Name: 66256-28-8|4-Fluoro-1-iodo-2-methylbenzene|97%
Brand: Ambeed
SKU: A231057
Price: 5.0 USD
Availability: InStock
Rating: 98 (29 reviews)

1
[ 352-70-5 ]
[ 452-79-9 ]
[ 66256-28-8 ]

Reference： [1]Journal of the Indian Chemical Society,1944,vol. 21,p. 112,114

2
[ 463-49-0 ]
[ 66256-28-8 ]
[ 51608-60-7 ]
<i>N</i>-[3-(4-fluoro-2-methyl-phenyl)-1-phenyl-but-3-enyl]-4-methyl-benzenesulfonamide [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
53%	With indium; trifuran-2-yl-phosphane In N,N-dimethyl-formamide

Reference： [1]Cooper, Ian R.; Grigg, Ronald; MacLachlan, William S.; Thornton-Pett, Mark; Sridharan, Visuvanathar [Chemical Communications, 2002, # 13, p. 1372 - 1373]

3
[ 877868-59-2 ]
[ 66256-28-8 ]
C₂₀H₁₅NSO₂F₂ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	With tris-(o-tolyl)phosphine In acetonitrile at 170℃; for 0.333333h; microwave irradiation;

Reference： [1]Wilson, Kevin J.; van Niel, Monique B.; Cooper, Laura; Bloomfield, Dawn; O'Connor, Desmond; Fish, L. Rebecca; MacLeod, Angus M. [Bioorganic and Medicinal Chemistry Letters, 2007, vol. 17, # 9, p. 2643 - 2648]

4
[ 680-15-9 ]
[ 66256-28-8 ]
[ 80245-26-7 ]

Yield	Reaction Conditions	Operation in experiment
	With copper(l) iodide In 4-methyl-morpholine at 120℃; for 5.5h;	169; a To a suspension (200 ml) of 5-fluoro-2-iodotoluene (110.6 g) and copper iodide (76.2 g) in N-methylmorpholine was added dropwise methyl fluorosulfonyl(difluoro)acetate (150 g) with stirring at 120° C. over 2 hr. The stirring was continued at the same temperature for 3.5 hr and the reaction solution was distilled under atmospheric pressure to give a yellow liquid. This was diluted with hexane (300 ml) and washed with saturated brine. The organic layer was dried over sodium sulfate and sodium sulfate was filtered off. The obtained hexane solution was added dropwise over 1.5 hr to a mixture of tetrahydrofuran (300 ml) and 1.0 M solution (600 ml) of s-butyllithium in hexane, which had been cooled to -78° C. and stirred. The stirring was continued for 1 hr and N,N-dimethylformamide (57 ml) was added dropwise. After completion of the dropwise addition, 2N aqueous hydrochloric acid (600 ml) was added and the mixture was allowed to warm to room temperature. This was extracted with hexane and washed with water and saturated brine. The organic layer was dried over sodium sulfate and sodium sulfate was filtered off. The filtrate was concentrated to give the title compound (61.54 g, 52%). 1H-NMR(CDCl3, 300 MHz)δ: 2.56(s, 3H), 7.14(d, J=10.7 Hz, 1H), 8.15(d, J=6.8 Hz, 1H), 10.32(s, 1H).

Reference： [1]Current Patent Assignee: JAPAN TOBACCO INC - US2005/59810, 2005, A1 Location in patent: Page/Page column 37

5
[ 66256-28-8 ]
[ 557-21-1 ]
[ 147754-12-9 ]

Yield	Reaction Conditions	Operation in experiment
	tetrakis(triphenylphosphine) palladium(0); In N,N-dimethyl-formamide; at 80℃; for 1.5h;	[0137] 5-Fluoro-2-iodotoluene (3 g, 12.7 mmol) was stirred in DMF (40 mL) under argon and Zn(CN)2 (1.94 g, 16.5 mmol) and Pd(PPh3)4 (1.47 g, 1.27 mmol) were added. The reaction was stirred at 80 °C for 1.5 hours. The reaction was partitioned between ethyl acetate and water and the organic layer was washed with brine and dried over anhydrous Na2-SO4. The solvent was removed under reduced pressure to afford a yellow solid (2.90 g), confirmed by GC MS.

Reference： [1]Patent: WO2006/20879,2006,A1 .Location in patent: Page/Page column 55

6
[ 66256-28-8 ]
[ 121459-86-7 ]
[ 1080649-28-0 ]

Yield	Reaction Conditions	Operation in experiment
32%	With norborn-2-ene; trifuran-2-yl-phosphane; palladium diacetate; caesium carbonate In acetonitrile at 105℃; for 11h;

Reference： [1]Martins, Andrew; Lautens, Mark [Journal of Organic Chemistry, 2008, vol. 73, # 22, p. 8705 - 8710]

7
[ 5625-67-2 ]
[ 66256-28-8 ]
[ 756818-04-9 ]

Yield	Reaction Conditions	Operation in experiment
10.58%	With potassium phosphate for 3h; Heating / reflux;	28 The 1-(4-fluoro-2-methylphenyl)-2-piperazinone used in the above synthesis was prepared in the following manner:; To a stirred mixture of 2-piperazinone (500mg, 4.99 mmol), 4-fluoro-1-iodo-2- methylbenzene (1000 mg, 4.24 mmol) in 1 ,4-dioxane (15 ml) was added potassium phosphate (5301 mg, 24.97 mmol), copper (I) iodide (951 mg, 4.99 mmol) and trans- N,N-dimethylcyclohexane-1 ,2-diamine (0.787 ml, 4.99 mmol) and the mixture was heated at reflux under argon for 3 hours. The mixture was cooled to room temperature and then diluted with MeOH. Reaction mixture was filtered through a pad of celite, washing with MeOH and then the filtrate evaporated in vacuo. Residue was dissolved in DCM and a solution of 0.88 aqueous NH3 (~10ml) in water(~100ml), and product was extracted into DCM (x2). Combined organic extracts were washed with water (x1 ) and dried (MgSθ4). Solvent was evaporated in vacuo to give a dark brown oil (~1g). Crude product was purified by reverse phase column chromatography, eluting with 5-100% acetonitrile in water. Relevant fractions were passed through an SCX cartridge, eluting first with MeOH and then with 2M NH3 /MeOH. Basic fractions were combined and solvent evaporated in vacuo to give a dark yellow oil. This was purified further by column chromatography on silica gel, eluting with 0-20% MeOH / DCM. Relevant fractions were combined and solvent evaporated in vacuo to give a yellow gum, 1-(4-fluoro-2-methylphenyl)-2- piperazinone (110 mg, 0.528 mmol, 10.58 % yield).

Reference： [1]Current Patent Assignee: GLAXOSMITHKLINE PLC - WO2009/53459, 2009, A1 Location in patent: Page/Page column 55-56

8
[ 66256-28-8 ]
[ 1261852-14-5 ]

Yield	Reaction Conditions	Operation in experiment
55%	With N-Bromosuccinimide; dibenzoyl peroxide In tetrachloromethane for 60h; Reflux;	2-(Bromomethyl)-4-fluoro-1-iodobenzene (11c) N-Bromosuccinimide (NBS, 4.15 g, 23.3 mmol) and benzoylperoxide (55 mg, 0.21 mmol) were added to a solution of 4-fluoro-1-iodo-2-methylbenzene 10c (5 g, 21.2 mmol) in CCl4(50 mL). The mixture was heated to reflux for 60 hours then cooled to room temperature. The mixture was concentrated under reduced pressure. Purification over silica eluting with pentane provided the title compound as a white solid (3.67 g, 55% yield). 1H NMR (400MHz, CDCl3): d 7.80(dd, 1H), 7.25 (dd, 1H), 6.75 (dd, 1H), 4.55 (s, 2H); Also a known commercially available compound
	With N-Bromosuccinimide; dibenzoyl peroxide In tetrachloromethane Reflux;

Reference： [1]Roberts, Lee R.; Corbett, Matthew S.; Fussell, Steven J.; Hitzel, Laure; Jessiman, Alan S.; Mason, Helen J.; Osborne, Rachel; Ralph, Michael J.; Stennett, Adam S.D.; Wheeler, Simon; Storer, R. Ian [Tetrahedron Letters, 2015, vol. 56, # 47, p. 6546 - 6550]
[2]Location in patent: scheme or table Roberts, Lee R.; Bryans, Justin; Conlon, Kelly; McMurray, Gordon; Stobie, Alan; Whitlock, Gavin A. [Bioorganic and Medicinal Chemistry Letters, 2008, vol. 18, # 24, p. 6437 - 6440]

9
[ 27007-53-0 ]
[ 66256-28-8 ]
[ 1254709-91-5 ]

Yield	Reaction Conditions	Operation in experiment
56%	With norborn-2-ene; palladium diacetate; caesium carbonate; triphenylphosphine In 1,2-dimethoxyethane at 90℃; for 12h; Sealed vial;

Reference： [1]Martins, Andrew; Candito, David A.; Lautens, Mark [Organic Letters, 2010, vol. 12, # 22, p. 5186 - 5188]

10
[ 2916-68-9 ]
[ 66256-28-8 ]
[ 1338215-44-3 ]

Yield	Reaction Conditions	Operation in experiment
92%	With copper(l) iodide; 1,10-Phenanthroline; caesium carbonate In toluene at 110℃; for 14h; Inert atmosphere; Sealed tube;	General procedure for coupling reaction General procedure: An oven-dried resealable Schlenk tube were charged with CuI (10 mol %), 1,10-phenanthroline (20% mol), Cs2CO3 (1.4-2.0 mmol),aryl iodide (1.0 mmol).The Schlenk tube was evacuated and back-filled with argon and 2-trimethylsilyl alcohol (3mmol) and toluene (0.5 ml) were added. Schlenk tube was then sealed with a Teflon screw cap and placed in a preheated oil bath at 110°C for 14 h. The resulting suspension was cooled to room temperature and filtered through a 0.5 x 1 cm pad of silica gel, eluting with diethyl ether. The filtrate was concentrated. Purification of the residue by flash chromatography on silica gel gave the desired product.

Reference： [1]Dibakar, Mullick; Prakash, Anjanappa; Selvakumar, Kumaravel; Ruckmani, Kandasamy; Sivakumar, Manickam [Tetrahedron Letters, 2011, vol. 52, # 41, p. 5338 - 5341]

11
[ 66256-28-8 ]
[ 452-72-2 ]

Reference： [1]Tetrahedron Letters,2011,vol. 52,p. 5338 - 5341

12
[ 71-23-8 ]
[ 66256-28-8 ]
[ 1363438-37-2 ]

Yield	Reaction Conditions	Operation in experiment
	Stage #1: propan-1-ol With potassium <i>tert</i>-butylate In N,N-dimethyl-formamide at 0 - 20℃; for 0.166667h; Stage #2: 4-fluoro-1-iodo-2-methylbenzene In N,N-dimethyl-formamide at 80℃; for 3h; Stage #3: With ammonium chloride In water; N,N-dimethyl-formamide	XXV.1 3.44 mL (45.8 mmol) 1 -propanol are added to 3.42 g (30.5 mmol) KOtBu in 18 mL DMF at 0°C. After stirring the solution for 10 min at rt, 1.80 g (7.63 mmol) 4-fluoro-1 - iodo-2-methylbenzene are added and the mixture is stirred at 80°C for 3 h. The reaction is quenched by the addition of sat. aq. NH4CI solution and extracted with EtOAc (2x). The combined organic layers are washed with sat. aq. NH4CI solution and brine, dried over sodium sulphate and the solvent is removed in vacuo. The crude product is purified by column chromatography (silica gel, heptane/ EtOAc 9/1 ). C10H13IO (M = 276.1 g/mol)EI-MS: 276 [M]+ Rt (GC): 4.31 min (method A)
	Stage #1: propan-1-ol With potassium <i>tert</i>-butylate In N,N-dimethyl-formamide at 0 - 20℃; for 0.166667h; Stage #2: 4-fluoro-1-iodo-2-methylbenzene In N,N-dimethyl-formamide at 80℃; for 3h;	XXV.XXV.1 Example XXVExample XXV.11-Iodo-2-methyl-4-propoxybenzene3.44 mL (45.8 mmol) 1-propanol are added to 3.42 g (30.5 mmol) KOtBu in 18 mL DMF at 0° C. After stirring the solution for 10 min at rt, 1.80 g (7.63 mmol) 4-fluoro-1-iodo-2-methylbenzene are added and the mixture is stirred at 80° C. for 3 h. The reaction is quenched by the addition of sat. aq. NH4Cl solution and extracted with EtOAc (2×). The combined organic layers are washed with sat. aq. NH4Cl solution and brine, dried over sodium sulphate and the solvent is removed in vacuo. The crude product is purified by column chromatography (silica gel, heptane/EtOAc 9/1).C10H13IO (M=276.1 g/mol)EI-MS: 276 [M]+Rt (GC): 4.31 min (method A)
	Stage #1: propan-1-ol With potassium <i>tert</i>-butylate In N,N-dimethyl-formamide for 0.166667h; Cooling with ice; Stage #2: 4-fluoro-1-iodo-2-methylbenzene In N,N-dimethyl-formamide at 80℃; for 3h;	I19.1 Intermediate 19; Example I19.1; General Route; 1-Iodo-2-methyl-4-propoxybenzene; 3.44 mL (45.8 mmol) 1-propanol is added to an ice cold mixture of 3.42 g (30.5 mmol) KOtBu in 18 mL DMF. After stirring the mixture for 10 min 1.80 g (7.63 mmol) 4-fluoro-1-iodo-2-methylbenzene are added and the reaction mixture is stirred at 80° C. for 3 h. The reaction is quenched by the addition of a sat. aq. NH4Cl solution and extracted with EtOAc (2×). The combined organic layers are washed with sat. aq. NH4Cl solution and brine, dried with Na2SO4 and the solvent is removed in vacuo. The crude product is purified by column chromatography (silica gel, heptane/EtOAc 9/1).C10H13IO (M=276.1 g/mol)EI-MS: 276 [M]+ Rt (GC): 4.31 min (method A)

Reference： [1]Current Patent Assignee: C.H. Boehringer Sohn AG & Co. KG - WO2012/32014, 2012, A1 Location in patent: Page/Page column 97
[2]Current Patent Assignee: C.H. Boehringer Sohn AG & Co. KG - US2012/214782, 2012, A1 Location in patent: Page/Page column 42
[3]Current Patent Assignee: C.H. Boehringer Sohn AG & Co. KG - US2012/214785, 2012, A1 Location in patent: Page/Page column 53

13
[ 1375501-74-8 ]
[ 66256-28-8 ]
[ 1375501-77-1 ]

Yield	Reaction Conditions	Operation in experiment
	With triethylamine In N,N-dimethyl-formamide at 20℃; for 16h;	48.4 Step 4: Synthesis of [4-(4-Fluoro-2-methyl-phenylethynyl)-pyridin-2-yl]-urea (4-Ethynyl-pyridin-2-yl)-urea (75 mg, 0.47 mmol), 4-fluoro-l-iodo-2-methyl-benzene (224 mg, 0.931 mmol), triethylamine (5.0 mL), palladium bis(triphenylphosphine) dichloride (16 mg, 0.023 mmol) and Copper (I) iodide (8.8 mg, 0.047 mmol) are mixed in DMF (1.8 mL). The reaction mixture is stirred for 16 hrs at room temperature before saturated NH4C1 solution (5 mL) is added along with water (25 mL). The mixture is extracted with EtOAc (3 x 20 mL) and the organic layers are combined and concentrated to give the crude product. Purification by silica flash column chromatography using MeOH in DCM (gradient from 0% to 5 ) affords 25 mg of the desired product.

Reference： [1]Current Patent Assignee: C.H. Boehringer Sohn AG & Co. KG - WO2012/64631, 2012, A1 Location in patent: Page/Page column 85-86

14
[ 66256-28-8 ]
3,4-dihydro-2H-pyrido[1,2-a]pyrazine-1,6-dione [ No CAS ]
C₁₅H₁₃FN₂O₂ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
60%	With potassium phosphate; copper(l) iodide; N,N-dimethylethylenediamine In N,N-dimethyl-formamide at 100℃; for 6h; Inert atmosphere;	A8.b b Preparation of intermediate 43 Cul (0.495 g, 2.6 mmol) was added to a solution of intermediate 42 (0.855 g, 5.2 mmol), 5-fluoro-2-iodotoluene (1.6 g, 6.77 mmol), N,N-dimethyl-l,2-ethane- diamine (0.56 mL, 5.2 mmol) and K3P04 (2.2 g, 10.4 mmol) in DMF (15 mL), while the reaction was degassed by bubbling N2 through the solution. The mixture was then heated a 100 °C for 6 h. Water was added and the aq. layer was extracted with EtOAc. The organic layer was dried over MgS04, filtered and the solvent was removed under reduced pressure. The crude product was purified by flash column chromatography (silica; EtOAc/hexane 0/100 to 100/0). The desired fractions were concentrated in vacuo to yield intermediate 43 as a brown solid (0.848 g, 60%).

Reference： [1]Current Patent Assignee: JOHNSON & JOHNSON INC; GLAXOSMITHKLINE PLC - WO2013/171712, 2013, A1 Location in patent: Page/Page column 93

15
[ 5798-75-4 ]
[ 66256-28-8 ]
C₁₆H₁₅FO₂ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
91%	Stage #1: 4-fluoro-1-iodo-2-methylbenzene With tert.-butyl lithium In diethyl ether; pentane at -78℃; for 0.5h; Inert atmosphere; Stage #2: With dimethylaluminum chloride In diethyl ether; hexane; pentane at -78 - 0℃; for 0.5h; Inert atmosphere; Stage #3: Ethyl 4-bromobenzoate In tetrahydrofuran at 110℃; for 24h; Inert atmosphere; chemoselective reaction;

Reference： [1]Minami, Hiroki; Saito, Tatsuo; Wang, Chao; Uchiyama, Masanobu [Angewandte Chemie - International Edition, 2015, vol. 54, # 15, p. 4665 - 4668][Angew. Chem., 2015, vol. 127, # 15, p. 4748 - 4751,4]

16
[ 353-83-3 ]
[ 66256-28-8 ]
[ 292638-85-8 ]
C₁₃H₁₂F₄O₂ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
61%	With norbornene; palladium diacetate; caesium carbonate; acetic acid; DavePhos In acetonitrile at 20 - 110℃; for 8.16667h; Sealed tube; Inert atmosphere;

Reference： [1]Zhang, Hao; Chen, Pinhong; Liu, Guosheng [Angewandte Chemie - International Edition, 2014, vol. 53, # 38, p. 10174 - 10178][Angew. Chem., 2014, vol. 126, # 38, p. 10338 - 10342,5]

17
[ 66256-28-8 ]
[ 22246-12-4 ]
2-(4-fluoro-2-methylphenyl)-6-methoxy-3,4-dihydroisoquinolin-1(2H)-one [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
34%	With trans-N,N'-dimethyl-1,2-cyclohexyldiamine; copper(l) iodide In N,N-dimethyl-formamide at 150℃; for 32h; Inert atmosphere;	II Intermediate A2 2-(4-fluoro-2-methylphenyl)-6-methoxy-3.4-dihvdroisoquinolin-l(2H)-one Intermediate A2 2-(4-fluoro-2-methylphenyl)-6-methoxy-3.4-dihvdroisoquinolin-l(2H)-one Method II: To a 40 mL vial was added 6-methoxy-3,4-dihydroisoquinolin- l(2H)-one (2 g, 11.29 mmol), dimethylformamide (20 mL), followed by 4-fluoro-l-iodo-2- methylbenzene (5.33 g, 22.57 mmol), and ?ras-N,N'-dimethylcyclohexane-l,2-diamine (892 μL, 5.64 mmol). The reaction vial was flushed with nitrogen, charged with copper(I) iodide (215 mg, 1.129 mmol), and heated at 150 °C for 16 h. LC/MS indicated 50% consumption of starting material. The reaction vial was charged with additional copper(I) iodide (215 mg, 1.129 mmol) and heated at 150 °C for an additional 16 h. LC/MS indicated no addition conversion. The reaction mixture was cooled to ambient temperature and was diluted with dichloromethane and water. The organic layer was passed through a phase separator and concentrated. The crude product was purified by silica gel chromatography (80 g, 0-100% ethyl acetate/heptanes) to afford 2-(4-fluoro-2-methylphenyl)-6-methoxy-3,4-dihydroisoquinolin-l(2H)-one (1.1 g, 34% yield) as a beige solid. LC/MS (m/z, MH+): 286.4. NMR (400 MHz, CHLOROFORM-^ δ 2.28 (s, 3 H), 3.05 (dt, J=15.92, 5.18 Hz, 1 H), 3.21 (ddd, J=15.66, 10.11, 5.56 Hz, 1 H), 3.70 (dt, J=12.00, 5.87 Hz, 1 H), 3.88 (s, 3 H), 3.92 - 4.06 (m, 1 H), 6.75 (d, J=2.53 Hz, 1 H), 6.83 - 7.06 (m, 3 H), 7.17 (dd, J=8.59, 5.56 Hz, 1 H), 8.10 (d, J=8.59 Hz, 1 H).

Reference： [1]Current Patent Assignee: Novartis (w/o Sandoz); NOVARTIS AG - WO2015/92634, 2015, A1 Location in patent: Paragraph 00257

18
[ 884-09-3 ]
[ 66256-28-8 ]
[5-fluoro-3-methyl-2-(phenylthio)phenyl](phenyl)methanone [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
53%	With norborn-2-ene; copper(l) iodide; trifuran-2-yl-phosphane; caesium carbonate; palladium dichloride In 1,4-dioxane at 120℃; for 12h; Inert atmosphere; regioselective reaction;

Reference： [1]Sun, Fenggang; Li, Miao; He, Congfa; Wang, Bin; Li, Bin; Sui, Xianwei; Gu, Zhenhua [Journal of the American Chemical Society, 2016, vol. 138, # 24, p. 7456 - 7459]

19
[ 4285-42-1 ]
[ 66256-28-8 ]
C₁₅H₁₂FNO [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
96%	With norborn-2-ene; palladium diacetate; caesium carbonate; triphenylphosphine In 1,2-dichloro-ethane at 95℃; for 6h;

Reference： [1]Li, Xinyao; Pan, Jun; Song, Song; Jiao, Ning [Chemical Science, 2016, vol. 7, # 8, p. 5384 - 5389]

20
cyclohexyloxy(iodomethyl)dimethylsilane [ No CAS ]
[ 66256-28-8 ]
[ 140-88-5 ]
C₂₁H₃₁FO₃Si [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
75%	With norborn-2-ene; P(p-CH₃OC₆H₄)3; palladium diacetate; potassium carbonate In acetonitrile at 95℃; for 30h; Inert atmosphere; Schlenk technique;

Reference： [1]Sui, Xianwei; Ding, Linlin; Gu, Zhenhua [Chemical Communications, 2016, vol. 52, # 97, p. 13999 - 14002]

21
[ 66256-28-8 ]
[ 105-58-8 ]
C₂₂H₁₉F₃O [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
75%	Stage #1: 4-fluoro-1-iodo-2-methylbenzene With n-butyllithium In hexane for 0.666667h; Schlenk technique; Inert atmosphere; Cooling with ice; Stage #2: Diethyl carbonate In hexane at 20℃; for 12h; Schlenk technique; Inert atmosphere; Cooling with ice;	2 (Example 2) Synthesis of Triphenylmethanol via Aryllithium Compound The inside of a 200 mL Schlenk tube was replaced with argon,4-Iodo-3-methylfluorobenzene (9.8 g, 0.0415 mol) and hexane (25 mL) were added and dissolved.While ice-cooling the Schlenk tube, 1.6 M hexane solution of n-butyllithium (26 mL) was added dropwise and the mixture was stirred for 40 minutes.4-lithio-3-methylfluorobenzene becomes insoluble and precipitatesIt became a white suspension.Diethyl carbonate (1.4 mL) was added thereto, and the mixture was stirred at room temperature for 12 hours. Further methanol (2 mL) was added and the mixture was stirred for 1 hour. Water (200 mL) was added to the reaction solution, and the mixture was extracted with ethyl acetate (100 mL × 3). After washing the organic layer with a saturated saline solution, anhydrous sodium sulfateAfter drying with umium, filtration and concentration of the filtrate to dryness, triphenylmethanol derivative (3. 7 g, 0.0104 mol) in a yield of 75%

Reference： [1]Current Patent Assignee: NAGOYA ELECTRICAL EDUCATIONAL FOUNDATION; KANEKA CORPORATION - JP2016/172702, 2016, A Location in patent: Paragraph 0029-0030; 0032

22
[ 7321-55-3 ]
[ 66256-28-8 ]
4-(2-cyanopropan-2-yl)-2-methylbenzonitrile [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
75%	Stage #1: 4-fluoro-1-iodo-2-methylbenzene With isopropylmagnesium chloride In tetrahydrofuran at 0℃; for 0.5h; Stage #2: 2,2-dimethylmalononitrile In tetrahydrofuran at 0 - 20℃; for 0.5h;

Reference： [1]Malapit, Christian A.; Luvaga, Irungu K.; Reeves, Jonathan T.; Volchkov, Ivan; Busacca, Carl A.; Howell, Amy R.; Senanayake, Chris H. [Journal of Organic Chemistry, 2017, vol. 82, # 9, p. 4993 - 4997]

23
[ 66256-28-8 ]
[ 111511-90-1 ]
4-(4-cyano-3-methylphenyl)tetrahydro-2H-pyran-4-carbonitrile [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
76%	Stage #1: 4-fluoro-1-iodo-2-methylbenzene With isopropylmagnesium chloride In tetrahydrofuran at 0℃; for 0.5h; Stage #2: dihydro-2H-pyran-4,4(3H)-dicarbonitrile In tetrahydrofuran at 0 - 20℃; for 0.5h;

Reference： [1]Malapit, Christian A.; Luvaga, Irungu K.; Reeves, Jonathan T.; Volchkov, Ivan; Busacca, Carl A.; Howell, Amy R.; Senanayake, Chris H. [Journal of Organic Chemistry, 2017, vol. 82, # 9, p. 4993 - 4997]

24
[ 5765-65-1 ]
[ 66256-28-8 ]
[ 67-64-1 ]
1-(4-fluoro-2-methyl-6-morpholinophenyl)propan-2-one [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
71%	With norborn-2-ene; trifuran-2-yl-phosphane; palladium diacetate; caesium carbonate at 100℃; for 18h; Schlenk technique; Sealed tube; Inert atmosphere; regiospecific reaction;

Reference： [1]Fu, Wai Chung; Zheng, Bin; Zhao, Qingyang; Chan, Wesley Ting Kwok; Kwong, Fuk Yee [Organic Letters, 2017, vol. 19, # 16, p. 4335 - 4338]

25
[ 1436-34-6 ]
[ 66256-28-8 ]
C₁₃H₁₇FO [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
44%	With (2-dicyclohexylphosphino-2’,6’-diisopropoxy-1,1‘-biphenyl)[2-(2’-methylamino-1,1’-biphenyl)]palladium(II) methanesulfonate; C₁₁H₁₆O₂; sodium acetate In N,N-dimethyl-formamide at 120℃; for 24h; Inert atmosphere; Glovebox;

Reference： [1]Li, Renhe; Dong, Guangbin [Angewandte Chemie - International Edition, 2018, vol. 57, # 6, p. 1697 - 1701][Angew. Chem., 2018, vol. 130, p. 1713 - 1717,5]

26
[ 4136-95-2 ]
[ 66256-28-8 ]
[ 109-52-4 ]
(E)-ethyl 3-(4-fluoro-2-methyl-6-(2,4,6-trichlorobenzoyl)phenyl)acrylate [ No CAS ]
(E)-ethyl-3-(4-fluoro-2-methyl-6-pentanoylphenyl)acrylate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
1: 29% 2: 19%	Stage #1: 2,4,6-trichlorobenzoyl chloride; valeric acid With caesium carbonate In 1,4-dioxane at 20℃; for 2h; Schlenk technique; Inert atmosphere; Stage #2: 4-fluoro-1-iodo-2-methylbenzene With norbornene; C₈H₈Cl₂O₂Pd In 1,4-dioxane at 100℃; for 18h; Schlenk technique; Inert atmosphere;

Reference： [1]Xu, Shibo; Jiang, Julong; Ding, Linlin; Fu, Yao; Gu, Zhenhua [Organic Letters, 2018, vol. 20, # 2, p. 325 - 328]

27
[ 66256-28-8 ]
2-methylbenzenecarboselenoic acid Se-phenyl ester [ No CAS ]
(5-fluoro-3-methyl-2-(phenylselanyl)phenyl)(o-tolyl)methanone [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
60%	With trifuran-2-yl-phosphane; norbornene; potassium carbonate; palladium dichloride at 100℃; for 16h; Inert atmosphere; Sealed tube;

Reference： [1]Fan, Xiaozhong; Gu, Zhenhua [Organic Letters, 2018, vol. 20, # 4, p. 1187 - 1190]

28
[ 66256-28-8 ]
[ 501-65-5 ]
[ 88-65-3 ]
3-fluoro-1-methyl-9,10-diphenylphenanthrene [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
67%	With norborn-2-ene; palladium diacetate; potassium carbonate; tris-(o-tolyl)phosphine In N,N-dimethyl-formamide at 130℃; for 20h; Schlenk technique; Inert atmosphere; Sealed tube; regioselective reaction;

Reference： [1]Zhao, Qingyang; Fu, Wai Chung; Kwong, Fuk Yee [Angewandte Chemie - International Edition, 2018, vol. 57, # 13, p. 3381 - 3385][Angew. Chem., 2018, vol. 130, p. 3439 - 3443,5]

29
[ 122-60-1 ]
[ 66256-28-8 ]
[ 140-88-5 ]
(E)-ethyl 3-(4-fluoro-2-(2-hydroxy-3-phenoxypropyl)-6-methylphenyl)acrylate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
69%	With potassium (1S,4S)-bicyclo[2.2.1]hept-5-ene-2-carboxylate; palladium diacetate; XPhos In 1-methyl-pyrrolidin-2-one at 60℃; for 12h; Glovebox; Inert atmosphere; Sealed tube;

Reference： [1]Cheng, Hong-Gang; Wu, Chenggui; Chen, Han; Chen, Ruiming; Qian, Guangyin; Geng, Zhi; Wei, Qiang; Xia, Yuanyuan; Zhang, Jingyang; Zhang, Yuming; Zhou, Qianghui [Angewandte Chemie - International Edition, 2018, vol. 57, # 13, p. 3444 - 3448][Angew. Chem., 2018, vol. 130, # 13, p. 3502 - 3506,5]

30
[ 244-76-8 ]
[ 66256-28-8 ]
C₁₈H₁₃FN₂ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
82.5%	With copper(l) iodide; 1,10-Phenanthroline; potassium carbonate In 5,5-dimethyl-1,3-cyclohexadiene at 140℃; for 7h;	1.1 (1) Synthesis of 9-(4-fluoro-2-methyl)-9H-pyrido[2,3-b]indole: 16.8 g of 9H-pyrido[2,3-b]indole,25.96 g of 4-fluoro-2-methyl iodobenzene was dissolved in 220 mL of xylene, followed by 8.4 g of potassium carbonate, 16.8 g of cuprous iodide, and 16.8 g of 1,10-phenanthroline.The reaction was carried out at 140° C. for 7 hours, allowed to stand for cooling to room temperature, the reaction liquid was washed with water and the organic phase was separated, and then recrystallized with ethyl acetate.9-(4-Fluoro-2-methyl)-9H-pyrido[2,3-b]indole was obtained in a yield of 82.5%;

Reference： [1]Current Patent Assignee: SHAANXI LIGHTE OPTOELECTRONICS MATERIAL CO.,LTD - CN107739380, 2018, A Location in patent: Paragraph 0011; 0013; 0017; 0021

31
[ 66256-28-8 ]
[ 833459-47-5 ]
9-fluoro-5,7-dimethyldibenzo[c,e][1,2]thiazine 5-oxide [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
80%	With norbornene; palladium diacetate; potassium carbonate; triphenylphosphine In acetonitrile at 85 - 105℃; for 12h; Schlenk technique; Inert atmosphere;
75%	With norborn-2-ene; palladium diacetate; potassium carbonate; triphenylphosphine In acetonitrile at 80℃; for 12h; Inert atmosphere;	14 Example 14 Specific operation: In a 25 mL reaction flask equipped with a magnetic stirrer, a metal catalyst palladium acetate (6.7 mg, 0.03 mmol), triphenylphosphine (20.0 mg, 0.075 mmol) was added,S-2-bromophenyl-S-methyliminosulfanone (70.0 mg, 0.3 mmol), norbornene (56.4 mg, 0.6 mmol), potassium carbonate (82.8 mg, 0.6 mmol),Protect with nitrogen (at least three nitrogen cycles), add acetonitrile (3 ml) and 5-fluoro-2-iodotoluene (85.0 mg, 0.36 mmol) successively in a nitrogen stream and close the vessel.The reaction solution was heated to 80° C. for about 12 h, and the reaction was complete by TLC.After the treatment, the reaction solution was first diluted with 15 ml of ethyl acetate, and then the inorganic substances such as the catalyst and the alkali were removed by suction filtration through a sand funnel containing silica gel.The resulting filtrate was separated by flash column chromatography to give the pure product 9-fluoro-5,7-dimethyldibenzo[c,e][1,2]thiazine-5-oxide compound 3k. Yield: 75%.

Reference： [1]Zhou, Hao; Chen, Weihao; Chen, Zhiyuan [Organic Letters, 2018, vol. 20, # 9, p. 2590 - 2594]
[2]Current Patent Assignee: JIANGXI NORMAL UNIVERSITY - CN107987034, 2018, A Location in patent: Paragraph 0081-0083

32
[ 134694-78-3 ]
[ 66256-28-8 ]
C₁₄H₁₇FO [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
70%	With bis(η3-allyl-μ-chloropalladium(II)); potassium carbonate; 5-carboxybicyclo<2.2.1>hept-2-ene; XPhos In acetonitrile at 70℃; chemoselective reaction;
70%	With bis(η3-allyl-μ-chloropalladium(II)); potassium carbonate; 5-norbornene-endo-2-carboxylic acid; XPhos In acetonitrile at 70℃; Inert atmosphere; Schlenk technique;	General procedure for the synthesis of compounds 3 General procedure: To a 25mL of oven-dried Schlenk tube equipped with a magnetic stir bar was charged with [Pd(C3H5)Cl]2 (3.7mg 0.01mmol, 0.05 equiv), XPhos (10.5mg, 0.022mmol, 0.11 equiv), K2CO3 (69.1mg, 0.5mmol, 2.5 equiv), and dry CH3CN (1mL). After stirring for about 15minat r.t. under argon, a solution of aryl iodide 1 (0.24mmol, 1.2 equiv), alkylating reagent 2 (0.2mmol, 1.0 equiv), 5-Norbornene-2-carboxylic acid N4 (5.5mg, 0.04mmol, 0.2 equiv) in dry MeCN (1mL) was added, then heated to 70°C and stirred for 5-24h. The reaction was monitored by TLC, after completion of the reaction, the mixture was cooled to r.t., filtered through a thin pad of celite eluting with ethyl acetate (10mL), and the combined filtrate was concentrated in vacuo. The residue was directly purified by column chromatography on silica gel or purified by PTLC to give the desired product 3.

Reference： [1]Liu, Ze-Shui; Qian, Guangyin; Gao, Qianwen; Wang, Peng; Cheng, Hong-Gang; Wei, Qiang; Liu, Qi; Zhou, Qianghui [ACS Catalysis, 2018, vol. 8, # 6, p. 4783 - 4788]
[2]Liu, Ze-Shui; Qian, Guangyin; Gao, Qianwen; Wang, Peng; Cheng, Hong-Gang; Hua, Yu; Zhou, Qianghui [Tetrahedron, 2019, vol. 75, # 12, p. 1774 - 1780]

33
[ 3634-89-7 ]
[ 66256-28-8 ]
[ 140-88-5 ]
ethyl-2-(6-fluoro-8-methyl-2-tosyl-1,2,3,4-tetrahydroisoquinolin-1-yl)acetate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
77%	With trifuran-2-yl-phosphane; N-(p-methylphenyl)bicyclo[2.2.1]hept-5-ene-endo-2,endo-3-dicarboximide; palladium diacetate; potassium carbonate In acetonitrile at 70℃; Inert atmosphere; Glovebox; Sealed tube; stereoselective reaction;

Reference： [1]Qian, Guangyin; Bai, Miao; Gao, Shijun; Chen, Han; Zhou, Siwei; Cheng, Hong-Gang; Yan, Wei; Zhou, Qianghui [Angewandte Chemie - International Edition, 2018, vol. 57, # 34, p. 10980 - 10984][Angew. Chem., 2018, vol. 130, # 34, p. 11146 - 11150,5]

34
[ 66256-28-8 ]
[ 88-65-3 ]
3-fluoro-1-methyltriphenylene [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
75%	With norborn-2-ene; bis-triphenylphosphine-palladium(II) chloride; potassium carbonate; p-benzoquinone In dimethyl sulfoxide at 140℃; for 3h; Schlenk technique; Inert atmosphere;

Reference： [1]Yang, Yuzhong; Zhou, Bang; Zhu, Xiaoming; Deng, Guobo; Liang, Yun; Yang, Yuan [Organic Letters, 2018, vol. 20, # 17, p. 5402 - 5405]

35
[ 61881-19-4 ]
[ 66256-28-8 ]
8-fluoro-10-methyl-6-(trifluoromethyl)phenanthridine [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
68%	With potassium phosphate; norbornene; palladium diacetate; P(p-C₆H₄F)3 In toluene at 100℃; for 12h; Inert atmosphere; Sealed tube;

Reference： [1]Wang, Zhuo; Li, Tongyu; Zhao, Jinghui; Shi, Xiaonan; Jiao, Dequan; Zheng, Han; Chen, Chen; Zhu, Bolin [Organic Letters, 2018, vol. 20, # 21, p. 6640 - 6645]

36
[ 66256-28-8 ]
[ 121-46-0 ]
[ 7154-66-7 ]
3-fluoro-1-methylphenanthrene [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
95%	With palladium diacetate; caesium carbonate; triphenylphosphine In N,N-dimethyl-formamide at 105℃; for 10h; Inert atmosphere;	General procedure for the preparation of products General procedure: A dried round-bottomed flask was charged with aryl iodide (0.30 mmol, 1.0 equiv), ortho-bromobenzoyl chlorides (0.36 mmol, 1.2 equiv), norbornadiene (0.60 mmol, 2.0 equiv), Pd(OAc)2 (5 mol %), triphenylphosphine (12.5 mol %), Cs2CO3 (0.675 mmol, 2.25 equiv), and DMF (4 mL). The mixture was stirred at 105 °C under nitrogen atmosphere for 10 h. After cooling to room temperature, the mixture was diluted with ethyl acetate (5 mL) and brine (10 mL), and extracted with ethyl acetate (3 × 10 mL). The combined organic phase was washed with brine, dried with anhydrous Na2SO4, filtered, and concentrated under reduced pressure. The crude product was purified by column chromatography on silica gel (petroleum ether/ethyl acetate as eluent) to afford the target compounds

Reference： [1]Zhong, Yue; Wu, Wen-Yu; Yu, Shao-Peng; Fan, Tian-Yuan; Yu, Hai-Tao; Li, Nian-Guang; Shi, Zhi-Hao; Tang, Yu-Ping; Duan, Jin-Ao [Beilstein Journal of Organic Chemistry, 2019, vol. 15, p. 291 - 298]

37
[ 66256-28-8 ]
C₁₄H₁₂F₂Se₂ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	With selenium; copper(II) oxide; potassium hydroxide In dimethyl sulfoxide at 90℃; Inert atmosphere;

Reference： [1]Fang, Jun-Dan; Yan, Xiao-Biao; Zhou, Li; Wang, Yu-Zhao; Liu, Xue-Yuan [Advanced Synthesis and Catalysis, 2019, vol. 361, # 9, p. 1985 - 1990]

38
[ 66256-28-8 ]
[ 17356-08-0 ]
C₈H₉FN₂S*HI [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	With bis(tricyclohexylphosphine)nickel(II) dichloride; 2-picoline borane complex In 1-methyl-pyrrolidin-2-one at 60℃; for 18h; Schlenk technique; Inert atmosphere; Sealed tube;

Reference： [1]Magné, Valentin; Ball, Liam T. [Chemistry - A European Journal, 2019, vol. 25, # 37, p. 8903 - 8910]

39
[ 1450-14-2 ]
[ 498-66-8 ]
[ 66256-28-8 ]
rac-((1R,2S,3S,4S)-3-(4-fluoro-2-methyl-6-(trimethylsilyl)phenyl)bicyclo[2.2.1]heptan-2-yl)trimethylsilane [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
83%	With potassium phosphate; palladium diacetate; triphenylphosphine In acetonitrile at 110℃; for 5h; Schlenk technique; Inert atmosphere;

Reference： [1]Xu, Yankun; Liu, Xiaodong; Chen, Wenqi; Deng, Guobo; Liang, Yun; Yang, Yuan [Journal of Organic Chemistry, 2018, vol. 83, # 22, p. 13930 - 13939]

40
[ 66256-28-8 ]
C₇H₆F₃I [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
73 %Spectr.	With potassium fluoride; trichloroisocyanuric acid In acetonitrile at 40℃; for 24h; chemoselective reaction;

Reference： [1]Häfliger, Joel; Pitts, Cody Ross; Bornemann, Dustin; Käser, Roland; Santschi, Nico; Charpentier, Julie; Otth, Elisabeth; Trapp, Nils; Verel, René; Lüthi, Hans Peter; Togni, Antonio [Chemical Science, 2019, vol. 10, # 30, p. 7251 - 7259]

41
[ 4746-97-8 ]
[ 66256-28-8 ]
8-(4-fluoro-2-methylphenyl)-1,4-dioxaspiro[4.5]decan-8-ol [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
71%	Stage #1: 4-fluoro-1-iodo-2-methylbenzene With isopropylmagnesium chloride In tetrahydrofuran; 2-methyltetrahydrofuran at 0 - 20℃; for 1h; Stage #2: cyclohexanedione monoethylene ketal In tetrahydrofuran; 2-methyltetrahydrofuran at 20℃; for 1.33333h; Cooling with ice; Inert atmosphere;	1 Intermediate 12. 2-r(cis)-4-(4-Lluoro-2-methylphenyl)cvclohexyl1ethan-l-ol. Step 1. 8-(4-Lluoro-2-methylphenyl)-l,4-dioxaspiro[4.5]decan-8-ol. To a solution of 4- fluoro-l-iodo-2-methylbenzene (43.6 mL, 330 mmol) in 2-methyltetrahydrofuran (650 mL) at 0°C was slowly added a solution of isopropylmagnesium chloride in tetrahydrofuran (2 M, 165 mL, 330 mmol) over 30 minutes. The reaction was allowed to warm to room temperature and stirred for an additional 30 minutes at room temperature. A suspension of l,4-dioxaspiro[4.5]decan-8- one (43.0 g, 275 mmol) in 2-methyltetrahydrofuran (65 mL) was added over 10 minutes. A mild reaction exotherm was observed and an ice bath was introduced for 10 minutes to prevent excess heating, then the ice bath was removed. The reaction mixture was stirred at room temperature for 1 h, poured into a saturated solution of ammonium chloride (1000 mL), extracted with EtOAc (3 x 200 mL), then the combined organics were dried (Na2S04) and concentrated under reduced pressure. The crude material taken up in a minimum amount of dichloromethane (200 mL) and the product precipitated upon standing. Hexanes (-100 mL) was added, the suspension was filtered and the solid was washed with additional hexanes (100 mL) to provide the title compound as a white powder (52 g, 71 %). 1H NMR (400 MHz, CDCb) d 7.42 (dd, 7 = 6.1, 8.7 Hz, 1H), 6.92 - 6.75 (m, 2H), 4.07 - 3.91 (m, 4H), 2.61 (s, 3H), 2.35 - 2.05 (m, 4H), 2.03 - 1.88 (m, 2H), 1.69 (d, J = 11.5 Hz, 2H). [M+H-H2O] = 249.2.

Reference： [1]Current Patent Assignee: DART NEUROSCIENCE LLC - WO2019/168866, 2019, A1 Location in patent: Page/Page column 108; 109

42
[ 18742-02-4 ]
[ 66256-28-8 ]
2-deutero-3-(2-ethyl-1,3-dioxolan)-5-fluorotoluene [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
71%	With potassium dihydrogenphosphate; norbornene; potassium acetate; palladium diacetate; sodium formate; triphenylphosphine In N,N-dimethyl-formamide at 50℃; for 16h; Inert atmosphere;	10 Example 10: Preparation method of 2-deuterated-3-(2-ethyl-1,3-dioxolan)-5-fluorotoluene Palladium acetate palladium (44.9 mg, 0.2 mmol) was added to a 25 mL eggplant bottle, triphenylphosphine (52.4 mg, 0.2 mmol),Sodium formate (276 mg, 4 mmol),Norbornene (188 mg, 2 mmol),Potassium phosphate (2.544 g, 12 mmol), Potassium acetate (392 mg, 4 mmol),2-iodo-5-fluorotoluene (472 mg, 2 mmol), 2-(2-Bromoethyl)-1,3-dioxane (1.448 g, 8 mmol) and dimethylformamide (10 ml). High purity nitrogen replacement three times,After 16 hours of reaction at 50oC,Extracting the mixture with dichloromethane and water,Combine the organic phase, concentrate the organic solvent,Further purification of the product by column chromatography,get2-deuterated-3-(2-ethyl-1,3-dioxolan)-5-fluorotolueneThe yield was 71%.

Reference： [1]Current Patent Assignee: ANHUI SHOLON NEW MATERIAL TECHNOLOGY CO LTD - CN110054541, 2019, A Location in patent: Paragraph 0022

43
[ 2969-81-5 ]
[ 66256-28-8 ]
C₁₃H₁₆⁽²⁾HFO₂ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
70%	With potassium dihydrogenphosphate; norbornene; potassium acetate; palladium diacetate; sodium formate; triphenylphosphine In N,N-dimethyl-formamide at 50℃; for 16h; Inert atmosphere;	11 Example 11: Preparation method of 2-deuterated-3-(ethyl butyrate)-5-fluorotoluene Palladium acetate palladium (44.9 mg, 0.2 mmol) was added to a 25 mL eggplant bottle.Triphenylphosphine (52.4 mg, 0.2 mmol),Sodium formate (276 mg, 4 mmol),Norbornene (188 mg, 2 mmol),Potassium phosphate (2.544 g, 12 mmol), potassium acetate (392 mg, 4 mmol),2-iodo-5-fluorotoluene (472 mg, 2 mmol),Ethyl bromobutyrate (1.56 g, 8 mmol) and dimethylformamide (10 ml).High-purity nitrogen was replaced three times, after reacting at 50oC for 16 hours,The mixture is extracted with dichloromethane and water, and the organic phases are combined.The organic solvent is concentrated, and the product is further purified by column chromatography.2-Deutero-3-(ethyl butyrate)-5-fluorotoluene was obtained in a yield of 70%.

Reference： [1]Current Patent Assignee: ANHUI SHOLON NEW MATERIAL TECHNOLOGY CO LTD - CN110054541, 2019, A Location in patent: Paragraph 0022

44
[ 66256-28-8 ]
(R)-3-(2-ethynyl-5-fluoro-3-methylphenyl)propane-1,2-diol [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 2 steps 1: palladium diacetate; XPhos; norborn-2-ene; potassium acetate; 1-methyl-pyrrolidin-2-one / 24 h / 60 °C / Glovebox; Inert atmosphere; Sealed tube 2: tetrabutyl ammonium fluoride / tetrahydrofuran / 3 h / 0 °C

Reference： [1]Wu, Chenggui; Yang, Xinjun; Shang, Yong; Cheng, Hong-Gang; Yan, Wei; Zhou, Qianghui [Organic Letters, 2019, vol. 21, # 22, p. 8938 - 8942]

45
[ 66256-28-8 ]
(1S,4R)-7-fluoro-1,9-dimethyl-1,3,4,5-tetrahydro-1,4-epoxybenzo[c]oxepine [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 3 steps 1: palladium diacetate; XPhos; norborn-2-ene; potassium acetate; 1-methyl-pyrrolidin-2-one / 24 h / 60 °C / Glovebox; Inert atmosphere; Sealed tube 2: tetrabutyl ammonium fluoride / tetrahydrofuran / 3 h / 0 °C 3: bis(benzonitrile)palladium(II) dichloride / tetrahydrofuran / 24 h / 20 °C / Glovebox; Inert atmosphere; Sealed tube

Reference： [1]Wu, Chenggui; Yang, Xinjun; Shang, Yong; Cheng, Hong-Gang; Yan, Wei; Zhou, Qianghui [Organic Letters, 2019, vol. 21, # 22, p. 8938 - 8942]

46
[ 122-60-1 ]
[ 66256-28-8 ]
[ 89343-06-6 ]
1-(5-fluoro-3-methyl-2-((triisopropylsilyl)ethynyl)phenyl)-3-phenoxypropan-2-ol [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
80%	With 1-methyl-pyrrolidin-2-one; norborn-2-ene; potassium acetate; palladium diacetate; XPhos at 60℃; for 24h; Glovebox; Inert atmosphere; Sealed tube; chemoselective reaction;

Reference： [1]Wu, Chenggui; Yang, Xinjun; Shang, Yong; Cheng, Hong-Gang; Yan, Wei; Zhou, Qianghui [Organic Letters, 2019, vol. 21, # 22, p. 8938 - 8942]

47
[ 893441-86-6 ]
[ 66256-28-8 ]
[ 80-48-8 ]
tert-butyl 4-(4-fluoro-2,6-dimethylphenyl)-1H-indole-1-carboxylate [ No CAS ]

Reference： [1]Journal of the American Chemical Society,2019,vol. 141,p. 15986 - 15993

48
[ 66256-28-8 ]
[ 89343-06-6 ]
[ 80-48-8 ]
((4-fluoro-2,6-dimethylphenyl)ethynyl)triisopropylsilane [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
86%	With tris-(dibenzylideneacetone)dipalladium⁽⁰⁾; trifuran-2-yl-phosphane; 5-norbornene-2-carbonitrile; potassium carbonate In acetonitrile at 100℃; for 15h; Inert atmosphere; Schlenk technique;

Reference： [1]Gao, Qianwen; Shang, Yong; Song, Fuzhen; Ye, Jinxiang; Liu, Ze-Shui; Li, Lisha; Cheng, Hong-Gang; Zhou, Qianghui [Journal of the American Chemical Society, 2019, vol. 141, # 40, p. 15986 - 15993]

49
[ 66256-28-8 ]
2-bromobenzaldehyde hydrazone [ No CAS ]
C₁₄H₁₁F [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
76%	With norborn-2-ene; palladium diacetate; potassium carbonate; cyclohexyldiphenylphosphine In N,N-dimethyl-formamide at 130℃; for 18h; Inert atmosphere; regioselective reaction;

Reference： [1]Fu, Wai Chung; Kwong, Fuk Yee [Chemical Science, 2020, vol. 11, # 5, p. 1411 - 1417]

50
[ 573-57-9 ]
[ 66256-28-8 ]
[ 74-95-3 ]
2-fluoro-4-methyl-5,10,10a,11-tetrahydro-4bH-5,10-epoxybenzo[b]fluorene [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
90%	With water; potassium acetate; palladium diacetate; potassium carbonate; isopropyl alcohol In N,N-dimethyl-formamide at 90℃; for 16h; Schlenk technique; Inert atmosphere;

Reference： [1]Ji, Xiaoming; Gu, Yichao; Cheng, Cang; Wu, Zhuo; Zhang, Yanghui [Advanced Synthesis and Catalysis, 2020, vol. 362, # 7, p. 1496 - 1501]

51
[ 498-66-8 ]
[ 22979-35-7 ]
[ 66256-28-8 ]
methyl 7-fluoro-5-methyl-9-phenyl-2,3,4,4a,9,9a-hexahydro-1H-1,4-methanofluorene-9-carboxylate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
95%	With palladium diacetate; caesium carbonate; tris-(o-tolyl)phosphine In N,N-dimethyl-formamide; acetonitrile at 90℃; for 16h; Schlenk technique; Inert atmosphere; diastereoselective reaction;

Reference： [1]Ji, Xiaoming; Gu, Yichao; Cheng, Cang; Wu, Zhuo; Zhang, Yanghui [Advanced Synthesis and Catalysis, 2020, vol. 362, # 7, p. 1496 - 1501]

52
[ 66256-28-8 ]
[ 829-85-6 ]
(4-fluoro-2-((triethylsilyl)methyl)phenyl)diphenylphosphane [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 2 steps 1: palladium diacetate; potassium acetate / 3 h / 130 °C / Schlenk technique; Inert atmosphere 2: [ruthenium(II)(η⁶-1-methyl-4-isopropyl-benzene)(chloride)(μ-chloride)]₂; cyclohexylamine; norbornene / tetrahydrofuran / 24 h / 100 °C / Schlenk technique; Inert atmosphere

Reference： [1]Dong, Ben; Shi, Zhuangzhi; Wen, Jian; Zhao, Yue; Zhu, Jinjun [Angewandte Chemie - International Edition, 2020, vol. 59, # 27, p. 10909 - 10912][Angew. Chem., 2020, vol. 132, # 27, p. 11001 - 11004,4]

53
[ 66256-28-8 ]
[ 829-85-6 ]
(4-fluoro-2-methylphenyl)diphenylphosphane [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
78%	With potassium acetate; palladium diacetate at 130℃; for 3h; Schlenk technique; Inert atmosphere;

Reference： [1]Dong, Ben; Shi, Zhuangzhi; Wen, Jian; Zhao, Yue; Zhu, Jinjun [Angewandte Chemie - International Edition, 2020, vol. 59, # 27, p. 10909 - 10912][Angew. Chem., 2020, vol. 132, # 27, p. 11001 - 11004,4]

54
[ 66256-28-8 ]
[ 92470-93-4 ]
[ 292638-85-8 ]
methyl (E)-3-(4-fluoro-2-methyl-6-((2R,3R,4R,5R,6R)-3,4,5-tris(benzyloxy)-6-((benzyloxy)methyl)tetrahydro-2H-pyran-2-yl)phenyl)acrylate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
84%	With trifuran-2-yl-phosphane; palladium diacetate; (1R,4R)-N-phenylbicyclo[2.2.1]hept-5-ene-2-carboxamide; caesium carbonate In tetrahydrofuran at 100℃; for 24h; Inert atmosphere;	11 Example 11methyl(E)-3-(4-fluoro-2-methyl-6-((2R,3R,4R,5R,6R)-3,4,5-tris(benzyloxy)-6-((benzyloxy)methyl)tetrahydro -2H-pyran-2-yl)phenyl)acrylatePreparation 0.3mmol of cesium carbonate,(1R, 4R)-N-phenylbicyclo[2.2.1]hept-5-ene-2-carboxamide 0.2mmol,Palladium acetate 0.01mmol,Tris(2-furyl)phosphine 0.02mmol,0.1mmol of 4-fluoro-1-iodo-2-toluene,Glycosyl chloride 0.15mmol,Methyl acrylate 0.2mmol,Add 1mL of tetrahydrofuranInto a 15mL reaction tube,Nitrogen is repeatedly filled 10 times,Placed in an oil bath at 100°C,React for 24h; cool to room temperature,The reaction solution was diluted with ethyl acetate,Wash three times,The organic phase was dried with anhydrous Na2SO4, filtered,Concentrate and purify by thin layer chromatography to obtain 60.1 mg of the target product.The yield was 84%.
84%	With trifuran-2-yl-phosphane; palladium diacetate; N-phenylbicyclo[2.2.1]hept-5-ene-2-carboxamide; caesium carbonate In tetrahydrofuran at 100℃; for 24h; Schlenk technique; Inert atmosphere; diastereoselective reaction;

Reference： [1]Current Patent Assignee: HUAQIAO UNIVERSITY - CN111269205, 2020, A Location in patent: Paragraph 0076; 0077; 0078; 0079; 0080
[2]Lv, Weiwei; Chen, Yanhui; Wen, Si; Ba, Dan; Cheng, Guolin [Journal of the American Chemical Society, 2020, vol. 142, # 35, p. 14864 - 14870]

55
[ 66256-28-8 ]
[ 85909-08-6 ]
(4-(4-fluoro-2-methylphenyl)-4-oxobutyl) tert-butyl carbamate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
80%	With isopropylmagnesium bromide In tetrahydrofuran at 20℃; for 19h; Cooling with ice;	8; 347 Intermediate (4-(4-fluoro-2-methylphenyl)-4-oxobutyl) tert-butyl carbamate Synthesis of (Int 347-1) Add dry THF (20 mL) to a reaction flask containing SM 5 (2.36 g, 10 mmol) and protect it with nitrogen.Add isopropyl magnesium bromide (10mL, 1M in THF) to the bottle under ice-water bath conditions, then remove the ice-water bath, stir at room temperature for 7 hours, and finally add N-Boc-2-pyrrolidone (1.85g, 10mmol), react at room temperature 12 hours. Pour the reaction solution into saturated aqueous ammonium chloride solution,Extract with 30mL (10mL×3) ethyl acetate,Combine the organic phases, dry with anhydrous sodium sulfate,After purification by column chromatography, Int 347-1 (2.36 g, 8 mmol) was obtained with a yield of 80%.

Reference： [1]Current Patent Assignee: HINOVA PHARMACEUTICALS - CN111217802, 2020, A Location in patent: Paragraph 0168-0172; 0828-0832

56
[ 66256-28-8 ]
[ 402955-77-5 ]
(R)-(4-(4-fluoro-2-methylphenyl)-1-methyl-4-oxobutyl) tert-butyl carbamate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
85%	With isopropylmagnesium bromide In tetrahydrofuran at 20℃; for 19h; Inert atmosphere; Cooling with ice;	21 Intermediate(R)-(4-(4-Fluoro-2-methylphenyl)-1-methyl-4-oxobutyl) tert-butyl carbamateSynthesis of (Int21-1) Dry THF (23mL) was added to a reaction flask containing SM 5 (2.36g, 10mmol) under nitrogen protection,Add isopropyl magnesium bromide (10mL, 1M in THF) to the bottle under ice water bath, then remove the ice water bath,Stir at room temperature for 7 hours, and finally add (R)-2-methyl-5-oxopyrrolidine-1-carboxylic acid tert-butyl ester (1.99g, 10mmol),React at room temperature for 12 hours. The reaction solution was poured into saturated aqueous ammonium chloride solution, extracted with 30 mL (10 mL×3) ethyl acetate, the organic phases were combined, and dried over anhydrous sodium sulfate.After purification by column chromatography, Int 21-1 (2.59 g, 8.5 mmol) was obtained with a yield of 85%.

Reference： [1]Current Patent Assignee: HINOVA PHARMACEUTICALS - CN111217802, 2020, A Location in patent: Paragraph 0252-0256

57
[ 66256-28-8 ]
[ 128372-77-0 ]
tert-butyl N-[5-(4-fluoro-2-methylphenyl)-5-oxopentan-2-yl]carbamate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
85%	With isopropylmagnesium bromide In tetrahydrofuran at 20℃; for 19h; Inert atmosphere; Cooling with ice;	353 Intermediate tert-butyl N-[5-(4-fluoro-2-methylphenyl)-5-oxopentan-2-yl]carbamate (Int 353-1) Synthesis Add dry THF (20 mL) to a reaction flask containing SM 5 (2.36 g, 10 mmol) and protect it with nitrogen.Add isopropyl magnesium bromide (10mL, 1M in THF) to the bottle under ice-water bath, then remove the ice-water bath, stir at room temperature for 7 hours, and finally add 2-methyl-5-oxopyrrolidine-1-carboxylic acid Tert-butyl ester (1.99 g, 10 mmol),React at room temperature for 12 hours. Pour the reaction solution into saturated aqueous ammonium chloride solution, extract with 30 mL (10 mL×3) ethyl acetate, combine the organic phases, and dry with anhydrous sodium sulfate.After purification by column chromatography, Int 353-1 (2.63 g, 8.5 mmol) was obtained with a yield of 85%.

Reference： [1]Current Patent Assignee: HINOVA PHARMACEUTICALS - CN111217802, 2020, A Location in patent: Paragraph 0896-0900

58
[ 122-60-1 ]
[ 66256-28-8 ]
[ 140-88-5 ]
C₂₁H₂₃FO₄ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
69%	With palladium diacetate; potassium bicyclo[2.2.1]hept-2-ene-5-carboxylate; XPhos In 1-methyl-pyrrolidin-2-one at 60℃; for 12h;

Reference： [1]Cheng, Hong-Gang; Wu, Chenggui; Zhou, Qianghui [Synlett, 2020, vol. 31, # 9, p. 829 - 837]

59
[ 778-28-9 ]
[ 1663-39-4 ]
[ 66256-28-8 ]
tert-butyl (E)-3-(2-butyl-4-fluoro-6-methylphenyl)acrylate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
75%	With tris-(dibenzylideneacetone)dipalladium⁽⁰⁾; bicyclo[2.2.1]hept-5-ene-2-carbonitrile; caesium carbonate; XPhos In acetonitrile at 80℃; for 15h; Schlenk technique; Inert atmosphere;	Compounds 4; General Procedure General procedure: A 25-mL oven-dried Schlenk tube equipped with a magnetic stir bar was charged with Pd2(dba)3 (4.6 mg, 0.005 mmol, 0.025 equiv), XPhos (2.4 mg, 0.005 mmol, 0.025 equiv), Cs2CO3 (162.9 mg, 0.5 mmol, 2.5 equiv), and anhydrous CH3CN (1.0 mL). After stirring for about 15 min at r.t. under argon, aryl iodide 1 (0.24 mmol, 1.2 equiv), alkyl tosylate 2 (0.4 mmol, 2.0 equiv), olefin 3 (0.2 mmol, 1.0 equiv), and 5-norbornene-2-carbonitrile (4.8 mg, 0.04 mmol, 0.2 equiv) were added, then the mixture was heated to 80 °C and stirred for 15 h. After completion of the reaction (monitored by TLC), the mixture was cooled to r.t., filtered through a thin pad of Celite, eluting with EtOAc (10 mL), and the combined filtrate was concentrated in vacuo. The residue was directly purified by column chromatography on silica gel or purified by PTLC to give the desired product .

Reference： [1]Cheng, Hong-Gang; Gao, Qianwen; Hua, Yu; Liu, Ze-Shui; Zhou, Qianghui; Zhou, Siwei [Synthesis, 2020, vol. 52, # 6, p. 834 - 846]

60
[ 5765-65-1 ]
[ 928-49-4 ]
[ 66256-28-8 ]
4-(5-fluoro-2-(hexa-3,4-dien-3-yl)-3-methylphenyl)morpholine [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
63%	With norborn-2-ene; dmap; palladium diacetate; caesium carbonate; triphenylphosphine; Trimethylacetic acid In toluene at 140℃; for 24h; Inert atmosphere;

Reference： [1]Zhang, Bo-Sheng; Li, Yuke; Gou, Xue-Ya; Zhang, Zhe; An, Yang; Wang, Xin-Gang; Liang, Yong-Min [Chemical Communications, 2020, vol. 56, # 64, p. 9202 - 9205]

61
[ 288-13-1 ]
[ 66256-28-8 ]
[ 1339551-70-0 ]

Yield	Reaction Conditions	Operation in experiment
6.7%	With copper(l) iodide; potassium carbonate; <i>L</i>-proline In dimethyl sulfoxide at 90℃; for 16h;	3 The synthesis of l-(4-fluoro-2-methylphenyl)-lH-pyrazole (0091-2). To a stirred solution of 0091-1 (3.0 g, 12.7 mmol) in DMSO (30 ml) was added 1H- pyrazole (1.0 g, 15.3 mmol), Cul (0.30 g), K2CO3 (2.6 g, 19.0 mmol) and L-proline (0.90 g). The resulting reaction mixture was stirred at 90 °C for 16 h. Water (30 mL) was added, the aqueous phase was extracted with EA, the combined organic phases were dried over anhydrous sodium sulfate, filtered, and concentrated in vacuo, purified by C.C. to give the desired product 0091-2 (150 mg, yield: 6.7%) as yellow oil.

Reference： [1]Current Patent Assignee: SHANGPHAMA INNOVATION; SHANGPHARMA INNOVATION INC; UNIVERSITY OF CALIFORNIA - WO2020/172324, 2020, A1 Location in patent: Paragraph 0646; 1240-1242

62
C₁₇H₁₉N₃O₃S₂ [ No CAS ]
[ 66256-28-8 ]
3-((4-fluoro-2-methylphenyl)thio)-N,N-dimethylbenzofuran-2-amine [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
36%	With copper(l) iodide; 1,8-diazabicyclo[5.4.0]undec-7-ene In 1,4-dioxane at 90℃; for 5h; Inert atmosphere; Sealed tube;

Reference： [1]Li, Xue; Mai, Shaoyu; Li, Xin; Xu, Jian; Xu, Hetao; Song, Qiuling [Organic Letters, 2020, vol. 22, # 20, p. 7874 - 7878]

63
[ 928-49-4 ]
[ 58105-38-7 ]
[ 66256-28-8 ]
2,3-diethyl-6-fluoro-1,4-dimethyl-1H-indole [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
54%	With trifuran-2-yl-phosphane; norbornene; palladium diacetate; caesium carbonate In toluene at 120℃; for 24h; Sealed tube; Inert atmosphere;

Reference： [1]Zhang, Bo-Sheng; Wang, Fan; Yang, Ying-Hui; Gou, Xue-Ya; Qiu, Yi-Feng; Wang, Xi-Cun; Liang, Yong-Min; Li, Yuke; Quan, Zheng-Jun [Organic Letters, 2020, vol. 22, # 21, p. 8267 - 8271]

64
[ 66256-28-8 ]
[ 89343-06-6 ]
[ 92470-93-4 ]
((4-fluoro-2-methyl-6-((2R,3R,4R,5R,6R)-3,4,5-tris(benzyloxy)-6-((benzyloxy)methyl)tetrahydro-2H-pyran-2-yl)phenyl)ethynyl)triisopropylsilane [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
26%	With trifuran-2-yl-phosphane; palladium diacetate; N-methylbicyclo[2.2.1]hept-5-ene-2-carboxamide; potassium carbonate In acetonitrile at 100℃; for 24h; Schlenk technique; Inert atmosphere; diastereoselective reaction;

Reference： [1]Lv, Weiwei; Chen, Yanhui; Wen, Si; Ba, Dan; Cheng, Guolin [Journal of the American Chemical Society, 2020, vol. 142, # 35, p. 14864 - 14870]

65
[ 66256-28-8 ]
[ 92470-93-4 ]
(2R,3R,4R,5R,6R)-3,4,5-tris(benzyloxy)-2-((benzyloxy)methyl)-6-(3-fluoro-5-methylphenyl)tetrahydro-2H-pyran [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
87%	With trifuran-2-yl-phosphane; palladium diacetate; N-phenylbicyclo[2.2.1]hept-5-ene-2-carboxamide; caesium carbonate; isopropyl alcohol In tetrahydrofuran at 100℃; for 24h; Schlenk technique; Inert atmosphere; diastereoselective reaction;

Reference： [1]Lv, Weiwei; Chen, Yanhui; Wen, Si; Ba, Dan; Cheng, Guolin [Journal of the American Chemical Society, 2020, vol. 142, # 35, p. 14864 - 14870]

66
[ 253185-04-5 ]
[ 66256-28-8 ]
C₁₇H₁₉FI⁽¹⁺⁾*Cl^(1-) [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	Stage #1: 4-fluoro-1-iodo-2-methylbenzene With oxone at 23℃; for 0.5h; Stage #2: With sulfuric acid at 5℃; for 0.5h; Stage #3: tert-butylbenzene Further stages;	5 3.80 parts of the compound represented by the formula (I-490-a) and 6.40 parts of Oxone (registered trademark) are mixed and mixed.After stirring at 23 ° C. for 30 minutes, the mixture was cooled to 5 ° C.After adding 23.56 parts of sulfuric acid to the obtained mixture, the mixture was stirred at 5 ° C. for 30 minutes. To the obtained mixture, a mixed solution of 3.68 parts of the compound represented by the formula (I-490-b) and 18.40 parts of chloroform is added, stirred at 5 ° C. for 30 minutes, and further at 23 ° C. for 2 Stir for hours. The obtained mixed solution was added to 120 parts of methanol, stirred at 23 ° C. for 30 minutes, and then filtered. After concentrating the obtained filtrate, 125 parts of chloroform and 25 parts of acetonitrile were added to the concentrated residue, and 30 at 23 ° C.After stirring for 1 minute, 60 parts of 5% hydrochloric acid was added, and the mixture was stirred at 23 ° C. for 30 minutes, and then separated to remove the organic layer. 40 parts of ion-exchanged water was added to the obtained organic layer, and the mixture was stirred at 23 ° C. for 30 minutes, and then separated to remove the organic layer. This washing operation was repeated 3 times. The obtained organic layer is concentrated, 45 parts of tert-butyl methyl ether is added to the concentrated mixture, the mixture is stirred at 23 ° C. for 30 minutes, and then filtered to obtain a salt 2 represented by the formula (I-490-c). .37 copies were obtained.
	Stage #1: 4-fluoro-1-iodo-2-methylbenzene With Oxone at 23℃; for 0.5h; Stage #2: With sulfuric acid at 5℃; for 0.5h; Stage #3: tert-butylbenzene Further stages;	6 Example 6: Synthesis of Salt Represented by Formula (I-236) 3.80 Parts of a compound represented by formula (I-236-a) and 6.40 parts of Oxone (registered trademark) were mixed, followed by stirring at 23° C. for 30 minutes and further cooling to 5° C. To the mixture thus obtained, 23.56 parts of sulfuric acid were added, followed by stirring at 5° C. for 30 minutes. To the mixture thus obtained, a mixed solution of 3.68 parts of a compound represented by formula (I-236-b) and 18.40 parts of chloroform was added, followed by stirring at 5° C. for 30 minutes and further stirring at 23° C. for 2 hours. The mixed solution thus obtained was added to 120 parts of methanol, followed by stirring at 23° C. for 30 minutes and further filtration. The filtrate thus obtained was concentrated and then 125 parts of chloroform and 25 parts of acetonitrile were added to the concentrated residue, and after stirring at 23° C. for 30 minutes, 60 parts of 5% hydrochloric acid was added. After stirring at 23° C. for 30 minutes, the organic layer was isolated through separation. To the organic layer thus obtained, 40 parts of ion-exchanged water was added, and after stirring at 23° C. for 30 minutes, the organic layer was isolated through separation. This water washing operation was repeated three times. The organic layer thus obtained was concentrated and then 45 parts of tert-butyl ethyl ether was added to the concentrated mixture, followed by stirring at 23° C. for 30 minutes and further filtration to obtain 2.37 parts of a salt represented by formula (I-236-c).
	Stage #1: 4-fluoro-1-iodo-2-methylbenzene With ozone at 23℃; for 0.5h; Stage #2: With sulfuric acid at 5℃; for 0.5h; Stage #3: tert-butylbenzene In chloroform at 5 - 23℃; for 2.5h;	3 Example 3: Synthesis of salt represented by the formula (I-274) 3.80 parts of the compound represented by the formula (I-274-a) and 6.40 parts of Ozon (registered trademark) were mixed, stirred at 23 ° C. for 30 minutes, and then cooled to 5 ° C. After adding 23.56 parts of sulfuric acid to the obtained mixture, the mixture was stirred at 5 ° C. for 30 minutes. To the obtained mixture, a mixed solution of 3.68 parts of the compound represented by the formula (I-274-b) and 18.40 parts of chloroform is added, stirred at 5 ° C. for 30 minutes, and further at 23 ° C. for 2 Stir for hours. The obtained mixed solution was added to 120 parts of methanol, stirred at 23 ° C. for 30 minutes, and then filtered. After concentrating the obtained filtrate, 125 parts of chloroform and 25 parts of acetonitrile are added to the concentrated residue, and the mixture is stirred at 23 ° C. for 30 minutes, 60 parts of 5% hydrochloric acid is added, and the mixture is stirred at 23 ° C. for 30 minutes and then minute. The liquid was applied and the organic layer was taken out. 40 parts of ion-exchanged water was added to the obtained organic layer, and the mixture was stirred at 23 ° C. for 30 minutes and then separated to remove the organic layer. This washing operation was repeated 3 times. The obtained organic layer is concentrated, 45 parts of tert-butylmethyl ether is added to the concentrated mixture, the mixture is stirred at 23 ° C. for 30 minutes, and then filtered to obtain a salt 2 represented by the formula (I-274-c). .37 copies were obtained.

	Stage #1: 4-fluoro-1-iodo-2-methylbenzene With oxone at 5 - 23℃; for 0.5h; Stage #2: With sulfuric acid at 5℃; for 0.5h; Stage #3: tert-butylbenzene at 5 - 23℃; for 2.5h;	4 Example 4: Synthesis of salt represented by the formula (I-1714) 3.80 parts of the compound represented by the formula (I-1714-a) and 6.40 parts of Oxone (registered trademark) are mixed and 23 ° C. After stirring for 30 minutes, the mixture was cooled to 5 ° C. After adding 23.56 parts of sulfuric acid to the obtained mixture, the mixture was stirred at 5 ° C. for 30 minutes. To the obtained mixture, a mixed solution of 3.68 parts of the compound represented by the formula (I-1714-b) and 18.40 parts of chloroform is added, stirred at 5 ° C. for 30 minutes, and further at 23 ° C. for 2 Stir for hours. The obtained mixed solution was added to 120 parts of methanol, stirred at 23 ° C. for 30 minutes, and then filtered. After concentrating the obtained filtrate, 125 parts of chloroform and 25 parts of acetonitrile are added to the concentrated residue, and the mixture is stirred at 23 ° C. for 30 minutes, 60 parts of 5% hydrochloric acid is added, and the mixture is stirred at 23 ° C. for 30 minutes and then minute. The liquid was applied and the organic layer was taken out. 40 parts of ion-exchanged water was added to the obtained organic layer, and the mixture was stirred at 23 ° C. for 30 minutes and then separated to remove the organic layer. This washing operation was repeated 3 times. The obtained organic layer is concentrated, 45 parts of tert-butylmethyl ether is added to the concentrated mixture, the mixture is stirred at 23 ° C. for 30 minutes, and then filtered to obtain a salt 2 represented by the formula (I-1714-c). .37 copies were obtained.
	Stage #1: 4-fluoro-1-iodo-2-methylbenzene With oxone at 23℃; for 0.5h; Stage #2: With sulfuric acid at 5℃; for 0.5h; Stage #3: tert-butylbenzene In chloroform at 5 - 23℃; for 2.5h;	3 Example 3: Synthesis of salt represented by the formula (I-274) 3.80 parts of the compound represented by the formula (I-274-a) and 6.40 parts of Ozon (registered trademark) are mixed, stirred at 23 ° C. for 30 minutes, and then stirred.It was cooled to 5 ° C. After adding 23.56 parts of sulfuric acid to the obtained mixture, the mixture was stirred at 5 ° C. for 30 minutes. In the resulting mixture,A mixed solution of 3.68 parts of the compound represented by the formula (I-274-b) and 18.40 parts of chloroform is added, and after stirring at 5 ° C. for 30 minutes,Further, the mixture was stirred at 23 ° C. for 2 hours. The obtained mixed solution,After adding to 120 parts of methanol and stirring at 23 ° C. for 30 minutes,Filtered. After concentrating the obtained filtrate, it is added to the concentrated residue.125 parts of chloroform and 25 parts of acetonitrile were added,After stirring at 23 ° C. for 30 minutes, 60 parts of 5% hydrochloric acid was added, and the mixture was stirred at 23 ° C. for 30 minutes, then separated and the organic layer was taken out.40 parts of ion-exchanged water was added to the obtained organic layer, and the mixture was stirred at 23 ° C. for 30 minutes and then separated to remove the organic layer.This washing operation was repeated 3 times. The obtained organic layer is concentrated andAdd 45 parts of tert-butyl methyl ether to the concentrated mixture and addBy stirring at 23 ° C. for 30 minutes and then filtering.2.37 parts of salt represented by the formula (I-274-c) was obtained.
	Stage #1: 4-fluoro-1-iodo-2-methylbenzene With ozone at 23℃; for 0.5h; Stage #2: With sulfuric acid at 5℃; for 0.5h; Stage #3: tert-butylbenzene Further stages;	3 Example 3: Synthetic formula of salt represented by the formula (I-667) 3.80 parts of the compound represented by (I-667-a) and 6.40 parts of Ozon (registered trademark) were mixed, stirred at 23 ° C. for 30 minutes, and then cooled to 5 ° C.After adding 23.56 parts of sulfuric acid to the obtained mixture, the mixture was stirred at 5 ° C. for 30 minutes.To the obtained mixture, a mixed solution of 3.68 parts of the compound represented by the formula (I-667-b) and 18.40 parts of chloroform is added, stirred at 5 ° C. for 30 minutes, and further at 23 ° C. for 2 Stir for hours.The obtained mixed solution was added to 120 parts of methanol, stirred at 23 ° C. for 30 minutes, and then filtered.After concentrating the obtained filtrate, 125 parts of chloroform and 25 parts of acetonitrile are added to the concentrated residue, and the mixture is stirred at 23 ° C. for 30 minutes, 60 parts of 5% hydrochloric acid is added, and the mixture is stirred at 23 ° C. for 30 minutes and then minute. The liquid was applied and the organic layer was taken out.40 parts of ion-exchanged water was added to the obtained organic layer, and the mixture was stirred at 23 ° C. for 30 minutes and then separated to remove the organic layer.This washing operation was repeated 3 times.The obtained organic layer was concentrated, 45 parts of tert-butylmethyl ether was added to the concentrated mixture, the mixture was stirred at 23 ° C. for 30 minutes, and then filtered.2.37 parts of salt represented by the formula (I-667-c) was obtained.
	Stage #1: 4-fluoro-1-iodo-2-methylbenzene With oxone at 23℃; for 0.5h; Stage #2: With sulfuric acid at 5℃; for 0.5h; Stage #3: tert-butylbenzene In chloroform at 5 - 23℃; for 2.5h;	3 Example 3: Synthesis of salt represented by the formula (I-667) 3.80 parts of the compound represented by the formula (I-667-a) and 6.40 parts of Ozon (registered trademark) are mixed, stirred at 23 ° C. for 30 minutes, and then stirred.It was cooled to 5 ° C. After adding 23.56 parts of sulfuric acid to the obtained mixture, the mixture was stirred at 5 ° C. for 30 minutes. In the resulting mixture,A mixed solution of 3.68 parts of the compound represented by the formula (I-667-b) and 18.40 parts of chloroform was added.After stirring at 5 ° C. for 30 minutes, the mixture was further stirred at 23 ° C. for 2 hours.The obtained mixed solution was added to 120 parts of methanol, stirred at 23 ° C. for 30 minutes, and then filtered. After concentrating the obtained filtrate, 125 parts of chloroform and 25 parts of acetonitrile were added to the concentrated residue.After stirring at 23 ° C. for 30 minutes, 60 parts of 5% hydrochloric acid was added, and the mixture was stirred at 23 ° C. for 30 minutes, then separated and the organic layer was taken out.40 parts of ion-exchanged water was added to the obtained organic layer, and the mixture was stirred at 23 ° C. for 30 minutes and then separated to remove the organic layer.This washing operation was repeated 3 times. The obtained organic layer is concentrated andAdd 45 parts of tert-butyl methyl ether to the concentrated mixture and addBy stirring at 23 ° C. for 30 minutes and then filtering.2.37 parts of salt represented by the formula (I-667-c) was obtained.
	Stage #1: 4-fluoro-1-iodo-2-methylbenzene With ozone at 23℃; for 0.5h; Stage #2: With sulfuric acid at 5℃; for 0.5h; Stage #3: tert-butylbenzene In chloroform at 5 - 23℃; for 2.5h;	3 Example 3: Synthesis of salt represented by the formula (I-667) 3.80 parts of the compound represented by the formula (I-667-a) and 6.40 parts of Ozon (registered trademark) were mixed, stirred at 23 ° C. for 30 minutes, and then cooled to 5 ° C. After adding 23.56 parts of sulfuric acid to the obtained mixture, the mixture was stirred at 5 ° C. for 30 minutes. To the obtained mixture, a mixed solution of 3.68 parts of the compound represented by the formula (I-667-b) and 18.40 parts of chloroform is added, stirred at 5 ° C. for 30 minutes, and further at 23 ° C. for 2 Stir for hours. The obtained mixed solution was added to 120 parts of methanol, stirred at 23 ° C. for 30 minutes, and then filtered. After concentrating the obtained filtrate, 125 parts of chloroform and 25 parts of acetonitrile are added to the concentrated residue, and the mixture is stirred at 23 ° C. for 30 minutes, 60 parts of 5% hydrochloric acid is added, and the mixture is stirred at 23 ° C. for 30 minutes and then minute. The liquid was applied and the organic layer was taken out. 40 parts of ion-exchanged water was added to the obtained organic layer, and the mixture was stirred at 23 ° C. for 30 minutes and then separated to remove the organic layer. This washing operation was repeated 3 times. The obtained organic layer was concentrated, 45 parts of tert-butylmethyl ether was added to the concentrated mixture, the mixture was stirred at 23 ° C. for 30 minutes, and then filtered.2.37 parts of salt represented by the formula (I-667-c) was obtained.
	Stage #1: 4-fluoro-1-iodo-2-methylbenzene With ozone at 23℃; for 0.5h; Stage #2: With sulfuric acid at 0 - 5℃; for 0.5h; Stage #3: tert-butylbenzene Further stages;	3 Example 3: Synthesis of salt represented by the formula (I-274) 3.80 parts of the compound represented by the formula (I-274-a) and 6.40 parts of Ozon (registered trademark) were mixed, stirred at 23 ° C. for 30 minutes, and then cooled to 5 ° C.After adding 23.56 parts of sulfuric acid to the obtained mixture, the mixture was stirred at 5 ° C. for 30 minutes.To the obtained mixture, a mixed solution of 3.68 parts of the compound represented by the formula (I-274-b) and 18.40 parts of chloroform is added, stirred at 5 ° C. for 30 minutes, and further at 23 ° C. for 2 Stir for hours.The obtained mixed solution was added to 120 parts of methanol, stirred at 23 ° C. for 30 minutes, and then filtered.After concentrating the obtained filtrate, 125 parts of chloroform and 25 parts of acetonitrile are added to the concentrated residue, and the mixture is stirred at 23 ° C. for 30 minutes, 60 parts of 5% hydrochloric acid is added, and the mixture is stirred at 23 ° C. for 30 minutes and then minute. The liquid was applied and the organic layer was taken out.40 parts of ion-exchanged water was added to the obtained organic layer, and the mixture was stirred at 23 ° C. for 30 minutes and then separated to remove the organic layer. This washing operation was repeated 3 times.The obtained organic layer is concentrated, 45 parts of tert-butylmethyl ether is added to the concentrated mixture, and the mixture is stirred at 23 ° C. for 30 minutes, and thenFiltration gave 2.37 parts of a salt represented by the formula (I-274-c).

Reference： [1]Current Patent Assignee: Sumitomo Chemical (w/o Dongwoo Fine-Chem); SUMITOMO CHEMICAL COMPANY LIMITED - JP2021/11479, 2021, A Location in patent: Paragraph 0226
[2]Current Patent Assignee: SUMITOMO CHEMICAL COMPANY LIMITED; Sumitomo Chemical (w/o Dongwoo Fine-Chem) - US2021/371376, 2021, A1 Location in patent: Paragraph 0843-0844
[3]Current Patent Assignee: SUMITOMO CHEMICAL COMPANY LIMITED; Sumitomo Chemical (w/o Dongwoo Fine-Chem) - JP2021/183597, 2021, A Location in patent: Paragraph 0254
[4]Current Patent Assignee: SUMITOMO CHEMICAL COMPANY LIMITED; Sumitomo Chemical (w/o Dongwoo Fine-Chem) - JP2021/181430, 2021, A Location in patent: Paragraph 0248
[5]Current Patent Assignee: Sumitomo Chemical (w/o Dongwoo Fine-Chem); SUMITOMO CHEMICAL COMPANY LIMITED - JP2021/183599, 2021, A Location in patent: Paragraph 0246
[6]Current Patent Assignee: SUMITOMO CHEMICAL COMPANY LIMITED; Sumitomo Chemical (w/o Dongwoo Fine-Chem) - JP2021/183598, 2021, A Location in patent: Paragraph 0268
[7]Current Patent Assignee: SUMITOMO CHEMICAL COMPANY LIMITED; Sumitomo Chemical (w/o Dongwoo Fine-Chem) - JP2021/183596, 2021, A Location in patent: Paragraph 0264
[8]Current Patent Assignee: SUMITOMO CHEMICAL COMPANY LIMITED; Sumitomo Chemical (w/o Dongwoo Fine-Chem) - JP2021/183602, 2021, A Location in patent: Paragraph 0269
[9]Current Patent Assignee: SUMITOMO CHEMICAL COMPANY LIMITED; Sumitomo Chemical (w/o Dongwoo Fine-Chem) - JP2021/183595, 2021, A Location in patent: Paragraph 0243

67
[ 253185-04-5 ]
[ 66256-28-8 ]
4-oxoadamantane 1-yl-oxycarbonyl(difluoro)methanesulfonate triethylamine [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	Stage #1: 4-fluoro-1-iodo-2-methylbenzene With oxone at 23℃; for 0.5h; Stage #2: With sulfuric acid at 5℃; for 0.5h; Stage #3: tert-butylbenzene Further stages;	7 3.80 parts of the compound represented by the formula (I-274-a) and 6.40 parts of Oxone (registered trademark) are mixed and mixed.After stirring at 23 ° C. for 30 minutes, the mixture was cooled to 5 ° C. After adding 23.56 parts of sulfuric acid to the obtained mixture, the mixture was stirred at 5 ° C. for 30 minutes. To the obtained mixture, a mixed solution of 3.68 parts of the compound represented by the formula (I-274-b) and 18.40 parts of chloroform is added, stirred at 5 ° C. for 30 minutes, and further at 23 ° C. for 2 Stir for hours. The obtained mixed solution was added to 120 parts of methanol, stirred at 23 ° C. for 30 minutes, and then filtered. After concentrating the obtained filtrate, 125 parts of chloroform and 25 parts of acetonitrile were added to the concentrated residue, and 30 at 23 ° C.After stirring for 1 minute, 60 parts of 5% hydrochloric acid was added, and the mixture was stirred at 23 ° C. for 30 minutes, and then separated to remove the organic layer. 40 parts of ion-exchanged water was added to the obtained organic layer, and the mixture was stirred at 23 ° C. for 30 minutes and then separated to remove the organic layer. This washing operation was repeated 3 times. The obtained organic layer is concentrated, 45 parts of tert-butyl methyl ether is added to the concentrated mixture, the mixture is stirred at 23 ° C. for 30 minutes, and then filtered to obtain a salt 2 represented by the formula (I-274-c). .37 copies were obtained.

Reference： [1]Current Patent Assignee: SUMITOMO CHEMICAL COMPANY LIMITED; Sumitomo Chemical (w/o Dongwoo Fine-Chem) - JP2021/11478, 2021, A Location in patent: Paragraph 0221

68
ethyl 3-(4-amino-3-ethynylphenyl)propanoate [ No CAS ]
[ 66256-28-8 ]
C₂₀H₂₀FNO₂ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
69%	With bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide; trimethylamine In N,N-dimethyl-formamide at 80℃; for 6h; Inert atmosphere;

Reference： [1]Zhao, Xiaodi; Yoon, Dong-Oh; Yoo, Jaeho; Park, Hyun-Ju [Journal of Medicinal Chemistry, 2021, vol. 64, # 7, p. 4130 - 4149]

69
[ 66256-28-8 ]
1-(2-bromo-3-methylphenyl)-1-phenylethan-1-ol [ No CAS ]
(S)-2-fluoro-4,6,10-trimethyl-6-phenyl-6H-benzo[c]chromene [ No CAS ]
1-(2-bromo-3-methylphenyl)-1-phenylethan-1-ol [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
1: 48% 2: 35%	With trifuran-2-yl-phosphane; palladium diacetate; potassium carbonate; methyl (1S)-bicyclo<2.2.1>hept-2-eno-2-carboxylate In toluene at 105℃; for 23h; Schlenk technique; Inert atmosphere; Resolution of racemate; enantioselective reaction;

Reference： [1]Cheng, Hong-Gang; Ding, Bo; Hong, Xin; Hua, Yu; Liu, Ze-Shui; Xie, Pei-Pei; Zhou, Qianghui [Angewandte Chemie - International Edition, 2021, vol. 60, # 23, p. 12824 - 12828][Angew. Chem., 2021, vol. 133, # 23, p. 12934 - 12938,5]

70
[ 869107-17-5 ]
[ 66256-28-8 ]
(2R,3R,4S,5R,6S)-2-(acetoxymethyl)-6-((4-fluoro-2-methyl-6-(4-methylbenzoyl)phenyl)selanyl)tetrahydro-2H-pyran-3,4,5-triyl triacetate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
45%	With 1,3-dimethyl-2-imidazolidinone; dichloro bis(acetonitrile) palladium(II); bicyclo[2.2.1]hept-5-ene-2-carbonitrile; potassium carbonate; tri(4-chlorophenyl)phosphine at 95℃; for 16h; Inert atmosphere; regioselective reaction;

Reference： [1]Ding, Ya-Nan; Huang, Yan-Chong; Shi, Wei-Yu; Zheng, Nian; Wang, Cui-Tian; Chen, Xi; An, Yang; Zhang, Zhe; Liang, Yong-Min [Organic Letters, 2021, vol. 23, # 15, p. 5641 - 5646]

71
[ 66256-28-8 ]
1-(2-bromo-3-methylphenyl)-1-phenylethan-1-ol [ No CAS ]
(S)-2-fluoro-4,6,10-trimethyl-6-phenyl-6H-benzo[c]chromene [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
35%	With trifuran-2-yl-phosphane; palladium diacetate; potassium carbonate; methyl (1S)-bicyclo<2.2.1>hept-2-eno-2-carboxylate In toluene at 105℃; for 23h; Inert atmosphere;	11 Example 1: Preparation of chiral benzopyran 3a and chiral tertiary alcohol 1a General procedure: Under the protection of argon, add palladium acetate (1.1mg, 0.005mmol), tris(2-furyl)phosphine (4.6mg, 0.02mmol), potassium carbonate (33.2mg) to a dry reaction tube equipped with a magnetic stirrer. , 0.24mmol) and dry toluene (1.0mL), then add (1S,4R)-2-norbornene-2-carboxylic acid methyl ester (N1*) (9.1mg, 0.06mmol), 1-iodonaphthalene (2a ) (40.6 mg, 0.16 mmol) and racemic aryl tertiary alcohol (1a) (58.2 mg, 0.2 mmol). The resulting mixture was reacted at 105°C under an argon atmosphere for 24 hours. After the reaction, it was cooled to room temperature, the mixture was filtered with celite, washed with ethyl acetate, and the solvent was distilled off under reduced pressure.Column chromatography is used to separate and purify the chiral benzopyran product (S)-3a and recover the unreacted chiral tertiary alcohol (R)-1a.Chiral benzopyran product (S)-3a: colorless oily liquid, 46% yield, 94% ee.

Reference： [1]Current Patent Assignee: WUHAN UNIVERSITY - CN113087691, 2021, A Location in patent: Paragraph 0032-0034; 0062-0064

72
[ 66256-28-8 ]
2-bromo-N-(2-(tert-butyl)phenyl)-3-methylbenzamide [ No CAS ]
5-(2-(tert-butyl)phenyl)-2-fluoro-4,10-dimethylphenanthridin-6(5H)-one [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
72%	With trifuran-2-yl-phosphane; palladium diacetate; (1S,4R)-2-norbornene-2-carboxylic acid ethyl ester; potassium carbonate In acetonitrile at 70℃; for 36h; Inert atmosphere; Sealed tube; enantioselective reaction;

Reference： [1]Chen, Jiangwei; Cheng, Hong-Gang; Hong, Xin; Hua, Yu; Liu, Ze-Shui; Ma, Yuanyuan; Wu, Chenggui; Xie, Pei-Pei; Zhou, Qianghui [Chem, 2021, vol. 7, # 7, p. 1917 - 1932]

73
[ 5765-65-1 ]
[ 121-46-0 ]
[ 66256-28-8 ]
4-(7-fluoro-4,4a,9,9a-tetrahydro-1H-1,4-methanofluoren-5-yl)morpholine [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
80%	Stage #1: 4-(benzoyloxy)morpholine; bicyclo[2.2.1]hepta-2,5-diene; 4-fluoro-1-iodo-2-methylbenzene With palladium diacetate; caesium carbonate; tricyclohexylphosphine; Trimethylacetic acid In 1,4-dioxane at 20℃; for 0.166667h; Inert atmosphere; Stage #2: In 1,4-dioxane at 140℃; for 12h; Inert atmosphere;

Reference： [1]An, Yang; Ding, Ya-Nan; Gou, Xue-Ya; Li, Qiao; Li, Yuke; Liang, Yong-Min; Zhang, Xiao-Yan; Zhang, Zhe [Organic Letters, 2021, vol. 23, # 20, p. 7961 - 7965]

74
[ 66256-28-8 ]
C₁₂H₁₅BF₉IO₂ [ No CAS ]
C₁₃H₁₀F₁₀O [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 2 steps 1: C₃₄H₅₀N₄; nickel(II) bromide dimethoxyethane; zinc; tetrabutyl-ammonium chloride / 1,2-dimethoxyethane / 12 h / 20 °C 2: dihydrogen peroxide; sodium hydroxide / 1,2-dimethoxyethane