[ CAS No. 146631-00-7 ] {[proInfo.proName]}

Name: 146631-00-7|(4-(Benzyloxy)phenyl)boronic acid|98%
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SKU: A113646
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Quality Control of [ 146631-00-7 ]

COA NMR CNMR HPLC LC-MS

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SDS Specification

Alternatived Products of [ 146631-00-7 ]

Product Details of [ 146631-00-7 ]

CAS No. :	146631-00-7	MDL No. :	MFCD01075705
Formula :	C₁₃H₁₃BO₃	Boiling Point :	-
Linear Structure Formula :	-	InChI Key :	DMJHEIDWSIAXCS-UHFFFAOYSA-N
M.W :	228.05	Pubchem ID :	2734314
Synonyms :		Chemical Name :	(4-(Benzyloxy)phenyl)boronic acid

Calculated chemistry of [ 146631-00-7 ]

Physicochemical Properties

Num. heavy atoms :	17
Num. arom. heavy atoms :	12
Fraction Csp3 :	0.08
Num. rotatable bonds :	4
Num. H-bond acceptors :	3.0
Num. H-bond donors :	2.0
Molar Refractivity :	67.25
TPSA :	49.69 Å²

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) :	-6.07 cm/s

Lipophilicity

Log Po/w (iLOGP) :	0.0
Log Po/w (XLOGP3) :	2.29
Log Po/w (WLOGP) :	0.79
Log Po/w (MLOGP) :	1.54
Log Po/w (SILICOS-IT) :	0.77
Consensus Log Po/w :	1.08

Druglikeness

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

Water Solubility

Log S (ESOL) :	-2.95
Solubility :	0.253 mg/ml ; 0.00111 mol/l
Class :	Soluble
Log S (Ali) :	-2.97
Solubility :	0.244 mg/ml ; 0.00107 mol/l
Class :	Soluble
Log S (SILICOS-IT) :	-3.96
Solubility :	0.0251 mg/ml ; 0.00011 mol/l
Class :	Soluble

Medicinal Chemistry

PAINS :	0.0 alert
Brenk :	1.0 alert
Leadlikeness :	1.0
Synthetic accessibility :	1.98

Safety of [ 146631-00-7 ]

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

Application In Synthesis of [ 146631-00-7 ]

* 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 [ 146631-00-7 ]
Downstream synthetic route of [ 146631-00-7 ]

[ 146631-00-7 ] Synthesis Path-Upstream 1~7

1
[ 6793-92-6 ]
[ 146631-00-7 ]

Yield	Reaction Conditions	Operation in experiment
92.1%	With Trimethyl borate; sulfuric acid; iodine; magnesium In tetrahydrofuran at -40 - 20℃; for 2 h; Heating / reflux	First, 5.07 g of magnesium and 80 ml of dehydrated tetrahydrofuran were put in an argon-replaced 500 ml flask. Some pieces of iodine were added to the mixture to activate the magnesium. Then, 100 ml of dehydrated tetrahydrofuran containing 45.7 g of 4-bromo-1-benzyloxybenzene obtained from the synthesis (10-a) above was dropped to the resultant mixture while being stirred. After the dropping, the reaction solution was stirred under reflux for 30 minutes, and cooled to -40° C. Then, 60 ml of dehydrated tetrahydrofuran containing 21.66 g of trimetyl borate was dropped to the reaction solution while being stirred. After being left to gradually resume room temperature, the reaction solution was stirred under reflux for 30 minutes. The reaction solution was then cooled to 0° C. again, and after the addition of 200 ml of 10percent sulfuric acid, stirred for one hour. Toluene was added to the resultant solution to separate an organic layer. The organic layer was washed with a saturated brine and dried with sodium sulfate. The solvent was then distilled off. The residue was recrystallized from toluene, to obtain 36.5 g (Y: 92.1percent) of 4-benzyloxyphenylboronic acid.

Reference： [1] Patent: US6388146, 2002, B1, . Location in patent: Page column 35
[2] Angewandte Chemie - International Edition, 2004, vol. 43, # 39, p. 5235 - 5238
[3] Organic and Biomolecular Chemistry, 2010, vol. 8, # 21, p. 4831 - 4833
[4] European Journal of Organic Chemistry, 2012, # 7, p. 1448 - 1454
[5] Journal of the American Chemical Society, 2011, vol. 133, # 39, p. 15674 - 15685
[6] Chemical Communications, 2014, vol. 50, # 69, p. 9903 - 9906
[7] Organic Letters, 2004, vol. 6, # 4, p. 485 - 488
[8] Organic letters, 2002, vol. 4, # 13, p. 2125 - 2127
[9] Synthetic Communications, 1999, vol. 29, # 15, p. 2719 - 2730
[10] Chemistry - A European Journal, 2011, vol. 17, # 47, p. 13182 - 13187

2
[ 6793-92-6 ]
[ 121-43-7 ]
[ 146631-00-7 ]

Yield	Reaction Conditions	Operation in experiment
29%	With hydrogenchloride In tetrahydrofuran; hexane	A. 4-Phenylmethyloxy-phenylboronic acid To a solution of 4-phenylmethyloxy-bromobenzene (6.0 g, 23 mmol) in tetrahydrofuran (25 mL) and ether (75 mL) at -78° C. under argon, butyllithium (1.6M solution in hexane, 14.25 mL) was added over 15 minutes. The mixture was stirred 15 minutes and transferred via cannula over 15 minutes to a solution of trimethylborate (4.73 g, 45.6 mmol) in 50 mL of ether at -78° C. under argon. After 30 minutes at -78° C., the solution was warmed to room temperature and stirred for a further 60 minutes. 10percent aqueous hydrochloric acid was added (150 mL) and after 10 min the solution was extracted with ether (3100 mL). The combined ether extracts were extracted with 1M sodium hydroxide (3100 mL) and the combined aqueous extracts were acidified with dilute hydrochloric acid to pH 2 and extracted with ether (3*100 mL). The combined ether extracts were washed once with water (100 mL), dried and evaporated to afford a white solid which was crystallized from ether/hexanes to provide 1.48 g (29percent) of pure compound A as a white solid in two crops, m.p. 187°-189° C.

Reference： [1] Molecular Crystals and Liquid Crystals, 2003, vol. 401, p. 111/[225]-121/[235]
[2] Synlett, 2015, vol. 26, # 13, p. 1905 - 1910
[3] Patent: US5514696, 1996, A,
[4] Journal of the Chemical Society - Perkin Transactions 1, 1999, # 17, p. 2513 - 2523

3
[ 106-41-2 ]
[ 146631-00-7 ]

Reference： [1] Journal of the American Chemical Society, 2011, vol. 133, # 39, p. 15674 - 15685
[2] Chemistry - A European Journal, 2011, vol. 17, # 47, p. 13182 - 13187
[3] European Journal of Organic Chemistry, 2012, # 7, p. 1448 - 1454
[4] Chemical Communications, 2014, vol. 50, # 69, p. 9903 - 9906
[5] Synlett, 2015, vol. 26, # 13, p. 1905 - 1910

4
[ 13675-18-8 ]
[ 6373-46-2 ]
[ 146631-00-7 ]

Reference： [1] Journal of Organic Chemistry, 2014, vol. 79, # 21, p. 10568 - 10580

5
[ 100-39-0 ]
[ 146631-00-7 ]

6
[ 6793-92-6 ]
[ 150-46-9 ]
[ 146631-00-7 ]

Reference： [1] Patent: US6365775, 2002, B1, . Location in patent: Page column 7-8

7
[ 100-44-7 ]
[ 146631-00-7 ]

Reference： [1] Chemical Communications, 2014, vol. 50, # 69, p. 9903 - 9906
[2] Synlett, 2015, vol. 26, # 13, p. 1905 - 1910

[ 146631-00-7 ] Synthesis Path-Downstream 1~60

1
[ 146631-00-7 ]
[ 174575-06-5 ]
[ 174575-10-1 ]

Yield	Reaction Conditions	Operation in experiment
	With palladium diacetate; sodium carbonate; triphenylphosphine In ethanol; toluene at 100℃; ultrasonic bath;

Reference： [1]Muller; Kipfer; Lowe; Urwyler [Helvetica Chimica Acta, 1995, vol. 78, # 8, p. 2026 - 2035]

2
[ 34328-47-7 ]
[ 146631-00-7 ]
[ 188112-53-0 ]

Reference： [1]Bioorganic and Medicinal Chemistry Letters,2001,vol. 11,p. 1709 - 1712

3
[ 38411-20-0 ]
[ 146631-00-7 ]
4'-benzyloxy-2,3,6-trichloro-biphenyl [ No CAS ]

Reference： [1]Bioorganic and Medicinal Chemistry Letters,2001,vol. 11,p. 1709 - 1712

4
[ 6793-92-6 ]
[ 146631-00-7 ]

Yield	Reaction Conditions	Operation in experiment
92.1%	With Trimethyl borate; sulfuric acid; iodine; magnesium In tetrahydrofuran at -40 - 20℃; for 2h; Heating / reflux;	10.b (10-b) Synthesis of compound 4-benzyloxyphenylboronic acid represented by formula: First, 5.07 g of magnesium and 80 ml of dehydrated tetrahydrofuran were put in an argon-replaced 500 ml flask. Some pieces of iodine were added to the mixture to activate the magnesium. Then, 100 ml of dehydrated tetrahydrofuran containing 45.7 g of 4-bromo-1-benzyloxybenzene obtained from the synthesis (10-a) above was dropped to the resultant mixture while being stirred. After the dropping, the reaction solution was stirred under reflux for 30 minutes, and cooled to -40° C. Then, 60 ml of dehydrated tetrahydrofuran containing 21.66 g of trimetyl borate was dropped to the reaction solution while being stirred. After being left to gradually resume room temperature, the reaction solution was stirred under reflux for 30 minutes. The reaction solution was then cooled to 0° C. again, and after the addition of 200 ml of 10% sulfuric acid, stirred for one hour. Toluene was added to the resultant solution to separate an organic layer. The organic layer was washed with a saturated brine and dried with sodium sulfate. The solvent was then distilled off. The residue was recrystallized from toluene, to obtain 36.5 g (Y: 92.1%) of 4-benzyloxyphenylboronic acid.
82%	Stage #1: p-benzyloxyphenylbromide With n-butyllithium In tetrahydrofuran; hexane at -65℃; for 1h; Stage #2: With Trimethyl borate In tetrahydrofuran; hexane at -65 - 20℃; Stage #3: With hydrogenchloride In tetrahydrofuran; hexane
82%	Stage #1: p-benzyloxyphenylbromide With n-butyllithium In tetrahydrofuran; hexane at -65℃; for 1h; Inert atmosphere; Stage #2: With Triisopropyl borate In tetrahydrofuran; hexane at -65 - 20℃; Inert atmosphere; Stage #3: With hydrogenchloride In tetrahydrofuran; hexane; water Inert atmosphere;

80%	Stage #1: p-benzyloxyphenylbromide With n-butyllithium In tetrahydrofuran; hexane at -78℃; for 1h; Inert atmosphere; Stage #2: With Trimethyl borate In tetrahydrofuran; hexane at 20℃; for 16h; Inert atmosphere; Stage #3: With hydrogenchloride In tetrahydrofuran; hexane; water
75%	Stage #1: p-benzyloxyphenylbromide With n-butyllithium In tetrahydrofuran; hexane at -78℃; Inert atmosphere; Stage #2: In tetrahydrofuran; hexane at -78 - 20℃; Inert atmosphere; Stage #3: With hydrogenchloride; water In tetrahydrofuran; hexane Inert atmosphere;
36%	Stage #1: p-benzyloxyphenylbromide With n-butyllithium In tetrahydrofuran at -80℃; Stage #2: With Trimethyl borate In tetrahydrofuran Stage #3: With hydrogenchloride In water
	Stage #1: p-benzyloxyphenylbromide With n-butyllithium In tetrahydrofuran; hexane at -78℃; Stage #2: With Trimethyl borate In tetrahydrofuran; hexane at -78 - 20℃; Stage #3: With hydrogenchloride In tetrahydrofuran; hexane at 20℃;
	Stage #1: p-benzyloxyphenylbromide With n-butyllithium In tetrahydrofuran Stage #2: With Triisopropyl borate In tetrahydrofuran Stage #3: With ammonium chloride In tetrahydrofuran; water Further stages.;
	Multi-step reaction with 2 steps 1.1: n-butyllithium / tetrahydrofuran / 0.5 h / -78 °C 1.2: tetrahydrofuran / 2 h / -78 °C 2.1: HCl; water / diethyl ether
	Multi-step reaction with 2 steps 1.1: n-butyllithium / tetrahydrofuran / -78 °C / Inert atmosphere 1.2: -78 - 20 °C / Inert atmosphere 2.1: hydrogenchloride; water / tetrahydrofuran

Reference： [1]Current Patent Assignee: HON HAI PRECISION INDUSTRY CO., LTD.; Sharp (in: Foxconn); KANTO KAGAKU HOLDINGS K.K. - US6388146, 2002, B1 Location in patent: Page column 35
[2]Gimeno, Nelida; Ros, Maria Blanca; Serrano, Jose Luis; De La Fuente, Maria Rosario [Angewandte Chemie - International Edition, 2004, vol. 43, # 39, p. 5235 - 5238]
[3]Sunden, Henrik; Olsson, Roger [Organic and Biomolecular Chemistry, 2010, vol. 8, # 21, p. 4831 - 4833]
[4]Hu, Wen-Jing; Zhao, Xiao-Li; Ma, Ming-Liang; Guo, Fang; Mi, Xian-Qiang; Jiang, Biao; Wen, Ke [European Journal of Organic Chemistry, 2012, # 7, p. 1448 - 1454]
[5]Chen, Wei-Hong; Chuang, Wei-Tsung; Jeng, U-Ser; Sheu, Hwo-Shuenn; Lin, Hong-Cheu [Journal of the American Chemical Society, 2011, vol. 133, # 39, p. 15674 - 15685]
[6]Geese, Karina; Prehm, Marko; Tschierske, Carsten [Chemical Communications, 2014, vol. 50, # 69, p. 9903 - 9906]
[7]Kozaki, Masatoshi; Okada, Keiji [Organic Letters, 2004, vol. 6, # 4, p. 485 - 488]
[8]Baldwin, Jack E; Adlington, Robert M; Conte, Aurelia; Irlapati, Nageswara Rao; Marquez, Rodolfo; Pritchard, Gareth J [Organic letters, 2002, vol. 4, # 13, p. 2125 - 2127]
[9]Donnelly, Dervilla M.X.; Finet, Jean-Pierre; Guiry, Patrick J.; Rea, Martin D. [Synthetic Communications, 1999, vol. 29, # 15, p. 2719 - 2730]
[10]Chen, Wei-Hong; Chang, Yi-Ting; Lee, Jey-Jau; Chuang, Wei-Tsung; Lin, Hong-Cheu [Chemistry - A European Journal, 2011, vol. 17, # 47, p. 13182 - 13187]

5
[ 35065-86-2 ]
[ 146631-00-7 ]
[ 809285-98-1 ]

Reference： [1]Angewandte Chemie - International Edition,2004,vol. 43,p. 5235 - 5238
[2]Journal of the American Chemical Society,2006,vol. 128,p. 3051 - 3066
[3]Journal of the American Chemical Society,2011,vol. 133,p. 15674 - 15685
[4]Chemistry - A European Journal,2011,vol. 17,p. 13182 - 13187
[5]Angewandte Chemie - International Edition,2002,vol. 41,p. 2408 - 2412
[6]Chemical Communications,2008,p. 2523 - 2525
[7]Soft Matter,2013,vol. 9,p. 4590 - 4597
[8]Molecular Crystals and Liquid Crystals,2015,vol. 609,p. 19 - 30

6
[ 38603-09-7 ]
[ 146631-00-7 ]
4,4''-bis-benzyloxy-2'-methoxy-[1,1';3',1'']terphenyl [ No CAS ]

Reference： [1]Advanced Synthesis and Catalysis,2003,vol. 345,p. 939 - 942

7
[ 6793-92-6 ]
[ 121-43-7 ]
[ 146631-00-7 ]

Yield	Reaction Conditions	Operation in experiment
86%	Stage #1: p-benzyloxyphenylbromide With iodine; magnesium In tetrahydrofuran for 0.75h; Heating; Stage #2: Trimethyl borate In tetrahydrofuran at -78℃; for 1h; Stage #3: With hydrogenchloride at 20℃; for 1h;
68%	Stage #1: p-benzyloxyphenylbromide With n-butyllithium In tetrahydrofuran at -78℃; for 1h; Sealed tube; Stage #2: Trimethyl borate In tetrahydrofuran at 20℃; for 8h; Sealed tube;
62%	Stage #1: p-benzyloxyphenylbromide With iodine; magnesium In tetrahydrofuran for 2.66667h; Reflux; Stage #2: Trimethyl borate In tetrahydrofuran at -10℃;

1.48 g (29%)	With hydrogenchloride In tetrahydrofuran; hexane	27.A A. A. 4-Phenylmethyloxy-phenylboronic acid To a solution of 4-phenylmethyloxy-bromobenzene (6.0 g, 23 mmol) in tetrahydrofuran (25 mL) and ether (75 mL) at -78° C. under argon, butyllithium (1.6M solution in hexane, 14.25 mL) was added over 15 minutes. The mixture was stirred 15 minutes and transferred via cannula over 15 minutes to a solution of trimethylborate (4.73 g, 45.6 mmol) in 50 mL of ether at -78° C. under argon. After 30 minutes at -78° C., the solution was warmed to room temperature and stirred for a further 60 minutes. 10% aqueous hydrochloric acid was added (150 mL) and after 10 min the solution was extracted with ether (3100 mL). The combined ether extracts were extracted with 1M sodium hydroxide (3100 mL) and the combined aqueous extracts were acidified with dilute hydrochloric acid to pH 2 and extracted with ether (3*100 mL). The combined ether extracts were washed once with water (100 mL), dried and evaporated to afford a white solid which was crystallized from ether/hexanes to provide 1.48 g (29%) of pure compound A as a white solid in two crops, m.p. 187°-189° C.
	With n-butyllithium In tetrahydrofuran N2; BuLi dropping into org. compd. soln. at -78°C, mixt. keeping 3 h, B-compd. soln. addn. dropwise at -78°C, mixt. allowing to warm to room temp. overnight , stirring 1 h with 10% HCl, extn. (Et2O); org. extracts washing (water), drying, solvent vac. removal;
	Stage #1: p-benzyloxyphenylbromide With isopropylmagnesium chloride-lithium chloride complex In tetrahydrofuran at -10 - 0℃; for 1h; Inert atmosphere; Stage #2: Trimethyl borate In tetrahydrofuran at 20℃; Inert atmosphere;	1 Under the protection of nitrogen, 24.7g (0.094mol) of the above solid was added to 80mL of tetrahydrofuran, which was completely dissolved under stirring, and then cooled to -10 to 0 .The 1.3M isopropylmagnesium chloride-lithium chloride / tetrahydrofuran solution (94mL, 0.122mol) was added dropwise. After the addition was complete, the heat preservation exchange reaction was continued for 1 hour.After the reaction was completed, the above solution was added dropwise to a solution (50 mL) of trimethyl borate (14.7 g, 0.141 mol) dissolved in tetrahydrofuran,After the dropwise addition was completed, the heat preservation was continued to stir for 5 hours, and then it was naturally raised to room temperature and stirred to react overnight.Add 10% hydrochloric acid to quench, adjust pH = 3-4, extract twice with ethyl acetate, and wash with saturated brine.The ethyl acetate layer (containing 19.6g of product in the external calibration solution) was transferred to the hydrogenation reactor,Add 0.8 grams of 10% wet palladium carbon, heat to 30-35 , fill with hydrogen pressure 0.3MPa, stir the reaction for 5 hours,After the reaction is completed, the palladium carbon is filtered off (for reuse), the filtrate is distilled under reduced pressure, and the crude product is slurried with acetone and heptane,11.30 g of white solid was obtained with a total yield of 87% in two steps and a purity of 99.4% by HPLC.

Reference： [1]Sharma, Sanjay; Lacey, David; Wilson, Paul [Molecular Crystals and Liquid Crystals, 2003, vol. 401, p. 111/[225]-121/[235]]
[2]Panda, Gautam; Srinivas Lavanya Kumar [European Journal of Organic Chemistry, 2019, vol. 2019, # 4, p. 753 - 758]
[3]Prodanov, Maksym F.; Diakov, Maksym Y.; Vlasenko, Ganna S.; Vashchenko, Valerii V. [Synlett, 2015, vol. 26, # 13, p. 1905 - 1910]
[4]Current Patent Assignee: BRISTOL-MYERS SQUIBB CO - US5514696, 1996, A
[5]Imrie, Christopher; Loubser, Christa; Engelbrecht, Pieter; McCleland, Cedric W. [Journal of the Chemical Society. Perkin transactions I, 1999, # 17, p. 2513 - 2523]
[6]Current Patent Assignee: CANGZHOU PURUIDONGFANG TECH - CN111072698, 2020, A Location in patent: Paragraph 0022-0023; 0025

8
[ 90050-59-2 ]
[ 146631-00-7 ]
[ 1010412-93-7 ]

Yield	Reaction Conditions	Operation in experiment
	With sodium carbonate;tetrakis(triphenylphosphine) palladium(0); In 1,2-dimethoxyethane; water; at 85℃; for 2h;	Intermediate 7a: 4'-(Benzyloxy)-4-methylbiphenyl-3-carbaldehydeA solution of 750 mg (3.77 mmol) <strong>[90050-59-2]5-bromo-2-methylbenzaldehyde</strong>, 1.03 g (4.52 mmol) 4-benzyloxyphenyl boronic acid, 87 mg Pd(PPh3)4, and 5 ml_ (9.42 mmol) of 2.0 M Na2CO3 (aq) in 15 ml_ DME was heated to 850C for 2 hrs. To the mixture was added 250 mg decolorizing carbon and the mixture stirred for 5 min then filtered through a pad of Celite and silica gel and concentrated to give 1.20 g of 4'-(benzyloxy)-4-methylbiphenyl-3- carbaldehyde as a beige solid: 1 H NMR (400 MHz, CDCI3). delta 10.36 (s, 1 H), 8.02 (s, 1 H), 7.69-7.62 (m, 1 H), 7.55 (d, 2H, J = 8.2 Hz), 7.49-7.43 (m, 1 H), 7.06 (d, 2H, J = 8.2 Hz), 5.13 (s, 2H), 2.71 (s, 3H.)

Reference： [1]Patent: WO2008/28118,2008,A1 .Location in patent: Page/Page column 53

9
[ 146631-00-7 ]
[ 179803-79-3 ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 2 steps 1: 79 percent / KOH / bis(dicyclohexylamine)palladium acetate / ethanol / 20 h / 40 °C 2: 47 percent / BBr₃ / CH₂Cl₂ / 24 h / 20 °C

Reference： [1]Zelzer, Mischa; Kappaun, Stefan; Zojer, Egbert; Slugovc, Christian [Monatshefte fur Chemie, 2007, vol. 138, # 5, p. 453 - 464]

10
[ 25109-28-8 ]
[ 146631-00-7 ]
4-benzyloxy-4'-cyclohexylbiphenyl [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
70.1%	With sodium carbonate;tetrakis(triphenylphosphine) palladium(0); In ethanol; water; benzene; for 8h;Heating / reflux;	First, 80 ml of ethanol containing 7.18 g of 4-benzyloxyphenylboronic acid obtained from the synthesis (10-b) above dissolved therein, 50 ml of benzene containing 5.00 g of <strong>[25109-28-8]1-bromo-4-cyclohexylbenzene</strong> dissolved therein, 21.0 ml of a sodium carbonate aqueous solution with a concentration of 2 mol/l, and 0.24 g of tetrakis(triphenylphosphine)palladium(0) were put in an argon-replaced 200 ml flask, and stirred under reflux for eight hours. After the reaction, water and toluene were added to the reaction solution for extraction. The resultant toluene layer was washed with a saturated brine and dried with sodium sulfate. The solvent was then distilled off. The residue was purified by silica gel column chromatography (eluent:toluene/hexane=1/4), to obtain 5.04 g (Y: 70.1%) of 4-benzyloxy-4'-cyclohexylbiphenyl. The purity of the resultant compound was 98.3% as measured by GC.

Reference： [1]Patent: US6388146,2002,B1 .Location in patent: Page column 36

11
[ 52334-81-3 ]
[ 146631-00-7 ]
[ 872254-81-4 ]

Yield	Reaction Conditions	Operation in experiment
77.4%	With cesium fluoride In 1,4-dioxane at 105℃;	18.A A mixture of 2-chloro-5-trifluoromethylpyridine (1.81 g, 10 mmol), 4- benzyloxyphenyl boronic acid (2.74 g, 12 mmol) and CsF (5.32 g, 35 mmol) in dioxane (40 mL) is degaseed and filled with nitrogen. PdCl2(dppf) (200 mg) is added under nitrogen, the reaction mixture is heated at 105 °C overnight. The mixture is cooled to room temperature, diluted with ethyl acetate (100 mL), filtered through a pad of Celite. The filtrate is concentrated and the residue is purified by column chromatography on silica gel giving the title compound (2.55g, 77.4 %).

Reference： [1]Current Patent Assignee: ELI LILLY & CO - WO2005/123668, 2005, A1 Location in patent: Page/Page column 45

12
[ 330794-31-5 ]
sodium carbonate monohydrate [ No CAS ]
[ 146631-00-7 ]
3-[4-(benzyloxy)phenyl]-1-cyclopentyl-1H-pyrazolo[3,4-d]pyrimidin-4-amine [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	tetrakis(triphenylphosphine) palladium(0); In 1,2-dimethoxyethane; water;	Example 86 3-[4-(Benzyloxy)phenyl]-1-cyclopentyl-1H-pyrazolo[3,4-d]pyrimidin-4-amine To a mixture of <strong>[330794-31-5]1-cyclopentyl-3-iodo-1H-pyrazolo[3,4-d]pyrimidin-4-amine</strong> (5.41 g, 17.1 mmol, 1 equiv) and 4-(benzyloxy)phenylboronic acid (4.87 g, 21.4 mmol, 1.2 equiv) in DME (100 mL) was added tetrakis(triphenylphosphine)palladium (1.19 g, 1.03 mmol, 0.06 equiv) and a solution of sodium carbonate monohydrate (5.09 g, 41 mmol, 2.4 equiv) in water (54 mL). The mixture was heated at 85 C. for 2 h. Additional tetrakis(triphenylphosphine)palladium (1.19 g, 1.03 mmol, 0.06 equiv) was added and the reaction mixture was heated at 85 C. for 3 h. The mixture was allowed to cool to ambient temperature and a white crystalline solid (3.868 g) was collected by filtration. In order to recover more product, the filtrate was concentrated in vacuo and the residue was partitioned between water (50 mL) and EtOAc (50 mL). The aqueous layer was extracted with three portions of EtOAc (150 mL each) and the combined organic extracts were washed with three portions of water (100 mL each) and brine (100 mL), dried over MgSO4, filtered, and concentrated to afford a yellow solid (0.916 g). The two solids were combined and recrystallized from hot EtOAc to afford 3-[4-(benzyloxy)phenyl]-1-cyclopentyl-1H-pyrazolo[3,4-d]pyrimidin-4-amine as a white solid (3.41 g, 8.8 mmol): 1H NMR (d6 DMSO, 400 MHz): deltaH 8.22 (1H, s), 7.19-7.62 (7H, m), 7.18 (2H, d, J=6.9 Hz), 5.18-5.23 (1H, m), 5.22 (2H, s), 2.00-2.10 (4H, m), 1.87-1.89 (2H, m), 1.66-1.70 (2H, m). RP-HPLC (Hypercil C18, 5 mum, 100 A, 15 cm; 5%-100% acetonitrile-0.1M ammonium acetate over 15 min, 1 mL/min). Rt 13.05 min.
	tetrakis(triphenylphosphine) palladium(0); In 1,2-dimethoxyethane; water;	Example 86 3-[4-(Benzyloxy)phenyl]-1-cyclopentyl-1H-pyrazolo[3,4-d]pyrimidin-4-amine To a mixture of <strong>[330794-31-5]1-cyclopentyl-3-iodo-1H-pyrazolo[3,4-d]pyrimidin-4-amine</strong> (5.41 g, 17.1 mmol, 1 equiv) and 4-(benzyloxy)phenylboronic acid (4.87 g, 21.4 mmol, 1.2 equiv) in DME (100 mL) was added tetrakis(triphenylphosphine)palladium (1.19 g, 1.03 mmol, 0.06 equiv) and a solution of sodium carbonate monohydrate (5.09 g, 41 mmol, 2.4 equiv) in water (54 mL). The mixture was heated at 85 C. for 2 h. Additional tetrakis(triphenylphosphine)palladium (1.19 g, 1.03 mmol, 0.06 equiv) was added and the reaction mixture was heated at 85 C. for 3 h. The mixture was allowed to cool to ambient temperature and a white crystalline solid (3.868 g) was collected by filtration. In order to recover more product, the filtrate was concentrated in vacuo and the residue was partitioned between water (50 mL) and EtOAc (50 mL). The aqueous layer was extracted with three portions of EtOAc (150 mL each) and the combined organic extracts were washed with three portions of water (100 mL each) and brine (100 mL), dried over MgSO4, filtered, and concentrated to afford a yellow solid (0.916 g). The two solids were combined and recrystallized from hot EtOAc to afford 3-[4-(benzyloxy)phenyl]-1-cyclopentyl-1H-pyrazolo[3,4-d]pyrimidin-4-amine as a white solid (3.41 g, 8.8 mmol): 1H NMR (d6 DMSO, 400 MHz): deltaH 8.22 (1H, s), 7.19-7.62 (7H, m), 7.18 (2H, d, J=6.9 Hz), 5.18-5.23 (1H, m), 5.22 (2H, s), 2.00-2.10 (4H, m), 1.87-1.89 (2H, m), 1.66-1.70 (2H, m). RP-HPLC (Hypercil C18, 5 mum, 100 A, 15 cm; 5%-100% acetonitrile-0.1M ammonium acetate over 15 min, 1 mL/min). Rt 13.05 min.

Reference： [1]Patent: US2002/156081,2002,A1
[2]Patent: US6921763,2005,B2

13
[ 603-35-0 ]
[ 32779-37-6 ]
[ 146631-00-7 ]
[ 152915-90-7 ]

Yield	Reaction Conditions	Operation in experiment
	With sodium carbonate; In ethanol; water; toluene;	Example 1 5-bromo-2-[4-(benzoxy)phenyl]pyrimidine STR33 A solution of 104 g of <strong>[32779-37-6]2,5-dibromopyrimidine</strong>, 100 g of 4-benzoxyphenylboronic acid, 4.75 g of Pd (10% on activated charcoal), 4.5 g of triphenylphosphene and 93 g of sodium carbonate in 1 l of toluene, 0.5 l of ethanol and 0.3 l of water is heated at 80 C. for 24 hours. After filtration, the organic phase is separated off and evaporated to dryness in vacuo. The residue is recrystallized from acetonitrile: 83 g of solids of melting point 153-155 C.

Reference： [1]Patent: US5872301,1999,A

14
[ 7440-05-3 ]
[ 32779-37-6 ]
[ 146631-00-7 ]
[ 152915-90-7 ]

Yield	Reaction Conditions	Operation in experiment
	With sodium carbonate; In ethanol; water; toluene;	COMPARATIVE EXAMPLE 1 Synthesis of 5-bromo-2-[4-(phenylmethoxy)phenyl]pyrimidine by the process described in DE 39 30 663 4.17 g (17.54 mmol) of <strong>[32779-37-6]2,5-dibromopyrimidine</strong>, 4.00 g (17.54 mmol) of 4-(phenylmethoxy)benzeneboronic acid, 0.19 g (0,175 mmol) of palladium (10%) on activated carbon and 3.72 g (35.10 mmol) of sodium carbonate are reacted in 42 ml of toluene, 21 ml of ethanol and 12.5 ml of water using a similar method to Example 1. Analysis (HPLC) of the crude product indicates a mixture which contains the starting materials <strong>[32779-37-6]2,5-dibromopyrimidine</strong>, 4-(phenylmethoxy)benzeneboronic acid and unidentified products in addition to 6.3% of the desired product 5-bromo-2-[4-(phenylmethoxy)phenyl]pyrimidine. - Example No. R1 A1 A2 A3 A4 R2 Yield Phase transitions 2 H17 C8

Reference： [1]Patent: US5550236,1996,A

15
[ 7440-44-0 ]
[ 32779-37-6 ]
[ 146631-00-7 ]
[ 152915-90-7 ]

Yield	Reaction Conditions	Operation in experiment
	With sodium carbonate; triphenylphosphine;palladium; In ethanol; water; toluene;	EXAMPLE 1 5-Bromo-2-[4-(phenylmethoxy)phenyl]pyrimidine 104.25 g (0.438 mol) of <strong>[32779-37-6]2,5-dibromopyrimidine</strong>, 100.00 g (0.438 mol) of 4-(phenylmethoxy)benzeneboronic acid, 4.75 g (0.00438 mol) of palladium (10%) on activated carbon, 4.50 g (0.01752 mol) of triphenylphosphine and 93.00 g (0.876 mol) of sodium carbonate are heated in 1000 ml of toluene, 500 ml of ethanol and 300 ml of water for 24 hours at 80 C. The palladium catalyst is subsequently separated off from the reaction mixture at 80 C. by filtration. The aqueous lower phase of the reaction mixture is separated off at 80 C., before the organic phase is freed of the solvents on a rotary evaporator and dried in a high vacuum. The crude product thus obtained is recrystallized from acetonitrile (3000 ml), giving 150.07 g (97% yield, based on 2,5-dibromopyridine) of 5-bromo-2-[4-(phenylmethoxy)phenyl]pyrimidine (purity according to HPLC: 98%).

Reference： [1]Patent: US5550236,1996,A

16
[ 19745-07-4 ]
[ 146631-00-7 ]
2-chloro-5-(4-benzyloxyphenyl)pyrazine [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
		2-(4-Benzyloxyphenyl)-5-(6-octyloxypyridin-3-yl)pyrazine STR50 Step 1 In accordance with scheme C-I, 30 g (201 mmol) of <strong>[19745-07-4]2,5-dichloropyrazine</strong> and 45.92 g (201 mmol) of 4-benzyloxyphenylboronic acid are coupled analogously to Example 4a to give 2-chloro-5-(4-benzyloxyphenyl)pyrazine.

Reference： [1]Patent: US5512207,1996,A

17
[ 1052271-60-9 ]
[ 146631-00-7 ]
[ 1059098-58-6 ]

Yield	Reaction Conditions	Operation in experiment
30%	With sodium hydroxide;tetrakis(triphenylphosphine) palladium(0); In 1,2-dimethoxyethane; water; for 24.0h;Heating / reflux;	Example 17; 8-(4-(benzyloxy)phenyl)H-imidazo[1,5-a]pyridine8-bromo-H-imidazo[1,5-a]pyridine (example 12) (0.1 g, 0.5 mmol, 1 eq) was dissolved in 10 mL of DME and kept under an argon atmosphere. To that solution [Pd(PPh3)4] (0.025 mmol, 0.05 eq), 4-(benzyloxy)phenyl boronic acid (0.171 g, 0.75 mmol, 1.5 eq) and an aqueous NaOH solution (0.2M, 5 mL) were added under stirring. The resulting mixture was refluxed for 24 h. After cooling, the mixture was diluted with water and the aqueous layer was extracted with CHCl3. The organic layers were dried (Na2SO4), filtered and evaporated under reduced pressure. Semi-preparative HPLC-chromatography afforded the pure product.Yield: 0.044 g (30%), 1H-NMR, 500 MHz, CDCl3: delta 5.09(2H); 6.93-6.95 (m, 2H); 7.01-7.07 (m, 2H); 7.28-7.41 (m, 5H); 7.48-7.50 (m, 2H); 7.71 (s, 1H); 8.01-8.03 (m, 1H); 8.96 (s, 1H) MS: m/z 301.5 [M+H]+; HPLC: Method [B]. (214 nm), rt: 10.65 min (100%)

Reference： [1]Patent: US2008/234313,2008,A1 .Location in patent: Page/Page column 30

18
[ 956434-30-3 ]
[ 146631-00-7 ]
tert-butyl 8-[(benzyloxy)phenyl]-2,3-dihydropyrido[3,2-f][1,4]oxazepine-4(5H)-carboxylate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
64%	With potassium carbonate;tetrakis(triphenylphosphine) palladium(0); In 1,2-dimethoxyethane; water; at 150℃; for 0.166667h;Microwave irradiation;	(Step 1) A solution of the compound (0.500 g) obtained in Example 29, step 1, 4-benzyloxyphenylboronic acid (0.600 g) and potassium carbonate (0.243 g) in DME (10 mL) and water (1 mL) was degassed with argon gas, tetrakis(triphenylphosphine)palladium(0) (Pd(PPh3)4) (0.203 g) was added, and the reaction container was irradiated in a microwave reaction apparatus at 150C for 10 min. The reaction mixture was poured into water, and the resultant product was extracted with ethyl acetate. The organic layer was washed with brine, dried over magnesium sulfate, and concentrated. The obtained solid was recrystallized from a mixed solution of ethyl acetate and hexane to give tert-butyl 8-[(benzyloxy)phenyl]-2,3-dihydropyrido[3,2-f][1,4]oxazepine-4(5H)-carboxylate (0.483 g, 64%) as a white powder. 1H-NMR(CDCl3): delta 1.32(9H,brs), 3.74(2H,brs), 4.24(2H,brs), 4.47(2H,brs), 5.17(2H,s), 7.09(2H,d,J=8.7Hz), 7.31-7.52(5H,m), 7.58(1H,m), 7.71(1H,m), 7.97(2H,d,J=8.7Hz) MS(ESI+):433(M+H)

Reference： [1]Patent: EP2018863,2009,A1 .Location in patent: Page/Page column 125

19
[ 885520-70-7 ]
[ 146631-00-7 ]
[ 1181566-98-2 ]

Yield	Reaction Conditions	Operation in experiment
	With oxygen; triethylamine;copper diacetate; In dichloromethane; at 20℃; for 16h;	Description 19. 4-bromo-6-fluoro-1-{4-[(phenylmethyl)oxy]phenyl}-1H-indole A mixture of 4-bromo-6-fluoro-1 H-indole (D16),(200 mg, 0.935 mmol), 4- benzyloxyphenylboronic acid (426 mg, 1.87 mmol), copper (II) acetate (332 mg, 1.87 mmol) and triethylamine (0.26 ml_, 188 mg, 1.87 mmol) in dichloromethane (5 ml.) was stirred in air at room temperature for 16 hours. The mixture was filtered through celite, concentrated and purified by chromatography on silica gel (elution with 0-20percent ethyl acetate in hexanes) to give the tite compound as a pink solid (D19), (205 mg). LC-MS: MH+ = 396/398 (C21H15BrFNO = 395/397)

Reference： [1]Patent: WO2009/103710,2009,A1 .Location in patent: Page/Page column 23

20
[ 623-00-7 ]
[ 146631-00-7 ]
[ 117571-49-0 ]

Yield	Reaction Conditions	Operation in experiment
	With potassium carbonate In methanol; toluene for 16h; Reflux;

Reference： [1]Bandini, Marco; Pietrangelo, Agostino; Sinisi, Riccardo; Umani-Ronchi, Achille; Wolf, Michael O. [European Journal of Organic Chemistry, 2009, # 21, p. 3554 - 3561]

21
[ 101935-40-4 ]
[ 146631-00-7 ]
[ 1202677-59-5 ]

Yield	Reaction Conditions	Operation in experiment
80%		4'-Benzyloxy-6-nitro-biphenyl-2-ol Error. Objects cannot be created from editing field codes.To a solution of <strong>[101935-40-4]2-bromo-3-nitrophenol</strong> (5.36 g) and 4-benzyloxyphenyl boronic acid (6.73 g) in dioxane (220 mL) was added 2 M aqueous Na2COs solution (55.4 mL) and the mixture was purged with argon. Pd(PPh3 )4 (1.42 g) was added and the mixture was purged again with argon. The reaction mixture was heated to reflux for 24 h. The mixture was cooled to room temperature and the organic solvent was removed under reduced pressure. The residue was diluted with water (150 mL), neutralized with 2 N HCl, filtered through a Celite plug, and washed with EtOAc. The filtrate was extracted with EtOAc (3 x 100 mL). The combined organic phases were washed with brine (50 mL) and dried over MgSO4. Concentration and purification by silica gel chromatography eluting with 5-40% EtO Ac/heptane provided 4'-benzyloxy-6-nitro-biphenyl-2-ol (6.35 g, 80 %) as yellow solid. 1H NMR (300 MHz, CDCI3/TMS) delta 7.52-7.30 (m, 7H), 7.27-7.15 (m, 3H), 7.09 (d, J= 7.8 Hz, 2H), 5.73 (s, IH), 5.09 (s, 2H); 13C NMR (75 MHz, CDCI3/TMS) delta 159.1, 154.1, 149.9, 136.3, 130.4, 128.7, 128.4, 127.9, 127.3, 122.7, 121.8, 119.4, 115.7, 115.5, 70.0.

Reference： [1]Patent: WO2009/158467,2009,A2 .Location in patent: Page/Page column 60; 91-92

22
[ 67853-37-6 ]
[ 146631-00-7 ]
[ 1202677-89-1 ]

Yield	Reaction Conditions	Operation in experiment
	With sodium carbonate;(1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; In 1,4-dioxane; for 24h;Inert atmosphere; Reflux;	Synthesis of 2-(\|2'-Methoxy-6'-(pyridin-4-yl)biphenyl-4- yloxy)methyl)quinoline (Example 385)4'-(Benzyloxy)-2-methoxy-6-nitrobiphenyl Error. Objects cannot be created from editing field codes.2-Bromo-3-nitroanisole (2.50 g), 4-benzyloxyphenyl boronic acid (2.94 g), and 2 M Na2COs solution (16.2 mL) in 150 ml dioxane was degassed four times before Pd(dppf)Cl2 (0.39 g) was added. The mixture was degassed four more times, then heated to reflux for 24 h. The mixture was cooled down to room temperature and the solvent was removed. The residue was washed with dichloromethane, and the filtrate was concentrated and purified by silica gel flash chromatography eluting with 50% ethyl acetate in heptane to give 4'-(benzyloxy)-2-methoxy-6-nitrobiphenyl (3.4 g) as a yellow solid. 1H NMR (300 MHz, CDCI3/TMS) delta 7.47-7.33 (m, 7H), 7.20 (d, J= 8.7 Hz, 2H), 7.13 (d, J= 7.8 Hz, IH), 7.02 (d, J= 8.7 Hz, 2H), 5.05 (s, 2H), 3.75 (s, 3H); 13C NMR (75 MHz, CDCI3/TMS) delta 158.83, 157.84, 151.48, 137.05, 130.63, 128.82, 128.24, 127.82, 124.97, 124.80, 115.56, 114.88, 114.44, 70.29, 56.74.

Reference： [1]Patent: WO2009/158467,2009,A2 .Location in patent: Page/Page column 88

23
[ 13389-03-2 ]
[ 146631-00-7 ]
[ 1257514-39-8 ]

Yield	Reaction Conditions	Operation in experiment
81%	With tris-(2-sulfophenyl)phosphine trisodium salt; palladium diacetate; sodium carbonate In water; acetonitrile at 80℃; for 4h; Inert atmosphere;

Reference： [1]Omumi, Alireza; Beach, Daniel G.; Baker, Michael; Gabryelski, Wojciech; Manderville, Richard A. [Journal of the American Chemical Society, 2011, vol. 133, # 1, p. 42 - 50]

24
[ 153463-65-1 ]
[ 146631-00-7 ]
[ 1266161-08-3 ]

Yield	Reaction Conditions	Operation in experiment
52%	With potassium phosphate;tetrakis(triphenylphosphine) palladium(0); In ISOPROPYLAMIDE; at 150℃; for 1h;Inert atmosphere;	Example 50; 4-(4-(4-Methoxyphenoxy)phenyl)-1H-pyrazolo[3,4-c]pyridin-3-amineStep 1:[00178] A mixture of 3,5-dichloroisonicotinonit?le (2.50 g, 14.45 mmol), 4- (benzyl oxy)phenylboronic acid (3.63 g, 15.90 mmol), potassium phosphate (6.13 g, 28.9 mmol) and palladium tetrakis(triphenylphosphme) (0.835 g, 0.723 mmol) was pumped and backfilled with nitrogen 3 times. N,N-Diraethylacetamide (40 mL) was added. The mixture was again pumped and backfilled with nitrogen 3 times and heated with a 150 C oil bath for 1 h. The mixture was diluted with ethyl acetate (400 mL), washed twice with 1: 1 mixture of brine and water (100 mL), brine (100 mL), dried (MgSO4) and concentrated. Silica gel chromatography, loading with toluene and eluting with 10-35% ethyl acetate in hexanes, gave 3-(4-(benzyloxy)phenyl)-5-chloroisoncotinonitrle as a white solid (2.387 g, 52% yield). 1B. NMR (500 MHz1 CDCl3) delta ppm 8.72 (1 H, s), 8.69 (1 H. s), 7.51 - 7.60 (2 H, m), 7.40 - 7.50 (4 H, m), 7.33 - 7.40 (1 H, m), 7.10 - 7.19 (2 H, m), 5.15 (2 H, s); MS (ES+) m/z: 321 (M+H); LC retention time: 4.323 min (analytical HPLC Method A).

Reference： [1]Patent: WO2011/19780,2011,A1 .Location in patent: Page/Page column 85-86

25
[ 36282-26-5 ]
[ 146631-00-7 ]
[ 1260389-33-0 ]

Yield	Reaction Conditions	Operation in experiment
78%	With sodium carbonate In 1,2-dimethoxyethane; water for 5h; Heating; Reflux;	4I-(Benzyloxy)-5-fluorobiphenyl-2-carbonitriIe (CAB06048) A mixture of 2-bromo-4-fluorobenzinitrile (4.50 g, 22.5 nimol), 4- benzyloxyphenylboronic acid (5.19 g, 22.76 mmol), dimethoxyethane (25 mL) and 2M Na2CO3 (40 mL) was heated to reflux before Pd2(dba)3 (0,05 g, 0.055 mmol) was added and heating was continued for 5 hours. After cooling to room temperature CHCl3 (ca. 100 mL) was added to dissolve the product, which crystallised from the organic layer. The mixture was filtered through celite, the organic layer was separated, dried (Na2SO4) and concentrated under reduced pressure. The residue was recrystallized from CHCl3/hexane to give CAB06048 (532 g, 78%) as colorless needles. Mp. 94-96 0C; 1H NMR (400 MHz, DMSO-^6) δ 5.12 (s, 2H), 7.06-7.12 (m, 3H), 7.18 (dd, J= 9.4, 2.7 Hz, IH)5 733-7,53 (m, 7H)5 7.74 (dd, J = 8.6, 5,7 Hz, IH); LRMS (ES+): m/z 326.4 (100%, [M+Naf), 3043 (60%, [M+H]+); HRMS (ES+) calcd for C20Hi5FNO [M+H]+: 304.1132, found 304.1125.
	With bis(dibenzylideneacetone)-palladium⁽⁰⁾

Reference： [1]Current Patent Assignee: ESTRYX PHARMA - WO2011/23989, 2011, A1 Location in patent: Page/Page column 97-98
[2]Location in patent: scheme or table Woo, L. W. Lawrence; Bubert, Christian; Purohit, Atul; Potter, Barry V. L. [ACS Medicinal Chemistry Letters, 2011, vol. 2, # 3, p. 243 - 247]

26
[ 1193-18-6 ]
[ 146631-00-7 ]
[ 1289577-09-8 ]
(S)-3-(4-benzyloxylphenyl)-3-methylcyclohexanone [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	With palladium(II) trifluoroacetate; 2-[(S)-4,5-dihydro-4-tert-butyl-1,3-oxazol-2-yl]pyridine In 1,2-dichloro-ethane at 60℃; for 18h; optical yield given as %ee; enantioselective reaction;
74 % ee	With palladium(II) trifluoroacetate; 2-[(S)-4,5-dihydro-4-tert-butyl-1,3-oxazol-2-yl]pyridine In 1,2-dichloro-ethane Heating; Overall yield = 96 %; enantioselective reaction;	5.4 8.5.4. (R)-3-(4-Benzyloxylphenyl)-3-methylcyclohexanone (38) General procedure: Synthesized according to the general procedure and purified by flash chromatography (hexanes/EtOAc=100:0 to 95:5) to afford a colorless oil (96% yield). 1H NMR (500 MHz, CDCl3) δ 7.43 (ddd, J=1.5, 2.0, 7.5 Hz, 2H), 7.39 (ddd, J=1.0, 7.0, 7.5, 2H), 7.33 (tt, J=1.5, 7.0 Hz, 1H), 7.22 (ddd, J=2.0, 3.5, 10.0 Hz, 2H), 6.93 (ddd, J=2.0, 3.5, 10.0 Hz, 2H), 5.04 (s, 2H), 2.85 (d, J=14.0 Hz, 1H), 2.42 (d, J=14.0 Hz, 1H), 2.30 (t, J=7.0 Hz, 2H), 2.18-2.13 (m, 1H), 1.92-1.83 (m, 2H), 1.71-1.62 (m, 1H), 1.30 (s, 3H), 0.97 (s, 9H), 0.19 (s, 6H); 13C NMR (125 MHz, CDCl3) δ 211.6, 157.0, 139.7, 137.0, 128.6, 127.9, 127.5, 126.7, 114.7, 70.0, 53.3, 42.3, 40.8, 38.0, 30.0, 22.0; IR (Neat Film, NaCl) 3066, 3027, 2947, 2873, 1710, 1609, 1579, 1510, 1453, 1426, 1379, 1312, 1290, 1246, 1181, 1021 cm-1; HRMS (MultiMode ESI/APCI) m/z calcd for C20H23O2 [M+H]+: 295.1693, found 295.1673; [α]D25 -26.8 (c 4.90, CHCl3, 74% ee). A screw-top 1 dram vial was charged with a stir bar, Pd(OCOCF3)2 (4.2 mg, 0.0125 mmol, 5 mol %), (S)-t-BuPyOx (3.1 mg, 0.015 mmol, 6 mol %), and PhB(OH)2 (61 mg, 0.50 mmol, 2.0 equiv). The solids were dissolved in dichloroethane (0.5 mL) and 3-methyl-2-cyclohexenone (29 mL, 0.25 mmol) was added. The walls of the vial were rinsed with an additional portion of dichloroethane (0.5 mL). The vial was capped with a Teflon/silicone septum and stirred at 60 °C in an oil bath for 12 h. Upon complete consumption of the starting material (monitored by TLC, 4:1 hexanes/EtOAc, p-anisaldehyde stain) the reaction was purified directly by column chromatography (5:1 hexanes/EtOAc) to afford a clear colorless oil (47 mg, 99% yield).
58 % ee	With ammonium hexafluorophosphate; 1,1,1,3',3',3'-hexafluoro-propanol In 1,2-dichloro-ethane at 60℃; for 24h; Overall yield = 59 percentSpectr.; enantioselective reaction;	2.4.1. General procedure for catalytic experiments General procedure: Arylboronic acid (0.91 mmol), enone substrate (0.45 mmol), catalyst(0.06 mmol of Pd) and HFIP (2.27 mmol) were mixed in 1,2-DCE(6 ml) and heated to 60 °C in a flask. The catalyst turned from a yellowishcolor to dark black immediately after the heating was initiated.After 24 h, catalyst was filtered off, washed with DCM and EtOH,conversion was determined by 1H NMR and the product was directlyisolated by flash chromatography (hexane→THF). Enantiomeric excesswas determined by chiral-phase HPLC.

74 % ee

With palladium(II) trifluoroacetate; 2-[(S)-4,5-dihydro-4-tert-butyl-1,3-oxazol-2-yl]pyridine In 1,2-dichloro-ethane at 60℃; for 12h; Overall yield = 96 percent; enantioselective reaction;

Reference： [1]Kikushima, Kotaro; Holder, Jeffrey C.; Gatti, Michele; Stoltz, Brian M. [Journal of the American Chemical Society, 2011, vol. 133, # 18, p. 6902 - 6905]
[2]Holder, Jeffrey C.; Goodman, Emmett D.; Kikushima, Kotaro; Gatti, Michele; Marziale, Alexander N.; Stoltz, Brian M. [Tetrahedron, 2015, vol. 71, # 35, p. 5781 - 5792]
[3]Bartáček, Jan; Váňa, Jiří; Drabina, Pavel; Svoboda, Jan; Kocúrik, Martin; Sedlák, Miloš [Reactive and functional polymers, 2020, vol. 153]
[4]Sardini, Stephen R.; Stoltz, Brian M. [Organic Syntheses, 2021, vol. 98, p. 117 - 130]

27
[ 33513-42-7 ]
[ 146631-00-7 ]
[ 52805-36-4 ]

Yield	Reaction Conditions	Operation in experiment
92%	With ammonium iodide; copper(II) nitrate trihydrate; oxygen; acetic acid at 130℃; for 18h;

Reference： [1]Kim, Jinho; Choi, Jiho; Shin, Kwangmin; Chang, Sukbok [Journal of the American Chemical Society, 2012, vol. 134, # 5, p. 2528 - 2531]

28
[ 129316-09-2 ]
[ 146631-00-7 ]
[ 1374356-47-4 ]

Reference： [1]European Journal of Organic Chemistry,2012,p. 1448 - 1454

29
[ 65977-55-1 ]
[ 146631-00-7 ]
[ 1093631-81-2 ]

Yield	Reaction Conditions	Operation in experiment
	With sodium carbonate;tetrakis(triphenylphosphine) palladium(0); In 1,2-dimethoxyethane; at 70℃; for 0.5h;	A mixture of 5-chlorothieno[3,2-delta]pyridine (115 mg, 0.68 mmol), {4- [(phenylmethyl)oxy]phenyl}boronic acid (230 mg. 1.02 mmol), tetrakis(triphenylphosphine)-palladium (0) (78 mg, 0.07 mmol), and sodium carbonate (2.0 M aq, 1.20 mL, 2.37 mmol) in 1 ,2-dimethoxyethane (3.5 mL) was stirred at 70 0C for 30 min. Ethyl acetate was added and the mixture filtered through a <n="93"/>pad of Celite and silica gel. The filtrate was washed with water and brine, then concentrated. The residue was purified by silica gel chromatography eluting with 1 : 1 ethyl acetate :hexanes to give 156 mg of a tan solid.

Reference： [1]Patent: WO2008/157270,2008,A1 .Location in patent: Page/Page column 91-92

30
[ 100487-82-9 ]
[ 146631-00-7 ]
[ 1093631-76-5 ]

Yield	Reaction Conditions	Operation in experiment
82%	With potassium carbonate;tetrakis(triphenylphosphine) palladium(0); In 1,2-dimethoxyethane; at 70℃; for 2h;	8b) Methyl {3-nitro-4'-[(phenylmethyl)oxy]-4-biphenylyl} acetate <n="87"/>A mixture of methyl (4-bromo-2-nitrophenyl)acetate (1.31 g, 4.78 mmol), {4- [(phenylmethyl)oxy]phenyl}boronic acid (1.64 g, 7.17 mmol), tetrakis(triphenylphosphine)-palladium (0) (550 mg, 0.48 mmol), and sodium carbonate (2.0 M aq, 8.40 mL) in 1 ,2-dimethoxyethane (30 mL) was stirred at 70 0C for 2 h. The mixture was filtered through a pad of Celite, and the pad washed with ethyl acetate. The combined filtrates were concentrated and the residue was purified by silica gel chromatography eluting with 2:3 ethyl acetate :hexanes to give 1.49 g (82%) of methyl {3-nitro-4'-[(phenylmethyl)oxy]-4-biphenylyl} acetate as a pale yellow solid. ESI-LCMS m/z 378 (M+H)+.

Reference： [1]Patent: WO2008/157270,2008,A1 .Location in patent: Page/Page column 86

31
[ 7677-24-9 ]
[ 146631-00-7 ]
[ 52805-36-4 ]

Yield	Reaction Conditions	Operation in experiment
90%	With copper(I) oxide; oxygen; N,N`-dimethylethylenediamine In acetonitrile at 25℃; for 12h; Schlenk technique;

Reference： [1]Ye, Yong; Wang, Yanhua; Liu, Pengtang; Han, Fushe [Chinese Journal of Chemistry, 2013, vol. 31, # 1, p. 27 - 30]

32
[ 146631-00-7 ]
[ 103-16-2 ]

Yield	Reaction Conditions	Operation in experiment
95.7%	With dihydrogen peroxide In dichloromethane; water at 20℃; for 4h; Inert atmosphere;	Conversion of the phenylboronic acid 9 to the phenol 10 using hydrogen peroxide (Scheme S2) A mixture of phenylboronic acid 9 (228 mg, 1.00 mmol) and 30% aqueous hydrogen peroxide solution (0.20 mL, 2.0 mmol) in dichloromethane (1 mL) was stirred under argon at ambient temperature for 4 h. Then, 10% aqueous sodium thiosulfate solution (10 mL) was added, and the mixture was extracted with dichloromethane (3 20 mL). The combined organic layers were washed with brine (10 mL), dried over anhydrous sodium sulfate, and concentrated under reduced pressure. Column chromatography (chloroform/methanol = 80:1) gave phenol 10 (192 mg, 0.956 mmol, 95.7% yield).
67%	With oxygen; triethylamine In 2-methyltetrahydrofuran at 20℃; for 24h; Green chemistry;
	With choline chloride; dihydrogen peroxide In water at 20℃; Green chemistry;	4.3 General procedure for synthesis of compound 2 General procedure: A mixture of arylboronic acid (1.0mmol), 30% H2O2 (5equiv, 0.5mL), water (2mL) and ChCl/ HFIP (10mol%, 2 drops) was stirred at room temperature for the time indicated in Scheme 2. After completion of the reaction (indicated by TLC), the reaction mixture was extracted with EtOAc (3×10mL). The organic layer was concentrated and the resulting crude products were purified by column chromatography on silica gel using PE/EtOAc as eluent to provide the desired products.

88 %	With tetrabutylammonium tetrafluoroborate; oxygen; N,N-dimethylethylenediamine In acetonitrile at 20℃; Electrolysis; Green chemistry;
70 %	With oxygen; triethylamine In 1,2-dichloro-ethane at 20℃; Irradiation;

Reference： [1]Karaki, Fumika; Kiguchi, Takuto; Itoh, Kennosuke; Sato, Noriko; Konishi, Kazuhide; Fujii, Hideaki [Tetrahedron, 2021, vol. 97]
[2]Xu, Yu-Ting; Li, Chen-Yuan; Huang, Xiao-Bo; Gao, Wen-Xia; Zhou, Yun-Bing; Liu, Miao-Chang; Wu, Hua-Yue [Green Chemistry, 2019, vol. 21, # 18, p. 4971 - 4975]
[3]Wang, Liang; Dai, Dong-Yan; Chen, Qun; He, Ming-Yang [Journal of Fluorine Chemistry, 2014, vol. 158, p. 44 - 47]
[4]Fu, Zhengjiang; Yi, Xuezheng; Fang, Ziqi; Zhong, Tingting; He, Dongdong; Guo, Shengmei; Cai, Hu [Chemistry - An Asian Journal, 2022, vol. 17, # 24]
[5]Xiao, Yonghong; Zhu, Can-Ming; Liang, Rong-Bin; Huang, Yong-Liang; Hai, Chun-Hua; Chen, Jian-Rui; Li, Mian; Zhong, Jian-Ji; Huang, Xiao-Chun [Chemical Communications, 2023, vol. 59, # 16, p. 2239 - 2242]

33
[ 105170-27-2 ]
[ 146631-00-7 ]
[ 1609016-02-5 ]

Reference： [1]Bioorganic and Medicinal Chemistry Letters,2014,vol. 24,p. 2212 - 2221

34
[ 610-97-9 ]
[ 146631-00-7 ]
[ 893736-49-7 ]

Yield	Reaction Conditions	Operation in experiment
	With bis-triphenylphosphine-palladium(II) chloride; sodium carbonate In tetrahydrofuran; water at 20 - 80℃; Schlenk technique; Inert atmosphere;

Reference： [1]Wang, Yang; Gulevich, Anton V.; Gevorgyan, Vladimir [Chemistry - A European Journal, 2013, vol. 19, # 47, p. 15836 - 15840]

35
[ 146631-00-7 ]
[ 167627-37-4 ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 2 steps 1: tetrakis(triphenylphosphine) palladium⁽⁰⁾; sodium hydrogencarbonate / 1,2-dimethoxyethane / 4 h / Inert atmosphere; Reflux 2: potassium hydroxide; water / ethanol / Reflux

Reference： [1]Güzeller, Dilek; Ocak, Hale; Bilgin-Eran, Belkiz; Prehm, Marko; Tschierske, Carsten [Journal of Materials Chemistry C, 2015, vol. 3, # 17, p. 4269 - 4282]

36
[ 146631-00-7 ]
[ 75-05-8 ]
[ 52805-36-4 ]

Yield	Reaction Conditions	Operation in experiment
71%	With N-iodo-succinimide; 1,10-Phenanthroline; 2,2,6,6-Tetramethyl-1-piperidinyloxy free radical; 1,1,1,2,2,2-hexamethyldisilane; oxygen; copper diacetate; diisopropylamine at 20 - 150℃; Schlenk technique;

Reference： [1]Zhu, Yamin; Li, Linyi; Shen, Zengming [Chemistry - A European Journal, 2015, vol. 21, # 38, p. 13246 - 13252]

37
[ 667-27-6 ]
[ 146631-00-7 ]
[ 915799-67-6 ]

Yield	Reaction Conditions	Operation in experiment
67%	With styrene; bis-triphenylphosphine-palladium(II) chloride; iron(III)-acetylacetonate; potassium carbonate; hydroquinone; 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene In 1,4-dioxane at 80℃; for 24h; Schlenk technique; Glovebox;

Reference： [1]Feng, Zhang; Min, Qiao-Qiao; Zhang, Xingang [Organic Letters, 2016, vol. 18, # 1, p. 44 - 47]

38
[ 38557-71-0 ]
[ 146631-00-7 ]
2-(4-(benzyloxy)phenyl)-6-methylpyrazine [ No CAS ]

Reference： [1]Organic Letters,2016,vol. 18,p. 3082 - 3085

39
[ 6968-28-1 ]
[ 146631-00-7 ]
4′-benzyloxybiphenyl-3,4-dicarboxylic acid [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
15.8 g	With bis-triphenylphosphine-palladium(II) chloride; sodium carbonate; triethylamine; triphenylphosphine In 1,4-dioxane; water for 2h; Inert atmosphere; Reflux;	3.1 3.1 4′-Benzyloxy-biphenyl-3,4-dicarboxylic acid 4′-benzyloxy-biphenyl-3,4-dicarboxylic acid is prepared from commercially available [4-(benzyloxy)phenyl]-boronic acid and 5-bromo-phthalic acid. To a solution of sodium carbonate (31.27 g, 295.1 mmol) in dist. water (135 ml) is added 1,4-dioxane (210 ml), 5-bromo-phthalic acid (14.46 g, 59.0 mmol) and [4-(benzyloxy)phenyl]-boronic acid (14.82 g, 65.0 mmol) followed by bis(triphenylphosphine)palladium(II) dichloride (0.83 g, 1.2 mmol), triphenylphosphine (0.31 g, 1.2 mmol) and triethylamine (0.12 g, 1.2 mmol) under nitrogen atmosphere. The reaction mixture is heated at reflux for 2 hs. After cooling to room temperature, 400 ml dist. water is added and the reaction mixture is neutralized with conc. HCl acid to pH1 under cooling. The precipitated crude product is filtrated, washed with dist. water, and further purified by recrystallization from acetonitrile to provide gray crystals of 4′-benzyloxy-biphenyl-3,4-dicarboxylic acid (15.8 g.

Reference： [1]Current Patent Assignee: MERCK KGAA - JP2015/7041, 2015, A Location in patent: Paragraph 0457; 0458

40
[ 23351-91-9 ]
[ 146631-00-7 ]
4′-benzyloxybiphenyl-3,5-dicarboxylic acid [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
17.4 g	With bis-triphenylphosphine-palladium(II) chloride; sodium carbonate; triethylamine; triphenylphosphine; In 1,4-dioxane; water; for 2h;Inert atmosphere; Reflux;	4?-benzyloxy-biphenyl-3,5-dicarboxylic acid is prepared from commercially available [4-(benzyloxy)phenyl]-boronic acid and <strong>[23351-91-9]5-bromo-isophthalic acid</strong>. To a solution of sodium carbonate (31.26 g, 295.0 mol) in dist. water (135 ml) is added 1,4-dioxane (210 ml), <strong>[23351-91-9]5-bromo-isophthalic acid</strong> (14.46 g, 59.0 mmol) and [4-(benzyloxy)phenyl]-boronic acid (14.82 g, 65.0 mol) followed by bis(triphenylphosphine)palladium(II) dichloride (0.83 g, 1.2 mmol), triphenylphosphine (0.31 g, 1.2 mmol) and triethylamine (0.12 g, 1.2 mmol) under nitrogen atmosphere. The reaction mixture is heated at reflux for 2 hs. After cooling to room temperature 400 ml dist. water is added, and the reaction mixture is neutralized with conc. HCl acid under cooling to pH1. The precipitated crude product is filtrated, washed with dist. water, and further purified by recrystallization from acetonitrile to provide gray crystals of 4?-benzyloxy-biphenyl-3,5-dicarboxylic acid (17.4 g).

Reference： [1]Patent: JP2015/7041,2015,A .Location in patent: Paragraph 0445; 0446; 0447

41
[ 146631-00-7 ]
2,2‐difluoro‐2‐(triphenylphosphonio)acetate [ No CAS ]
[ 915799-67-6 ]

Yield	Reaction Conditions	Operation in experiment
80%	With tetrakis(triphenylphosphine) palladium⁽⁰⁾; 1,3-cyclopentadione; calcium hydroxide In para-xylene; water at 90℃; for 3h; Schlenk technique; Inert atmosphere;

Reference： [1]Deng, Xiao-Yun; Lin, Jin-Hong; Xiao, Ji-Chang [Organic Letters, 2016, vol. 18, # 17, p. 4384 - 4387]

42
[ 102127-34-4 ]
[ 146631-00-7 ]
C₂₀H₁₈O₃ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
8.6 g	With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; sodium carbonate; In 1,4-dioxane; water;Inert atmosphere; Reflux;	1a: To a solution of <strong>[102127-34-4]4-bromo-3-methoxylphenol</strong> (10.00 g, 49.2 mmol) and 4-benzyloxyphenylboronic acid (13.00 g, 54.2 mmol) in 170 ml 1,4-dioxane was added sodium carbonate (10.44 g, 98.5 mmol) and 40 ml distilled water. After thoroughly degassing with argon, [1,1?-bis(diphenylphosphino)ferrocene]-dichloropalladium(II) (1.08 g, 1.50 mmol) is added. The reaction mixture is heated to reflux and stirred overnight. After cooling to room temperature, the reaction mixture is carefully neutralized with 2 M HCl. The aqueous phase is separated and extracted with ethyl acetate. The organic phase is combined, dried over anhydrous sodium sulfate, and filtrated through silica gel. After removing solvent in vacuo, the obtained crude product is recrystallized from heptane/toluene solvent mixture to provide the product as off-white crystal (8.6 g).

Reference： [1]Patent: US2016/362606,2016,A1 .Location in patent: Paragraph 0527

43
[ 75-45-6 ]
[ 146631-00-7 ]
[ 915799-67-6 ]

Yield	Reaction Conditions	Operation in experiment
91%	With tris-(dibenzylideneacetone)dipalladium⁽⁰⁾; potassium carbonate; hydroquinone; 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene In 1,4-dioxane at 110℃; for 48h; Inert atmosphere; Sealed tube;	General procedure for palladium-catalysed difluoromethylation of ArB(OH)₂ or Ar-Beg with ClCF₂H. General procedure: To a 25 ml sealed tube were added anhydrous K2CO3 (powder, 4.0 equiv.), hydroquinone (2.0 equiv.), Pd2(dba)3 (2.5 mol%), Xantphos (7.5 mol%) and ArB(OH)2 (0.3 or 0.5 mmol) or Ar-Beg (0.3 or 0.5 mmol) under argon. A solution of ClCF2H in 1,4-dioxane (2.0 M, 1.5 ml for 0.3 mmol scale or 2.5 ml for 0.5 mmol scale, 10 equiv.) and fresh distilled 1,4-dioxane (1.0 ml for 0.3 mmol scale or 2.5 ml for 0.5 mmol scale) were added subsequently. The sealed tube was screw capped and heated to 110 °C (oil bath). After stirring for 48 h, the reaction was cooled to room temperature and fluorobenzene (1.0 equiv.) was added. The yield was determined by 19F NMR before working up. The reaction mixture was then diluted with ethyl acetate, filtered through a pad of Celite and concentrated. The residue was purified with silica gel chromatography to provide the desired product.

Reference： [1]Feng, Zhang; Min, Qiao-Qiao; Fu, Xia-Ping; An, Lun; Zhang, Xingang [Nature Chemistry, 2017, vol. 9, # 9, p. 918 - 923]

44
[ 349-03-1 ]
[ 146631-00-7 ]
C₂₀H₁₄F₃NO₃ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
90%	With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In 1,4-dioxane; water;Inert atmosphere; Reflux;	General procedure: 2-halonitrobenzene (1 or 2) (1.0 equiv.), the appropriate substituted boronic acid (1.2 equiv.) and K2CO3 (2 equiv.) were taken up in 1.5-2.5mL of dioxane/H2O (2:1) and sparged with N2 for 5min. Then, Pd(PPh3)4 (0.05 equiv.) was added, and N2 sparging continued for an additional 5min before the reaction was fitted with a condenser and immersed in an oil bath overnight. The reaction mixture was cooled, diluted with Et2O (50mL) and filtered. The filtrate was washed with H2O (2×20mL) and brine, dried over MgSO4 and concentrate under reduced pressure. HPLC purification was performed by semi-preparative reversed-phase HPLC (on a Synergi Fusion C18 column: 250×10.00mm, 10mu, 80A, flow rate=4mL/min; NUCLEODUR 100-5 C8 ec) using the gradient conditions reported below for each compound. The final products were obtained with high purity (>97%) as detected by HPLC analysis and were fully characterized by ESMS and NMR spectra. The compound 1a was selected as representative for fully NMR characterization of the series.

Reference： [1]European Journal of Medicinal Chemistry,2018,vol. 143,p. 1419 - 1427

45
[ 1511-62-2 ]
[ 146631-00-7 ]
[ 915799-67-6 ]

Yield	Reaction Conditions	Operation in experiment
68%	With dmap; dibromobis(triphenylphosphine)nickel(II); 5,5'-dibromo-2,2'-dipyridyl; potassium carbonate In tetrahydrofuran at 80℃; for 17h; Schlenk technique; Inert atmosphere; Sealed tube;

Reference： [1]Fu, Xia-Ping; Xiao, Yu-Lan; Zhang, Xingang [Chinese Journal of Chemistry, 2018, vol. 36, # 2, p. 143 - 146]

46
[ 762-51-6 ]
[ 146631-00-7 ]
1-benzyloxy-4-(2-fluoroethyl)benzene [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
89%	With potassium phosphate; 4,4'-Dimethoxy-2,2'-bipyridin; nickel dibromide; In diethylene glycol dimethyl ether; at 80℃; for 24h;Inert atmosphere; Sealed tube;	Under the nitrogen atmosphere,In a sealed tube, p-benzyloxyphenylboronic acid (3.421 g, 15.0 mmol) was added in sequence.Potassium phosphate anhydrous(6.368g, 30.0mmol),After adding solvent diethylene glycol dimethyl ether (50mL) and stirring,<strong>[762-51-6]1-fluoro-2-iodoethane</strong> (1.739 g, 10.0 mmol) was added in sequence,4,4'-Dimethoxy-2,2'-bipyridine (0.238 g, 1.1 mmol)And NiBr2 (0.219 g, 1.0 mmol),After sealing, the reaction is stirred for 24 hours in an oil bath at 80C.Cool the reaction solution to room temperatureThe insoluble matter in the reaction solution was filtered off with a celite sand core funnel.A small amount of ether was rinsed and the filtrate was collected. To the filtrate was added 60 mL of water,The aqueous phase was extracted with ether (40 mL×3).The organic phase is combined and the organic phase isIt is washed with saturated saline, dried over anhydrous sodium sulfate and filtered.The solvent is recovered by rotary evaporation and the residue is separated by silica gel column chromatography.The product was 2.050 g and the yield was 89%.

Reference： [1]Patent: CN107628926,2018,A .Location in patent: Paragraph 0135-0139

47
[ 4068-75-1 ]
[ 146631-00-7 ]
4′-benzyloxy-4-hydroxybiphenyl-3-carboxylic acid [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
80%	With palladium diacetate; potassium carbonate; triphenylphosphine In water; N,N-dimethyl-formamide at 100℃; for 24h; Inert atmosphere; Sealed tube;

Reference： [1]Moya-Garzón, María Dolores; Martín Higueras, Cristina; Peñalver, Pablo; Romera, Manuela; Fernandes, Miguel X.; Franco-Montalbán, Francisco; Gómez-Vidal, José A.; Salido, Eduardo; Díaz-Gavilán, Mónica [Journal of Medicinal Chemistry, 2018, vol. 61, # 16, p. 7144 - 7167]

48
[ 16870-28-3 ]
[ 146631-00-7 ]
4-(4-benzyloxyphenyl)-2-hydroxybenzoic acid potassium salt [ No CAS ]

Reference： [1]Journal of Medicinal Chemistry,2018,vol. 61,p. 7144 - 7167

49
[ 16870-28-3 ]
[ 146631-00-7 ]
4-[4'-(benzyloxy)phenyl]-2-hydroxybenzoic acid [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
100%	With palladium diacetate; potassium carbonate; triphenylphosphine; In water; N,N-dimethyl-formamide; at 100℃; for 3h;Microwave irradiation; Inert atmosphere; Sealed tube;	<strong>[16870-28-3]2-hydroxy-4-iodobenzoic acid</strong> (50 mg, 0.189 mmol), acid 4-(benzyloxy)phenylboronic (51.8 mg, 0.227 mmol), PPh3 (7.4 mg, 0.028 mmol), K2CO3 (91.4 mg, 0.662 mmol), Pd(AcO)2 (2.12 mg, 0.0095 mmol), 1:1 DMF: H2O (2 ml) were used. In this case, prior to chromatographic purification, the residue from evaporating the filtrate was resuspended in acetonitrile. The precipitate was separated from the liquid phase and the latter was discarded. The solid was then purified by flash chromatography (elution with AcOEt: CH3CN:H2O:CH3OH 60:10:10:10 mixture). 95 was obtained in the form of a white solid. Yield after purification: 100 % (62 mg). 1H NMR (400 MHz, acetone-d6) delta 7.93 (d, J = 8.3 Hz, 1H), 7.70 (m, 2H), 7.51 (m, 2H), 7.41 (m, 2H), 7.34 (m, 1H), 7.23 (dd, J = 8.28, 1.82 Hz, 1H), 7.19 (d, J = 1.8 Hz, 1H), 7.14 (m, 2H), 5.21 (s, 2H). 13C NMR (101 MHz, acetone-d6) delta 172.5 (CO), 163.3 (C), 160.4 (C), 149.0 (C), 138.2 (C), 132.7 (C), 131.8(CH), 129.3 (CH), 129.2 (CH), 128.7 (CH), 128.5 (CH), 118.3 (CH), 116.2 (CH), 115.2 (CH), 111.4 (C), 70.6 (CH2). HRMS (TOF, ES-): Calculated for C20H15O4: (M-H)-: m/z 319.0970. 319.0964 found (deviation 1.9 ppm).

Reference： [1]Patent: EP3593803,2020,A2 .Location in patent: Paragraph 0074; 0080
[2]Journal of Medicinal Chemistry,2018,vol. 61,p. 7144 - 7167

50
[ 146631-00-7 ]
5-bromo-3-thiocyanatoindole [ No CAS ]
[ 52805-36-4 ]

Yield	Reaction Conditions	Operation in experiment
90%	With N,N,N-trimethyl-2-(sulfooxy)ethanaminium palladium(II) chloride; sodium carbonate In tetrahydrofuran; 5,5-dimethyl-1,3-cyclohexadiene; water for 2h;

Reference： [1]Vaghasiya, Beena K.; Satasia, Shailesh P.; Thummar, Rahul P.; Kamani, Ronak D.; Avalani, Jemin R.; Sapariya, Nirav H.; Raval, Dipak K. [Journal of Sulfur Chemistry, 2018, vol. 39, # 5, p. 507 - 515]

51
[ 3226-37-7 ]
[ 146631-00-7 ]
[ 52805-36-4 ]

Yield	Reaction Conditions	Operation in experiment
89%	With N,N,N-trimethyl-2-(sulfooxy)ethanaminium palladium(II) chloride; sodium carbonate In tetrahydrofuran; 5,5-dimethyl-1,3-cyclohexadiene; water for 2h;

52
[ 2132-62-9 ]
[ 19099-54-8 ]
[ 146631-00-7 ]
(E)-4,4'-(1-(4-(benzyloxy)phenyl)-2-(2-isopropylphenyl)ethene-1,2-diyl)bis(methoxybenzene) [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
53%	With tetrakis(triphenylphosphine) palladium⁽⁰⁾; sodium carbonate; bis[2-(diphenylphosphino)phenyl] ether In N,N-dimethyl-formamide at 120℃; for 24h; Inert atmosphere;	9 Example 9; (E)-4,4'-(1-(4-(Benzyloxy)phenyl)-2-(2-isopropylphenyl)ethene-1,2-diyl)bis(methoxybenzene) Preparation 0.3 mmol of sodium carbonate and 0.1 mmol of 1,2-bis(4-methoxyphenyl)acetylene,Tetrakis(triphenylphosphine palladium) 0.005 mmol, bis(2-diphenylphosphinophenyl)ether 0.005 mmol,0.2 mmol of (4-(benzyloxy)phenyl)boronic acid, 0.3 mmol of 2-isopropyliodobenzene, and 1 mL of N,N-dimethylformamide were added to a 15 mL reaction tube.Nitrogen was repeatedly filled 10 times, placed in an oil bath at 120 ° C, and reacted for 24 hours;Cooled to room temperature, the reaction was diluted with ethyl acetate, washed with water three times, the organic phase dried over anhydrous Na2SO4, filtered, and concentratedPurification by thin layer chromatography to give 31.8mg of the desired product, yield 53%.
53%	With tetrakis(triphenylphosphine) palladium⁽⁰⁾; sodium carbonate; bis[2-(diphenylphosphino)phenyl] ether In N,N-dimethyl-formamide at 120℃; for 24h; Inert atmosphere;

Reference： [1]Current Patent Assignee: HUAQIAO UNIVERSITY - CN109879713, 2019, A Location in patent: Paragraph 0055-0058
[2]Chen, Yanhui; Cheng, Guolin; Lan, Yu; Liu, Shihan; Lv, Weiwei; Wen, Si [ACS Catalysis, 2020, vol. 10, # 18, p. 10516 - 10522]

53
[ 618-58-6 ]
[ 146631-00-7 ]
C₃₃H₂₆O₄ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
80%	With bis-triphenylphosphine-palladium(II) chloride; sodium carbonate; triethylamine In 1,4-dioxane; water for 3h; Reflux;	3 14: 12 (30 g, 107 mmol), 13 (48.9 g, 214 mmol), sodium carbonate (113.6 g, 1.07 mol), bis(triphenylphosphine)palladium dichloride (2 g, 4.2 m) A mixture of 750 ml of dioxane, 48 ml of water and 0.5 ml of triethylamine was heated under reflux for 3 hours. After cooling to room temperature, add 200 ml of distilled water and mix the reaction The material was neutralized to pH 1 with concentrated HCl acid under cooling. The precipitate was filtered and dried in vacuo. At room temperature in 300 mlStir in 1:1 toluene/n-heptane and filter for further purification (removal of residual catalyst) and drying to obtain 55.8 g (80%) of 14 as a colorless solid.

Reference： [1]Current Patent Assignee: MERCK KGAA - CN106414665, 2019, B Location in patent: Paragraph 0669; 0670; 0671; 0672; 0673

54
[ 1276110-38-3 ]
[ 146631-00-7 ]
tert-butyl (R)-3-(4-amino-3-(4-(benzyloxy)phenyl)-1H-pyrazolo[3,4-d]pyrimidin-1-yl)piperidine-1-carboxylate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
85%	With tetrakis(triphenylphosphine) palladium⁽⁰⁾; potassium carbonate In 1,4-dioxane; water at 80℃; for 6h;	1.1-5.1 As shown in Figure 1, a method for preparing ibrutinib-d5 comprises the following steps: (1) 20 g of (3R)-1-Boc-3-(4-amino-3-iodo-1H-pyrazolo[3,4-D]pyrimidin-1-yl)piperidine was suspended in 300 mL of 1 , in 4-dioxane and 40 mL of water, 12.5 g of 4-benzyloxybenzeneboronic acid was added, 10 g of potassium carbonate and 1.2 g of tetrakistriphenylphosphine palladium were sequentially added, and the mixture was reacted at 80 ° C for 6 hours. TLC showed the reaction was complete, the reaction solution was concentrated to remove 1,4-dioxane, and 50 mL of water was added to room temperature for 3 hours. After suction filtration, the filter cake was washed with water and dried to obtain 20 g of Compound C in a yield of 85%;
73%	With chloro(2-dicyclohexylphosphino-2′,6′-diisopropoxy-1,1′-biphenyl)[2-(2′-amino-1,1′-biphenyl)]palladium(II); potassium carbonate In 1,4-dioxane; water at 95℃; for 1.5h; Sealed tube;

Reference： [1]Current Patent Assignee: TLC NANJING PHARMACEUTICAL RES AND DEVELOPMENT - CN109988175, 2019, A Location in patent: Paragraph 0010-0013
[2]Kriegelstein, Michal; Hroch, Miloš; Marek, Aleš [Journal of labelled compounds and radiopharmaceuticals, 2021, vol. 64, # 13, p. 500 - 512]

55
[ 40396-54-1 ]
[ 146631-00-7 ]
1-(3'-(benzyloxy)-[1,1'-biphenyl]-3-yl)-2-phenylethane-1,2-dione [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
79%	With bis-triphenylphosphine-palladium(II) chloride; potassium carbonate In 1,4-dioxane; water at 100℃; for 3h; Inert atmosphere;	1-([1,1':4',1''-terphenyl]-3-yl)-2-phenylethane-1,2-dione(T-2) General procedure: A dried radius flask was charged with T-1 (115.2 mg, 0.4 mmol, 1.0 equiv.),4-biphenylboronic acid (158.4 mg, 0.8 mmol, 2.0 equiv.), Pd(PPh3)2Cl2(28.08 mg, 0.04 mmol, 10 mol %), K2CO3 (165.6mg, 1.2 mmol, 3 equiv.), H2O (100 μL) and 1,4-dioxane (4.0 mL). Themixture was stirred at 100 °C for 3 h under nitrogen. Upon completion of thereaction as monitored by TLC, the reaction was allowed to cool to roomtemperature, and extracted with ethyl acetate (20 mL × 3). The organic phasewas collected and washed with brine, dried over with anhydrous Na2SO4,ltered, and concentrated. The filtrate was evaporated under reduced pressure,and the residue was purified by column chromatography on silica gel usingpetroleum ether/ethyl acetate as eluent to afford the desired product T-2 (136.4 mg, 94 %) as yellow solid.

Reference： [1]Fan, Tian-Yuan; Wu, Wen-Yu; Yu, Shao-Peng; Zhong, Yue; Zhao, Chao; Chen, Min; Li, He-Min; Li, Nian-Guang; Chen, Zhi; Chen, Sai; Sun, Zhi-Hui; Duan, Jin-Ao; Shi, Zhi-Hao [Bioorganic and Medicinal Chemistry Letters, 2019, vol. 29, # 24]

56
[ 146631-00-7 ]
[ 71597-85-8 ]

Yield	Reaction Conditions	Operation in experiment
87%	With palladium 10% on activated carbon; hydrogen; In ethyl acetate; at 30 - 35℃; under 2250.23 Torr; for 5h;	Under the protection of nitrogen, 24.7g (0.094mol) of the above solid was added to 80mL of tetrahydrofuran, which was completely dissolved under stirring, and then cooled to -10 to 0 .The 1.3M isopropylmagnesium chloride-lithium chloride / tetrahydrofuran solution (94mL, 0.122mol) was added dropwise. After the addition was complete, the heat preservation exchange reaction was continued for 1 hour.After the reaction was completed, the above solution was added dropwise to a solution (50 mL) of trimethyl borate (14.7 g, 0.141 mol) dissolved in tetrahydrofuran,After the dropwise addition was completed, the heat preservation was continued to stir for 5 hours, and then it was naturally raised to room temperature and stirred to react overnight.Add 10% hydrochloric acid to quench, adjust pH = 3-4, extract twice with ethyl acetate, and wash with saturated brine.The ethyl acetate layer (containing 19.6g of product in the external calibration solution) was transferred to the hydrogenation reactor,Add 0.8 grams of 10% wet palladium carbon, heat to 30-35 , fill with hydrogen pressure 0.3MPa, stir the reaction for 5 hours,After the reaction is completed, the palladium carbon is filtered off (for reuse), the filtrate is distilled under reduced pressure, and the crude product is slurried with acetone and heptane,11.30 g of white solid was obtained with a total yield of 87% in two steps and a purity of 99.4% by HPLC.

Reference： [1]Patent: CN111072698,2020,A .Location in patent: Paragraph 0022-0023; 0025

57
[ 235426-30-9 ]
[ 146631-00-7 ]
2-(4-(benzyloxy)phenyl)-1,4-dimethyl-1H-imidazole [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
63%	With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; potassium carbonate In 1,4-dioxane; water at 100℃; for 18h;	1 Step 1. 2-(4-(benzyloxy)phenyl)-l,4-dimethyl-lH-imidazole [00203] To a solution of (4-(benzyloxy)phenyl)boronic acid (1.30 g, 5.70 mmol) in 1,4- dioxane (20 mL) was added 2-bromo-l, 4-dimethyl- lH-imidazole (1.00 g, 5.71 mmol), Pd(dppf)Cl2 (417 mg, 0.58 mmol), potassium carbonate (1.60 g, 11.6 mmol), and water (6 mL). The resulting mixture was stirred for 18 h at 100 °C and then cooled to rt. The reaction mixture was poured into water (20 mL) and then extracted with ethyl acetate (3 x 30 mL). The combined organic layers were dried over anhydrous sodium sulfate, filtered, and concentrated under vacuum. The resulting crude product was purified by silica gel chromatography (eluting with 0: 100 to 40:60 ethyl acetate/petroleum ether) to afford 2-(4-(benzyloxy)phenyl)-l,4-dimethyl- lH-imidazole as a black solid (1.00 g, 63%). LCMS (ESI, m/z ) 279 [M+H]+.

Reference： [1]Current Patent Assignee: FORMA THERAPEUTICS, INC. - WO2020/139988, 2020, A1 Location in patent: Paragraph 00203

58
[ 146631-00-7 ]
[ 40503-90-0 ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 2 steps 1.1: potassium carbonate; tetrakis(triphenylphosphine) palladium⁽⁰⁾ / toluene / 6 h / 80 °C / Inert atmosphere 2.1: 5%-palladium/activated carbon; hydrogen / ethanol; water / 6 h / 30 - 105 °C / 750.08 - 6000.6 Torr / Autoclave 2.2: 1 h / 0 - 10 °C

Reference： [1]Current Patent Assignee: HEBEI MILESTONE ELECTRONIC MATERIAL CO LTD - CN112898133, 2021, A

59
[ 126937-43-7 ]
[ 146631-00-7 ]
1-benzyl 2-methyl 4-(4-(benzyloxy)phenyl)piperazine-1,2-dicarboxylate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
40%	With pyridine; oxygen; In dichloromethane; at 20℃; for 48.0h;Molecular sieve;	A mixture of <strong>[126937-43-7]1-benzyl 2-methyl piperazine-1,2-dicarboxylate</strong> (2 g, 7.19 mmol), (4-(benzyloxy)phenyl)boronic acid (3.3 g, 14.37 mmol) and copper (II) acetate (1.30 g, 7.19 mmol) in dichloromethane (60 mL) was added pyridine (1.2 mL, 14.37 mmol) and 2 g of 4A molecular sieves. The reaction mixture was stirred at room temperature for 48 h under oxygen atmosphere. The resulting suspension was filtered through Celite pad, washed with 50 mL of dichloromethane and filtrate was evaporated under reduced pressure to give the crude residue. The crude residue was purified by flash chromatography (0 - 10% EtOAc in pet ether) to afford 1-benzyl 2-methyl 4-(4- (benzyloxy)phenyl)piperazine-1,2-dicarboxylate (2.2 g, 8.90 mmol, 40% yield) as off- white solid. LC-MS, [M+H]+= 461.1, (Method F, tR= 3.37 min).1H NMR (300MHz, CDCl3): δ ppm 7.48 - 7.29 (m, 10H), 6.97 - 6.84 (m, 4H), 5.27 - 5.16 (m, 2H), 5.07 - 5.00 (m, 2H), 4.96 - 4.77 (m, 1H), 4.16 - 3.93 (m, 2H), 3.77 (s, 3H), 3.51 - 3.23 (m, 2H), 2.93 - 2.65 (m, 2H). (Mixture of rotamers).
40%	With pyridine; oxygen; In dichloromethane; at 20℃; for 48.0h;Molecular sieve;	A mixture of <strong>[126937-43-7]1-benzyl 2-methyl piperazine-1,2-dicarboxylate</strong> (2 g, 7.19 mmol), (4-(benzyloxy)phenyl)boronic acid (3.3 g, 14.37 mmol) and copper (II) acetate (1.30 g, 7.19 mmol) in dichloromethane (60 mL) was added pyridine (1.2 mL, 14.37 mmol) and 2 g of 4A molecular sieves. The reaction mixture was stirred at room temperature for 48 h under oxygen atmosphere. The resulting suspension was filtered through Celite pad, washed with 50 mL of dichloromethane and filtrate was evaporated under reduced pressure to give the crude residue. The crude residue was purified by flash chromatography (0 - 10% EtOAc in pet ether) to afford 1-benzyl 2-methyl 4-(4- (benzyloxy)phenyl)piperazine-1,2-dicarboxylate (2.2 g, 8.90 mmol, 40% yield) as off- white solid. LC-MS, [M+H]+= 461.1, (Method F, tR= 3.37 min).1H NMR (300MHz, CDCl3): δ ppm 7.48 - 7.29 (m, 10H), 6.97 - 6.84 (m, 4H), 5.27 - 5.16 (m, 2H), 5.07 - 5.00 (m, 2H), 4.96 - 4.77 (m, 1H), 4.16 - 3.93 (m, 2H), 3.77 (s, 3H), 3.51 - 3.23 (m, 2H), 2.93 - 2.65 (m, 2H). (Mixture of rotamers).

Reference： [1]Patent: WO2021/231243,2021,A1 .Location in patent: Page/Page column 58-59
[2]Patent: WO2021/231243,2021,A1 .Location in patent: Page/Page column 58-59

60
[ 3102-33-8 ]
[ 146631-00-7 ]
C₁₈H₂₀O₂ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
68%	With tripotassium phosphate tribasic; bis[chlorido(η2,η2-cycloocta-1,5-diene)rhodium(I)] In 1,4-dioxane; lithium hydroxide monohydrate at 60℃; Inert atmosphere;

Reference： [1]Dong, Guangbin; Xu, Yan; Zhou, Xukai [Journal of the American Chemical Society, 2021, vol. 143, # 48, p. 20042 - 20048] Zhou, Xukai; Yu, Tingting; Dong, Guangbin [Journal of the American Chemical Society, 2022, vol. 144, # 22, p. 9570 - 9575]

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[ 146631-00-7 ] Synthesis Path-Upstream 1~7

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Organoboron

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