 283 - 286
  • 150
  • [ 76-09-5 ]
  • [ 1150114-52-5 ]
  • [ 1398923-95-9 ]
Reference: [1] Patent: WO2012/120469, 2012, A1, . Location in patent: Page/Page column 54; 55
  • 151
  • [ 76-09-5 ]
  • [ 951677-39-7 ]
  • [ 1073353-78-2 ]
Reference: [1] Organic Letters, 2013, vol. 15, # 6, p. 1346 - 1349
  • 152
  • [ 76-09-5 ]
  • [ 1150114-78-5 ]
  • [ 1112209-14-9 ]
Reference: [1] Molecules, 2013, vol. 18, # 10, p. 12346 - 12367
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