Name: 62336-24-7|(2-Bromophenyl)diphenylphosphine|98%
Brand: Ambeed
SKU: A855892
Price: 11.0 USD
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1
[ 1079-66-9 ]
[ 583-53-9 ]
[ 62336-24-7 ]

Yield	Reaction Conditions	Operation in experiment
81%	Stage #1: 2,3-dibromobenzene With n-butyllithium In tetrahydrofuran; diethyl ether; hexane at -110℃; for 0.833333h; Stage #2: chloro-diphenylphosphine In tetrahydrofuran; diethyl ether; hexane at -110 - 20℃; Further stages.;
76%	Stage #1: 2,3-dibromobenzene With n-butyllithium In tetrahydrofuran; diethyl ether; hexane at -120℃; for 0.75h; Stage #2: chloro-diphenylphosphine In tetrahydrofuran; diethyl ether; hexane at -120 - -80℃; for 1h;
72%	Stage #1: 2,3-dibromobenzene With n-butyllithium In tetrahydrofuran; diethyl ether; hexane at -110℃; for 1.25h; Inert atmosphere; Schlenk technique; Stage #2: chloro-diphenylphosphine In tetrahydrofuran; diethyl ether; hexane at -110 - 20℃; Inert atmosphere; Schlenk technique;

72%	Stage #1: 2,3-dibromobenzene With n-butyllithium In tetrahydrofuran; diethyl ether; hexane at -110℃; for 0.5h; Stage #2: chloro-diphenylphosphine In tetrahydrofuran; diethyl ether; hexane at 20℃;	2.2.1. Synthesis of (2-bromophenyl)diphenylphosphine This compound was synthesized from a modification of the literature protocol [34]. A solutionof n-BuLi (1.6 M in hexanes, 6.22 mL, 9.95 mmol) was added dropwise over 45 min to a solutionof 1,2-dibromobenzene (2.35 g, 9.95 mmol) in Et2O/THF (1/1 v/v, 50 mL) at -110 °C. After30 min of stirring at the same temperature, a white precipitate appeared and chlorodiphenylphosphine(2.20 g, 9.95 mmol) was added dropwise. The mixture was then allowed towarm to room temperature overnight and the volatile components were removed undervacuum. The residue was taken up into CH2Cl2/Et2O (1/2 v/v, 15 mL) and filtered throughsilica which was then washed with CH2Cl2/Et2O (1/2 v/v, 9 mL). The filtrate was evaporatedunder reduced pressure to give the pure product as a white solid (2.44 g, 72%). The characterizationdata were identical to those previously reported in the literature [35].
65.5%	Stage #1: 2,3-dibromobenzene With TurboGrignard In tetrahydrofuran at -17 - -13℃; for 3h; Stage #2: chloro-diphenylphosphine In tetrahydrofuran at -20 - 20℃; for 16.5h;	General Procedure for Obtaining 1-Bromo-2-Diphenylphosphinoarenes by the Case of 1-Bromo-2-Diphenylphosphino-4,5-Dimethylbenzene General procedure: A solution of 6.00 g (22.8 mmol) of 1,2-dibromo-4,5-dimethylbenzene in 12 mL of tetrahydrofuran wasadded to preliminary prepared 30 mL of a 1M solutionof iso-PrMgLiCl in tetrahydrofuran and stirred at -17to -13°C. After 3 h, 5.12 g (23.25 mmol) of chlorodiphenylphosphinewas added dropwise to the solutionat -20 to -10°C. The obtained solution was stirred for30 min at -10°C, and then it was allowed to warm upto room temperature, stirred for additional 16 h, andevaporated. 30 mL of methylene chloride and 20 mLof a saturated aqueous solution of ammonium chloridewere added to the residue. The organic phase wasseparated and dried over anhydrous sodium sulfate.The residue after the evaporation was recrystallizedusing an ethanol-acetone mixture.
65.5%	Stage #1: 2,3-dibromobenzene With isopropylmagnesium chloride; lithium chloride In tetrahydrofuran at -17 - -13℃; for 3h; Inert atmosphere; Schlenk technique; Stage #2: chloro-diphenylphosphine In tetrahydrofuran at -20 - -10℃; for 16.5h; Inert atmosphere; Schlenk technique;	Synthesis of 1-bromo-2-diphenylphosphinobenzene A solution of 5.38 g (22.8 mmol) of 1,2-dibromobenzene in 12 mL of tetrahydrofuran was added to30 mL of a preliminarily prepared 1 M iso-PrMgLiCl solution in tetrahydrofuran and stirred at -17 to-13°C. After 3 h, 5.12 g (23.25 mmol) of chlorodiphenylphosphine was added dropwise to the solution at -20 to -10°C. The resulting solution was stirred for 30 min at -10°C, allowed to warm up to room temperature, stirred for additional 16 h, and evaporated. To the residue, 30 mL of dichloromethane and 20 mLof a saturated aqueous solution of ammonium chloride were added. The organic phase was separated and dried over anhydrous sodium sulfate. The residue after the evaporation was recrystallized from an ethanol-acetone mixture. The yield of 1-bromo-2-diphenylphosphinobenzene was 65.5%. 1H NMR (300 MHz, CDCl3): δ(ppm) 7.60 (m, J = 4 Hz, 1H), 7.41-7.26 (m, J = 3 Hz,10H), 7.20 (m, J = 4 Hz, 2H), 6.75 (q, J = 4 Hz, 1H).31P{1H} NMR (121.49 MHz, CDCl3): δ (ppm)-5.12 (s).
61%	Stage #1: 2,3-dibromobenzene With n-butyllithium In tetrahydrofuran; diethyl ether; hexane at -110℃; for 0.833333h; Inert atmosphere; Stage #2: chloro-diphenylphosphine In tetrahydrofuran; diethyl ether; hexane at -110 - 20℃; Inert atmosphere;
	(i) nBuLi, (ii) /BRN= 512032/; Multistep reaction;
	With n-butyllithium 1.) hexane, Et₂O, THF, -115 to -110 deg C, 40 min, 2.) hexane, Et₂O, THF, -110 to -105 deg C, 15 min; Yield given. Multistep reaction;
	With n-butyllithium 1.) THF, hexane, -100 deg C, 2.) THF, hexane, from -100 deg C to RT; Yield given. Multistep reaction;
	With n-butyllithium 1.) THF, hexane, -130 deg C, 20 min, 2.) THF, hexane, from -130 deg C to RT; Yield given; Multistep reaction;
	With n-butyllithium

Reference： [1]Luo, Xiancai; Zhang, Heng; Duan, Hui; Liu, Qiang; Zhu, Lizheng; Zhang, Tony; Lei, Aiwen [Organic Letters, 2007, vol. 9, # 22, p. 4571 - 4574]
[2]Quintard, Delphine; Keller, Manfred; Breit, Bernhard [Synthesis, 2004, # 6, p. 905 - 908]
[3]Nol-Duchesneau, Ludovik; Lugan, Nol; Lavigne, Guy; Labande, Agns; Csar, Vincent [Organometallics, 2014, vol. 33, # 19, p. 5085 - 5088]
[4]Chen, Bu-Lin; Liu, Li; Zhong, Xin-Xin; Asiri, Abdullah M.; Alamry, Khalid A.; Li, Guang-Hua; Li, Fa-Bao; Zhu, Nian-Yong; Wong, Wai-Yeung; Qin, Hai-Mei [Journal of Coordination Chemistry, 2017, vol. 70, # 23, p. 3907 - 3919]
[5]Cheredilin; Sheloumov; Senin; Kozlova; Afanas’ev; Bespalova [Petroleum Chemistry, 2019, vol. 59, p. S72 - S87][Neftekhimiya]
[6]Afanas’ev, V. V.; Bespalova, N. B.; Cheredilin, D. N.; Kozlova, G. A.; Senin, A. A.; Sheloumov, A. M. [Petroleum Chemistry, 2020, vol. 60, # 1, p. 55 - 68][Neftekhimiya, 2020, vol. 60, # 1, p. 61 - 75,15]
[7]Wilkins, Lewis C.; Kim, Youngmin; Litle, Elishua D.; Gabbaï, François P. [Angewandte Chemie - International Edition, 2019, vol. 58, # 50, p. 18266 - 18270][Angew. Chem., 2019, vol. 131, p. 18434 - 18438,5]
[8]Hart,F.A. [Journal of the Chemical Society, 1960, p. 3324 - 3328]
[9]Harder, Sjoerd; Brandsma, Lambert; Kanters, Jan A.; Duisenberg, Albert; Lenthe, Joop H. van [Journal of Organometallic Chemistry, 1991, vol. 420, # 2, p. 143 - 154]
[10]Ravindar; Hemling; Schumann; Blum [Synthetic Communications, 1992, vol. 22, # 10, p. 1453 - 1459]
[11]Reetz, Manfred T.; Gosberg, Andreas [Tetrahedron Asymmetry, 1999, vol. 10, # 11, p. 2129 - 2137]
[12]Wilders, Alison M.; Contrella, Nathan D.; Sampson, Jessica R.; Zheng, Mingfang; Jordan, Richard F. [Organometallics, 2017, vol. 36, # 24, p. 4990 - 5002]

2
[ 583-55-1 ]
[ 17154-34-6 ]
[ 62336-24-7 ]

Yield	Reaction Conditions	Operation in experiment
82%	With dichloro bis(acetonitrile) palladium(II) In benzene at 70℃; for 100h;
62%	In benzene at 60 - 70℃; for 100h;
61%	With dichloro bis(acetonitrile) palladium(II)

In toluene

R.1.a (a) (a) Synthesis of (2-diphenylphosphinophenyl)diethylphosphonite According to the method described in a literature (S. E. Tunney and J. K. Stille, J. Org. Chem., 1987, 52, 748), (2-bromophenyl)diphenylphosphine was obtained by reacting 2-bromoiodobenzene and (trimethylsilyl)diphenylphosphine in toluene in the presence of dichlorobis(acetonitrile)palladium. Into a four-necked flask was weighed 10.00 g (29.3 mmol) of (2-bromophenyl)diphenylphosphine obtained in the above. The atmosphere of the reaction vessel fitted with a thermometer, a condenser tube, and a dropping funnel with a pressure-equalizing tube was completely replaced with nitrogen, and 100 mL of anhydrous tetrahydrofuran (hereinafter referred to as THF) was added thereto.

Reference： [1]Tunney, S. E.; Stille, J. K. [Journal of Organic Chemistry, 1987, vol. 52, # 5, p. 748 - 753]
[2]Meprathu, Bindu V.; Justik, Michael W.; Protasiewicz, John D. [Tetrahedron Letters, 2005, vol. 46, # 31, p. 5187 - 5190]
[3]Bennett, Martin A.; Bhargava, Suresh K.; Hockless, David C. R.; Welling, Lee L.; Willis, Anthony C. [Journal of the American Chemical Society, 1996, vol. 118, # 43, p. 10469 - 10478]
[4]Current Patent Assignee: TAKASAGO INTERNATIONAL CORPORATION - US2003/120067, 2003, A1

3
[ 583-55-1 ]
[ 829-85-6 ]
[ 62336-24-7 ]

Yield	Reaction Conditions	Operation in experiment
98%	With tetrakis-(triphenylphosphine)-palladium; triethylamine In toluene at 80℃; for 12h; Inert atmosphere;
98%	With tetrakis-(triphenylphosphine)-palladium; triethylamine In toluene at 85℃; for 17h; Inert atmosphere;
97%	With tetrakis-(triphenylphosphine)-palladium; triethylamine In acetonitrile for 6h; Inert atmosphere; Reflux;	1.1 Pd (PPh 3) 4 (0.463 g, 0.400 mmol) was placed in a 100 mL two-necked eggplant-shaped flask, and under a nitrogen atmosphere,60 ml of acetonitrile, diphenylphosphine (7.11 g, 38.2 mmol), triethylamine (4.69 g, 46.4 mmol) and 2-bromoiodobenzene (12.0 g, 42.3 mmol)The reaction was carried out under heating reflux conditions for 6 hours.Water was added to the reaction solution, the organic phase was extracted with dichloromethane, and dried over anhydrous magnesium sulfate. After distilling off the organic solvent under reduced pressure, compound 1 was isolated by silica gel column chromatography. Yield 12.3 g, yield 97%.

95%	With tetrakis-(triphenylphosphine)-palladium; triethylamine In toluene at 80℃; for 16h; Sealed tube;	1 2-Iodobromobenzene (24.1 g, 85.3 mmol), diphenylphosphine (15.9 g, 85.3 mmol),Triethylamine (101 g, 100 mmol) and a catalytic amount of Pd (PPh3) 4 (513.0 mg, 0.45 mmol)Dissolve in 15 mL of toluene to give a clear, bright yellow solution.The solution was heated with stirring in a sealed reactor at 80 ° C for 16 hours to give triethyl ammonium iodide precipitate. The resulting orange solution was vacuum dried at 50 ° C,Extracted into ether (400 mL) and filtered through a pad of silica gel to give a clear pale yellow solution,The volatiles were removed in vacuo to give a cream colored powder (27.6 g, 95%).Characterization data matched previously reported data for this compound.
95%	With tetrakis-(triphenylphosphine)-palladium; triethylamine In toluene at 80℃; for 16h;
95%	With tetrakis-(triphenylphosphine)-palladium; triethylamine In toluene at 80℃; for 16h; Autoclave; Schlenk technique; Inert atmosphere;
94%	With triethylamine In toluene at 80℃; for 14h;
92%	With anhydrous Sodium acetate In N,N-dimethyl acetamide at 130℃; for 72h;
92%	With tetrakis-(triphenylphosphine)-palladium; triethylamine In toluene at 80℃; for 14h; Inert atmosphere; Sealed tube;
92%	With N,N-dimethyl acetamide; anhydrous Sodium acetate; palladium diacetate at 130℃; for 72h; Inert atmosphere;
92%	With anhydrous Sodium acetate; palladium diacetate In N,N-dimethyl acetamide at 130℃; for 72h; Inert atmosphere; Schlenk technique;
92%	With tetrakis-(triphenylphosphine)-palladium; triethylamine In toluene at 80℃; for 16h; Sealed tube;
91%	With tetrakis-(triphenylphosphine)-palladium; triethylamine In acetonitrile for 6h; Inert atmosphere; Reflux;	1.1; 4.1 (1) Preparation of compound 1-1 In a flask, 1-bromo-2-iodobenzene(310g, 1.1mol), diphenylphosphine (185g, 1mol), triethylamine (121g, 1.2mol) were dissolved in 1.5L acetonitrile,After replacing the nitrogen, Pd(PPh3)4 (11.5 g, 10 mmol) was added. After the addition, the nitrogen was replaced three times, and the reaction was heated to reflux for 6 hours under stirring. TLC detected that the reaction was complete. After cooling to room temperature, the reaction was quenched by adding water to the above reaction system, extracted with dichloromethane, and the organic phase was dried with anhydrous sodium sulfate and purified by column chromatography to obtain compound 1-1 (309 g, 91%).
91.2%	With tetrakis-(triphenylphosphine)-palladium; triethylamine In toluene at 85℃; for 17h; Schlenk technique;
90%	With tetrakis-(triphenylphosphine)-palladium; triethylamine In toluene for 10h; Reflux; Inert atmosphere;
86%	With triethylamine In toluene at 80℃; for 16h;
84%	Stage #1: diphenylphosphane With copper (I) iodide In toluene Stage #2: 1-Bromo-2-iodobenzene With Cs₂CO₃ In toluene at 110℃; for 24h;
75%	With anhydrous potassium acetate; palladium diacetate In N,N-dimethyl acetamide at 130℃; for 120h;
74%	With anhydrous potassium acetate In N,N-dimethyl-formamide at 200℃; for 0.166667h; microwave irradiation;
70%	With anhydrous Sodium acetate; palladium diacetate In N,N-dimethyl acetamide at 130℃; for 72h; Inert atmosphere;	22 Reference Example 22 Under argon atmosphere, N,N-dimethylacetamide (55.0 mL) was added to 1-bromo-2-iodobenzene (7.23 g, 25.6 mmol), diphenyl phosphine (4.71 g, 25.3 mmol), palladium (II) acetate (30.4 mg, 0.135 mmol) and sodium acetate (2.28 g, 27.8 mmol), and [the mixture] was stirred at 130° C. for 3 days. Water (100 mL) was poured into the reactant mixture, and an aqueous layer was extracted with chloroform (60 mL) twice. After combined organic layers were washed with 100 mL of water four times, the layers were dried with sodium sulfate, and then these were concentrated under reduced pressure. A white solid of (2-bromophenyl) diphenyl phosphine was obtained by refining the obtained crude product by silica gel column chromatography (eluent: hexane/ethyl acetate) (yield amount: 6.07 g, yield: 70%). 1H-NMR (400 MHz, CDCl3), δ (ppm): 7.59 (m, 1H), 7.38˜7.32 (m, 6H), 7.30˜7.25 (m, 4H), 7.21˜7.16 (m, 2H), 6.76 (m, 1H). 31P-NMR (162 MHz, CDCl3), δ (ppm): -5.1 (s).
57%	With tetrakis-(triphenylphosphine)-palladium; triethylamine In toluene at 80℃; for 12h; Inert atmosphere;
	With tetrakis-(triphenylphosphine)-palladium; triethylamine In toluene at 80℃;

Reference： [1]Zhang, Fushi; Wang, Liduo; Chang, Shih-Han; Huang, Kuan-Lin; Chi, Yun; Hung, Wen-Yi; Chen, Chih-Ming; Lee, Gene-Hsiang; Chou, Pi-Tai [Dalton Transactions, 2013, vol. 42, # 19, p. 7111 - 7119]
[2]Bischof, Daniel; Breuer, Tobias; Grell, Yvonne; Hofmann, Philipp E.; Ivlev, Sergei I.; Koert, Ulrich; Schiller, Anna L. C.; Tripp, Matthias W.; Witte, Gregor [Angewandte Chemie - International Edition, 2020, vol. 59, # 38, p. 16501 - 16505][Angewandte Chemie, 2020, vol. 132, # 38, p. 16644 - 16648,5]
[3]Current Patent Assignee: NATIONAL INSTITUTE OF ADVANCED INDUSTRIAL SCIENCE AND TECHNOLOGY - JP5791040, 2015, B2 Location in patent: Paragraph 0018
[4]Current Patent Assignee: SOUTHERN UNIVERSITY OF SCIENCE AND TECHNOLOGY OF CHINA - CN107417724, 2017, A Location in patent: Paragraph 0026; 0028; 0029
[5]Tan, Xuefeng; Zeng, Weijun; Zhang, Xiaoyong; Chung, Lung Wa; Zhang, Xumu [Chemical Communications, 2018, vol. 54, # 5, p. 535 - 538]
[6]Li, Jia-Wei; Wang, Liang-Neng; Li, Ming; Tang, Pan-Ting; Luo, Xiao-Peng; Kurmoo, Mohamedally; Liu, Yue-Jin; Zeng, Ming-Hua [Organic Letters, 2019, vol. 21, # 8, p. 2885 - 2889]
[7]Bonnaventure, Isabelle; Charette, Andre B. [Journal of Organic Chemistry, 2008, vol. 73, # 16, p. 6330 - 6340]
[8]Baillie, Colin; Xiao, Jianliang [Tetrahedron, 2004, vol. 60, # 19, p. 4159 - 4168]
[9]Location in patent: experimental part Conifer, Christopher M.; Law, David J.; Sunley, Glenn J.; White, Andrew J. P.; Britovsek, George J. P. [Organometallics, 2011, vol. 30, # 15, p. 4060 - 4066]
[10]Xue, Mei; Li, Jiayun; Peng, Jiajian; Bai, Ying; Zhang, Guodong; Xiao, Wenjun; Lai, Guoqiao [Applied Organometallic Chemistry, 2014, vol. 28, # 2, p. 120 - 126]
[11]Li, Jiayun; Xue, Mei; Bai, Ying; Peng, Jiajian; Xiao, Wenjun [Applied Organometallic Chemistry, 2016, vol. 30, # 11, p. 905 - 910]
[12]An, Jiangzhen; Jia, Chunqi; Li, Gang; Wang, Junjie; Yan, Bingxu; Yang, Suling; Zhong, Lei [Organic Letters, 2020, vol. 22, # 24, p. 9450 - 9455]
[13]Current Patent Assignee: BEIJING ETERNAL MATERIAL TECHNOLOGY CO LTD - CN113402556, 2021, A Location in patent: Paragraph 0102-0106; 0123-0127
[14]Ma, Xufeng; Wang, Han; Liu, Yao; Zhao, Xing; Zhang, Jun [ChemCatChem, 2021, vol. 13, # 24, p. 5134 - 5140]
[15]Xu, Bing; Zhang, Zhan-Ming; Han, Jie; Gu, Guangxin; Zhang, Junliang [Chinese Journal of Chemistry, 2022, vol. 40, # 12, p. 1407 - 1412]
[16]Whited, Matthew T.; Rivard, Eric; Peters, Jonas C. [Chemical Communications, 2006, # 15, p. 1613 - 1615]
[17]Gelman, Dmitri; Jiang, Lei; Buchwald, Stephen L. [Organic Letters, 2003, vol. 5, # 13, p. 2315 - 2318]
[18]Machnitzki, Peter; Nickel, Thomas; Stelzer, Othmar; Landgrafe, Claudia [European Journal of Inorganic Chemistry, 1998, # 7, p. 1029 - 1034]
[19]Stadler, Alexander; Kappe, C. Oliver [Organic Letters, 2002, vol. 4, # 20, p. 3541 - 3543]
[20]Current Patent Assignee: SAGAMI CHEMICAL RESEARCH INSTITUTE; TOSOH CORPORATION - US2020/354389, 2020, A1 Location in patent: Paragraph 0362-0364
[21]Saes, Bartholomeus W. H.; Verhoeven, Dide G. A.; Lutz, Martin; Klein Gebbink, Robertus J. M.; Moret, Marc-Etienne [Organometallics, 2015, vol. 34, # 12, p. 2710 - 2713]
[22]Cannon, Austin T.; Saouma, Caroline T. [Polyhedron, 2021, vol. 207]

4
[ 814-49-3 ]
[ 62336-24-7 ]
[ 182625-37-2 ]

Yield	Reaction Conditions	Operation in experiment
73%	Stage #1: (2-bromophenyl)diphenylphosphane With n-butyllithium In tetrahydrofuran; hexane at -78℃; Stage #2: diethyl chlorophosphate at 20℃; for 4h; Further stages.;
69%	Stage #1: (2-bromophenyl)diphenylphosphane With n-butyllithium In tetrahydrofuran; hexane at -78℃; for 0.166667h; Stage #2: diethyl chlorophosphate In tetrahydrofuran; hexane at -78 - 20℃; Further stages.;
	Stage #1: (2-bromophenyl)diphenylphosphane With n-butyllithium Stage #2: diethyl chlorophosphate

	Stage #1: (2-bromophenyl)diphenylphosphane With n-butyllithium In tetrahydrofuran at -78℃; Stage #2: diethyl chlorophosphate In tetrahydrofuran at 20℃;
	With n-butyllithium

Reference： [1]Ellis, Dianne D.; Harrison, Gayle; Guy Orpen; Phctmung, Hirihattaya; Pringle, Paul G.; Dcvries, Johannes G.; Oevering, Henk [Journal of the Chemical Society, Dalton Transactions, 2000, # 5, p. 671 - 675]
[2]Bonnaventure, Isabelle; Charette, Andre B. [Journal of Organic Chemistry, 2008, vol. 73, # 16, p. 6330 - 6340]
[3]Basra, Sandeep; De Vries, Johannes G.; Hyett, David J.; Harrison, Gayle; Heslop, Katie M.; Orpen, A. Guy; Pringle, Paul G.; Von Der Luehe, Karl [Dalton Transactions, 2004, # 12, p. 1901 - 1905]
[4]Reisinger, Corinna M.; Nowack, Ruediger J.; Volkmer, Dirk; Rieger, Bernhard [Dalton Transactions, 2007, # 2, p. 272 - 278]
[5]Wilders, Alison M.; Contrella, Nathan D.; Sampson, Jessica R.; Zheng, Mingfang; Jordan, Richard F. [Organometallics, 2017, vol. 36, # 24, p. 4990 - 5002]

5
[ 3348-44-5 ]
[ 62336-24-7 ]
[ 358974-18-2 ]

Yield	Reaction Conditions	Operation in experiment
96%	Stage #1: (2-bromophenyl)diphenylphosphane With n-butyllithium In diethyl ether; hexane at 20℃; for 0.333333h; Stage #2: bis(N,N-dimethylamino)chlorophosphine In toluene at -78 - 20℃; for 1h;

Reference： [1]Kottsieper, Konstantin W.; Kuehner, Uwe; Stelzer, Othmar [Tetrahedron Asymmetry, 2001, vol. 12, # 8, p. 1159 - 1169]

6
[ 62336-24-7 ]
[ 98-80-6 ]
[ 13885-09-1 ]

Reference： [1]Tetrahedron Letters,2001,vol. 42,p. 9085 - 9088

7
[ 16419-60-6 ]
[ 62336-24-7 ]
[ 402822-72-4 ]

Reference： [1]Tetrahedron Letters,2007,vol. 48,p. 2025 - 2027
[2]Journal of Organometallic Chemistry,2008,vol. 693,p. 3135 - 3140
[3]Journal of Organometallic Chemistry,2002,vol. 645,p. 14 - 26
[4]Tetrahedron Letters,2009,vol. 50,p. 5470 - 5473
[5]Angewandte Chemie - International Edition,2013,vol. 52,p. 11892 - 11895
Angew. Chem.,2013

8
[ 5720-05-8 ]
[ 62336-24-7 ]
(4'-methyl-[1,1'-biphenyl]-2-yl)diphenylphosphane [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
73%	With palladium diacetate; potassium carbonate In toluene at 80℃; for 72h;
63%	With potassium carbonate In toluene at 80℃; for 72h;
44%	With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; potassium phosphate In 1,4-dioxane for 15h; Inert atmosphere; Reflux;

Reference： [1]An, Jiangzhen; Jia, Chunqi; Li, Gang; Wang, Junjie; Yan, Bingxu; Yang, Suling; Zhong, Lei [Organic Letters, 2020, vol. 22, # 24, p. 9450 - 9455]
[2]Brauer, David J.; Hingst, Martin; Kottsieper, Konstantin W.; Liek, Christian; Nickel, Thomas; Tepper, Michael; Stelzer, Othmar; Sheldrick, William S. [Journal of Organometallic Chemistry, 2002, vol. 645, # 1-2, p. 14 - 26]
[3]Bissember, Alex C.; Canty, Allan J.; Ho, Curtis C.; Horne, James; Lucas, Nigel T.; Olding, Angus [Angewandte Chemie - International Edition, 2021, vol. 60, # 27, p. 14897 - 14901][Angew. Chem., 2021, vol. 133, # 27, p. 15023 - 15027]

9
[ 27081-10-3 ]
[ 62336-24-7 ]
[2-(cyclohepta-2,4,6-trienyl)phenyl]diphenylphosphane [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
75%	Stage #1: (2-bromophenyl)diphenylphosphane With n-butyllithium In tetrahydrofuran for 0.75h; Stage #2: tropylium tetrafluoroborate In tetrahydrofuran; hexane at -78 - 20℃; for 3h;

Reference： [1]Tamm, Matthias; Baum, Kim; Luegger, Thomas; Froehlich, Roland; Bergander, Klaus [European Journal of Inorganic Chemistry, 2002, # 4, p. 918 - 928]

10
[ 75-78-5 ]
[ 62336-24-7 ]
[ 713147-59-2 ]

Yield	Reaction Conditions	Operation in experiment
	Stage #1: (2-bromophenyl)diphenylphosphane With n-butyllithium In diethyl ether; hexane; toluene at 20℃; for 0.166667h; Stage #2: dimethylsilicon dichloride In diethyl ether; hexane; toluene
	Stage #1: (2-bromophenyl)diphenylphosphane With n-butyllithium In diethyl ether; hexane at -78℃; for 3h; Inert atmosphere; Stage #2: dimethylsilicon dichloride In diethyl ether; hexane at 20℃;	3 Compound 1 (1.02 g, 2.98 mmol) was placed in a 100 ml two-necked eggplant-shaped flask, 30 ml of diethyl ether was added under a nitrogen atmosphere, and the mixture was cooled to -78 ° C. 2 ml (1.55 M, 3.10 mmol) of n-butyllithium in hexane was added dropwise, and the mixture was stirred for 3 hours. Thereafter, dimethyldichlorosilane (4.26 g, 33.0 mmol) was added and the temperature was raised to room temperature. After completion of the reaction, the solvent and the excess dimethyldichlorosilane were distilled off under reduced pressure.30 ml of diethyl ether was added to the reaction system, and the mixture was cooled to 0 ° C. 2-Propanol (1.56 g, 26.0 mmol) and triethylamine (0.426 g, 4.31 mmol) were added and stirred for 30 minutes, then the temperature was raised to room temperature. The by-produced salt was removed by filtration, and the solvent was distilled off under reduced pressure. Compound X was isolated by silica gel column chromatography. Yield 0.784 g, yield 70%.

Reference： [1]Quintard, Delphine; Keller, Manfred; Breit, Bernhard [Synthesis, 2004, # 6, p. 905 - 908]
[2]Current Patent Assignee: NATIONAL INSTITUTE OF ADVANCED INDUSTRIAL SCIENCE AND TECHNOLOGY - JP5791040, 2015, B2 Location in patent: Paragraph 0020

11
[ 7751-38-4 ]
[ 62336-24-7 ]
chlorodiisopropyl(2'-diphenylphosphanyl)phenylsilane [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
97%	Stage #1: (2-bromophenyl)diphenylphosphane With n-butyllithium In diethyl ether; hexane; toluene at 20℃; for 0.25h; Stage #2: Diisopropylsilyl dichloride In diethyl ether; hexane; toluene for 2h;

Reference： [1]Quintard, Delphine; Keller, Manfred; Breit, Bernhard [Synthesis, 2004, # 6, p. 905 - 908]

12
[ 62336-24-7 ]
[ 88652-74-8 ]

Yield	Reaction Conditions	Operation in experiment
100%	With dihydrogen peroxide In methanol at 20℃; for 1h;
100%	With dihydrogen peroxide In methanol; water at 0 - 20℃; for 1h; Inert atmosphere; Schlenk technique; Sealed tube;
94%	With dihydrogen peroxide In dichloromethane at 0 - 20℃; for 1h;	22 Reference Example 22 The (2-bromophenyl) diphenyl phosphine (6.07 g, 17.8 mmol) was dissolved into dichloromethane (35 mL), and after [the obtainment] was cooled down to 0° C., a 30% hydrogen peroxide solution (10 mL) was added, and [the mixture] was stirred at room temperature for 1 hour. Water (20 mL) was poured into the reactant mixture, and after organic layers were separated, chloroform (50 mL) was added to an aqueous layer, and a chloroform layer was separated. This operation was repeated twice. The organic layers were combined, and after these were dried with sodium sulfate, they were concentrated under reduced pressure. By refining the obtained crude product by silica gel column chromatography (eluent: chloroform/methanol), (2-bromophenyl) diphenylphosphine oxide (yield amount: 6.00 g, yield: 94%) was obtained. 1H-NMR (400 MHz, CDCl3), δ (ppm): 7.74˜7.66 (m, 5H), 7.59˜7.7.55 (m, 2H), 7.51˜7.46 (m, 4H), 7.41˜7.32 (m, 3H). 31P-NMR (162 MHz, CDCl3), δ (ppm): 30.5 (s).

93%

With dihydrogen peroxide In dichloromethane; water at 20℃; for 3h; Glovebox; Inert atmosphere;

Reference： [1]Baillie, Colin; Xiao, Jianliang [Tetrahedron, 2004, vol. 60, # 19, p. 4159 - 4168]
[2]Li, Jia-Wei; Wang, Liang-Neng; Li, Ming; Tang, Pan-Ting; Luo, Xiao-Peng; Kurmoo, Mohamedally; Liu, Yue-Jin; Zeng, Ming-Hua [Organic Letters, 2019, vol. 21, # 8, p. 2885 - 2889]
[3]Current Patent Assignee: SAGAMI CHEMICAL RESEARCH INSTITUTE; TOSOH CORPORATION - US2020/354389, 2020, A1 Location in patent: Paragraph 0362; 0365-0366
[4]Landais, Yannick; Laye, Claire; Lusseau, Jonathan; Robert, Frédéric [Advanced Synthesis and Catalysis, 2021, vol. 363, # 12, p. 3035 - 3043]

13
[ 62336-24-7 ]
[ 88652-75-9 ]

Yield	Reaction Conditions	Operation in experiment
71%	Stage #1: (2-bromophenyl)diphenylphosphane With n-butyllithium In tetrahydrofuran at -78℃; Stage #2: With iodine In tetrahydrofuran

Reference： [1]Meprathu, Bindu V.; Justik, Michael W.; Protasiewicz, John D. [Tetrahedron Letters, 2005, vol. 46, # 31, p. 5187 - 5190]

14
[ 111060-66-3 ]
[ 62336-24-7 ]
(1S,2S)-2-(dibenzylamino)-3-methyl-1-(2-(diphenylphosphino)phenyl)butan-1-ol [ No CAS ]
(1R,2S)-2-(dibenzylamino)-3-methyl-1-(2-(diphenylphosphino)phenyl)butan-1-ol [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
1: 63% 2: 13%	Stage #1: (2-bromophenyl)diphenylphosphane With n-butyllithium In diethyl ether; hexane at 20℃; for 0.416667h; Stage #2: L-dibenzylvalinal In diethyl ether; hexane at -5℃; for 9h;

Reference： [1]Hajra, Alakananda; Yoshikai, Naohiko; Nakamura, Eiichi [Organic Letters, 2006, vol. 8, # 18, p. 4153 - 4155]

15
(S)-2-(dibenzylamino)propanal [ No CAS ]
[ 62336-24-7 ]
[ 910448-13-4 ]
[ 910448-12-3 ]

Yield	Reaction Conditions	Operation in experiment
1: 65% 2: 9%	Stage #1: (2-bromophenyl)diphenylphosphane With n-butyllithium In diethyl ether; hexane at 20℃; for 0.416667h; Stage #2: (S)-2-(dibenzylamino)propanal In diethyl ether; hexane at -5℃; for 9h;

Reference： [1]Hajra, Alakananda; Yoshikai, Naohiko; Nakamura, Eiichi [Organic Letters, 2006, vol. 8, # 18, p. 4153 - 4155]

16
[ 589-57-1 ]
[ 62336-24-7 ]
[ 490040-63-6 ]

Yield	Reaction Conditions	Operation in experiment
92%	Stage #1: (2-bromophenyl)diphenylphosphane With n-butyllithium In tetrahydrofuran; hexane at -78℃; for 1h; Stage #2: diethyl phosphorylchloridite In tetrahydrofuran; hexane at -78 - 20℃; Further stages.;

Reference： [1]Matsumura, Kazuhiko; Shimizu, Hideo; Saito, Takao; Kumobayashi, Hidenori [Advanced Synthesis and Catalysis, 2003, vol. 345, # 1-2, p. 180 - 184]

17
[ 33513-42-7 ]
[ 62336-24-7 ]
[ 50777-76-9 ]

Yield	Reaction Conditions	Operation in experiment
70%	Stage #1: (2-bromophenyl)diphenylphosphane With n-butyllithium In diethyl ether; hexane at -78℃; for 0.333333h; Stage #2: N,N-dimethyl-formamide In diethyl ether; hexane at -78 - 20℃; Further stages.;
	Stage #1: (2-bromophenyl)diphenylphosphane Stage #2: N,N-dimethyl-formamide Further stages.;

Reference： [1]Luo, Xiancai; Zhang, Heng; Duan, Hui; Liu, Qiang; Zhu, Lizheng; Zhang, Tony; Lei, Aiwen [Organic Letters, 2007, vol. 9, # 22, p. 4571 - 4574]
[2]Pei, Yuxin; Brule, Emilie; Moberg, Christina [Organic and Biomolecular Chemistry, 2006, vol. 4, # 3, p. 544 - 550]

18
[ 583-55-1 ]
[ 1079-66-9 ]
[ 62336-24-7 ]

Yield	Reaction Conditions	Operation in experiment
90%	Stage #1: 1-Bromo-2-iodobenzene With isopropylmagnesium chloride In tetrahydrofuran at -35 - -30℃; for 1h; Stage #2: chloro-diphenylphosphine In tetrahydrofuran at 20℃; for 0.5h;	a 17.5 ml (35 mmol) of i-propylmagnesium chloride (2.0 M in THF) are added dropwise to a solution of 5 ml (35 mmol) of 2-bromoiodobenzene in 25 ml of THF while stirring at from -300C to -35°C. The temperature is maintained and the reaction mixture is stirred for a further 1 hour. 9.3 g (42 mmol) of diphenylphosphine chloride are then added slowly, the mixture is stirred for a further 30 minutes and the cooling is then removed. After stirring at room temperature for 1 hour, 20 ml of water are added, the mixture is extracted with ethyl acetate, the organic phase is washed with saturated aqueous NaHCO3 and NaCI solution and dried over sodium sulphate. Distilling off the solvent gives a colourless oil which becomes solid on addition of 100 ml of ethanol. Filtration and washing with a little ethanol gives the desired product as a white powder in a yield of 90%. 1H-NMR (C6D6, 300 MHz), characteristic signals: 7.38-7.30 (m, 5H), 7.06-7.02 (m, 6H), 6.91-6.86 (m, 1 H), 6.79-6.73 (m, 1 H), 6.71-6.65 (m, 1 H). 31P-NMR (C6D6, 121 MHz): -3.79 (s).
73%	Stage #1: 1-Bromo-2-iodobenzene With isopropylmagnesium chloride In tetrahydrofuran at -35℃; for 1h; Stage #2: chloro-diphenylphosphine In tetrahydrofuran; tert-butyl methyl ether at -78 - 25℃;
60%	Stage #1: 1-Bromo-2-iodobenzene With isopropylmagnesium bromide Stage #2: chloro-diphenylphosphine Further stages.;

Stage #1: 1-Bromo-2-iodobenzene With isopropylmagnesium chloride In tetrahydrofuran Stage #2: chloro-diphenylphosphine In tetrahydrofuran

Reference： [1]Current Patent Assignee: SOLVIAS AG - WO2008/815, 2008, A1 Location in patent: Page/Page column 27
[2]Müller, Valentin; Ghorai, Debasish; Capdevila, Lorena; Messinis, Antonis M.; Ribas, Xavi; Ackermann, Lutz [Organic Letters, 2020, vol. 22, # 17, p. 7034 - 7040]
[3]Pei, Yuxin; Brule, Emilie; Moberg, Christina [Organic and Biomolecular Chemistry, 2006, vol. 4, # 3, p. 544 - 550]
[4]Location in patent: experimental part Landert, Heidi; Spindler, Felix; Wyss, Adrian; Blaser, Hans-Ulrich; Pugin, Benoit; Ribourduoille, Yann; Gschwend, Bjoern; Ramalingam, Balamurugan; Pfaltz, Andreas [Angewandte Chemie - International Edition, 2010, vol. 49, # 38, p. 6873 - 6876]

19
[ 62336-24-7 ]
[ 887605-60-9 ]

Yield	Reaction Conditions	Operation in experiment
66%	Stage #1: (2-bromophenyl)diphenylphosphane With n-butyllithium In diethyl ether; hexane at -80 - 20℃; for 0.666667h; Stage #2: With phosphorus trichloride In diethyl ether; hexane at 20℃; for 3h; Further stages.;

Reference： [1]Whited, Matthew T.; Rivard, Eric; Peters, Jonas C. [Chemical Communications, 2006, # 15, p. 1613 - 1615]

20
[ 62336-24-7 ]
[ 951040-33-8 ]

Yield	Reaction Conditions	Operation in experiment
87%	With n-butyllithium; trichlorosilane In diethyl ether; hexane; toluene at 110℃; for 15h;

Reference： [1]Mankad, Neal P.; Whited, Matthew T.; Peters, Jonas C. [Angewandte Chemie - International Edition, 2007, vol. 46, # 30, p. 5768 - 5771]

21
[ 62336-24-7 ]
[ 13885-09-1 ]

Reference： [1]Tetrahedron,2004,vol. 60,p. 4159 - 4168
[2]Organic Letters,2019,vol. 21,p. 2885 - 2889

22
[ 62336-24-7 ]
[ 402822-72-4 ]

Reference： [1]Tetrahedron,2004,vol. 60,p. 4159 - 4168
[2]Organic Letters,2019,vol. 21,p. 2885 - 2889

23
[ 62336-24-7 ]
[ 240417-00-9 ]

Reference： [1]Tetrahedron,2004,vol. 60,p. 4159 - 4168

24
[ 859839-97-7 ]
[ 62336-24-7 ]
(SFe, Rp, αS)-2-[(2-methoxyphenyl)phenylphosphino]-1-[(diphenylphosphinophenyl)]ferrocenemethanol [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	Stage #1: (SFe-Rp)-2-[(2-methoxyphenyl)phenylphosphino]ferrocenecarboxaldehyde; (2-bromophenyl)diphenylphosphane With magnesium In tetrahydrofuran at -78 - 20℃; Stage #2: With ammonium chloride In tetrahydrofuran; water	46 A suspension of magnesium turnings (63 mg, 2.6 mmol) and 2- bromophenyl) diphenylphosphine 50 (887 mg, 2.6 mmol) in THF (10 mL) was refluxed until magnesium was dissolved (about 30 min). The resulting Gragnard reagent solution was cooled to-78 °C, and a solution of (SFe, Rp)-2-[(2- methoxyphenyl) phenylphosphino] ferrocenecarbaoxaldehyde [(SFe, Rp)-48] (856 mg, 2.0 mmol) in THF (10 mL) was added slowly via a syringe. After stirring for 5 h at-78 °C, the mixture was allowed to warm to room temperature and stirred overnight at room temperature. The reaction was quenched with saturated NH4CI solution, and extracted with CH2CI2 (2x20 mL). The combined extracts were washed with brine (20 mL), dried (MgS04), and evaporated under reduced pressure. The residue was purified by flash chromatography (Si02, hexane-EtOAc = 6: 1) to give yellow crystals (1.297 g, 96%) as a mixture of two diastereomers (-9 : 1). Major product :'H NMR (CDCl3, 250 MHz): 6 2.91 (br. s, 1H), 3.57 (m, 1H), 3.59 (s, 3H), 4.05 (m, 1H), 4.14 (t, 1H, J = 2.4 Hz), 4.18 (s, 5H), 4.22 (m, 1 H), 6. 48-4. 56 (m, 2H), 6. 68No.6. 80 (m, 2H), 7. 02-7. 37 (m, 13H); 7. 49No.7. 58 (m, 2H), 7.67 (m, 1H). 31P NMR (CDCl3, 101 MHz): No.-18. 69 (d, J = 14.6 Hz),-32. 85 (d, J = 14.6 Hz).

Reference： [1]Current Patent Assignee: SOLVIAS AG - WO2005/68477, 2005, A1 Location in patent: Page/Page column 72-73

25
[ 859839-98-8 ]
[ 62336-24-7 ]
(SFe, Rp, αS)-2-[(1-naphthyl)phenylphosphino]-1-[α-(diphenylphosphinophenyl)]ferrocenemethanol [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	Stage #1: (S(Fc),R(P))-2-(1-naphthylphenylphosphanyl)ferrocenecarboxaldehyde; (2-bromophenyl)diphenylphosphane With magnesium In tetrahydrofuran at -78 - 20℃; Stage #2: With ammonium chloride In tetrahydrofuran; water	47 A suspension of magnesium turnings (63 mg, 2.6 mmol) and 2- bromophenyl) diphenylphosphine 50 (887 mg, 2.6 mmol) in THF (10 mL) was refluxed until magnesium was dissolved (about 30 min). The resulting Gragnard reagent solution was cooled to-78 °C, and a solution of (SFe, Rp)-2- [ (1- naphthyl) phenylphosphino]ferrocenecarbaoxaldehyde [(SFe, RP)-49] (897 mg, 2.0 mmol) in THF (10 mL) was added slowly via a syringe. After stirring for 5 h at-78 °C, the mixture was allowed to warm to room temperature and stirred overnight at room temperature. The reaction was quenched with saturated NH4CI solution, and extracted with CH2CI2 (2x20 mL). The combined extracts were washed with brine (20 mL), dried (MgS04), and evaporated under reduced pressure. The residue was purified by flash chromatography (Si02, hexane- EtOAc = 6: 1) to give yellow crystals (1.322 g, 93%) as a mixture of two diastereomers (-9 : 1). Major product : H NMR (CDCI3, 250 MHz): 6 2.39 (br. s, 1H), 3.66 (m, 1H), 4.24 (s, 5H), 4.29 (t, 1H, J = 2.4 Hz), 4.57 (m, 1H), 4.22 (m, 2H), 6. 40No.4. 49 (m, 3H), 6. 61-6. 67 (m, 2H), 6. 83 No. 7. 01 (m, 4H); 7. 10No.7. 59 (m, H), 7.75 (br. D, 1H, J = 7.8 Hz), 8.28 (m, 1H). 31P NMR (CDCI3, 101 MHz) : 6- 18.54 (d, J = 21.0 Hz), -29.56 (d, J = 21.0 Hz).

Reference： [1]Current Patent Assignee: SOLVIAS AG - WO2005/68477, 2005, A1 Location in patent: Page/Page column 73-74

26
[ 216019-76-0 ]
[ 62336-24-7 ]
(S)Fc-α-S(C5H5)Fe(C5H3BrCH(OH)C6H4(PPh2)) [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
98%	Stage #1: (S<SUB>p</SUB>)-1-bromo-2-vinylferrocene; (2-bromophenyl)diphenylphosphane With magnesium In tetrahydrofuran; diethyl ether at -78 - 20℃; Stage #2: With ammonium chloride In tetrahydrofuran; diethyl ether; water	49 A suspension of Mg (729 mg, 30 mmol) in THF (10 mL) was added dropwise a solution of 2-bromophenyldiphenylphosphine (50) (9.42 g, 27.6 mmol) in THF (30 mL) at about 50 °C. After addition, the mixture was refluxed for 1 h, cooled room temperature, and added to a solution of (SFe)-2- bromoferrocenecarboxaldehyde [ (SFe)-54] (6.74 g, 23 mmol) in Et2O (20 mL) at- 78 °C. After stirring for 6 h at-78 °C, the mixture was warmed to room temperature, and stirred overnight at room temperature. The reaction was quenched with saturated NH4CI solution (50 mL), and diluted with EtOAc (100 mL). The organic layer was separated, washed with brine (50 mL), dried (Na2SO4), and evaporated under reduced pressure. The residue was purified by chromatography (SiO2, hexane-EtOAc = 5: 1) to give yellow crystals (12.51 g, 98%) as a single diastereomer. 1H NMR (CDCl3, 250 MHz): 5 2.67 (dd, 1H, J = 3.5 and 2.0 Hz), 4.04 (t, 1H, J = 2.5 Hz), 4.18 (m, 1H), 4.27 (s, 5H), 4.40 (m, 1H), 6.47 (dd, 1H, J = 6.5 and 3.5 Hz), 7.00 (m, 1H), 7.18 (m, 1H), 7. 15 No. 7. 37 (m, 12H); 31P NMR (CDC13, 101 MHz): õ-17. 30.

Reference： [1]Current Patent Assignee: SOLVIAS AG - WO2005/68477, 2005, A1 Location in patent: Page/Page column 75-76

27
(R,S(p))-1-bromo-2-[1-(N,N-dimethylamino)ethyl]ferrocene [ No CAS ]
[ 62336-24-7 ]
C₄₅H₄₃FeNOP₂ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
80%	Stage #1: (2-bromophenyl)diphenylphosphane With n-butyllithium In tetrahydrofuran; hexane; tert-butyl methyl ether at -70 - -40℃; for 1h; Stage #2: (R,S(p))-1-bromo-2-[1-(N,N-dimethylamino)ethyl]ferrocene In tetrahydrofuran; hexane; tert-butyl methyl ether at -70℃; for 0.25h;	C.1 1 ml (1.6 mmol) of n-BuLi (1.6 molar in hexane) is added dropwise to a solution of 0.532 g (1.6 mmol) of the compound 2-diphenylphosphino-1-bromobenzene in a mixture of 5 ml of THF and 5 ml of TBME at a temperature of -700C while stirring. The red reaction solution is stirred at a temperature of from -700C to -40°C for 1 hour. This solution is then slowly added to a solution of 0.54 g (1.2 mmol) of the compound B1 in 5 ml of TBME and the mixture stirred further at -700C. After 15 minutes, the cooling is removed and the mixture is stirred at room temperature for another 1.5 hours. The reaction mixture is admixed with 20 ml of water, the organic phase is washed with saturated, aqueous NaCI, dried over sodium sulphate and the solvent is distilled off on a rotary evaporator. An NMR spectrum of the crude product shows that virtually only one of two possible diastereomers has been formed. Purification by chromatography (silica gel; eluent = EA/heptane 1 :2 containing 1 % of triethylamine) gives the title compound in the form of a pure diastereomer as an orange foam in a yield of 80%. 1H-NMR (C6D6, 300 MHz), characteristic signals: 7.81-6.58 (various m, 24 aromatic H), 4.46 (q, 1 H), 4.22 (m, 1 H), 4.09 (m, 1 H), 4.04 (s, 5H), 1.85 (s, 6H), 0.96 (d, 3H). 31P-NMR (C6D6, 121 MHz): -15.9 (d), -24.6 (d).

Reference： [1]Current Patent Assignee: SOLVIAS AG - WO2008/815, 2008, A1 Location in patent: Page/Page column 33

28
1-[(dimethylamino)eth-1-yl]-2-formyl-3-(dicyclohexylphosphino)ferrocene [ No CAS ]
[ 62336-24-7 ]
C₄₅H₅₅FeNOP₂ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
55%	Stage #1: (2-bromophenyl)diphenylphosphane With n-butyllithium In tetrahydrofuran; hexane; tert-butyl methyl ether at -70 - -40℃; for 1h; Stage #2: 1-[(dimethylamino)eth-1-yl]-2-formyl-3-(dicyclohexylphosphino)ferrocene In tetrahydrofuran; hexane; tert-butyl methyl ether at -70℃; for 1h;	C.5 0.9 ml (1.4 mmol) of n-BuLi (1.6 molar in hexane) is added dropwise to a solution of 1.7 g (5 mmol) of 2-diphenylphosphino-1-bromobenzene in a mixture of 20 ml of THF and 30 ml of TBME at a temperature of -700C while stirring. The red reaction solution is stirred at a temperature of from -700C to -400C for 1 hour. This solution is then slowly added to a solution of 2 g (4.2 mmol) of the compound B3 in 30 ml of TBME and the mixture is stirred at -700C. After 1 hour, the temperature is allowed to rise to -500C. The reaction mixture is admixed with 20 ml of water, the organic phase is washed with saturated aqueous NaCI, dried over sodium sulphate and the solvent is distilled off on a rotary evaporator. An NMR spectrum of the crude product shows that virtually only one of two possible diastereomers has been formed. Purification by chromatography (silica gel; eluent = acetone/toluene 1 :10) gives the title compound in the form of a pure diastereomer as an orange foam in a yield of 55%. 1H-NMR (CeD6, 300 MHz), characteristic signals: 7.86-7.04 (diverse m, 14 aromatic H), 5.67 (broad s, 1 H), 4.58 (q, 1 H), 4.33 (m, 1 H), 4.31 (s, 5H), 4.24 (m, 1 H), 1.96 (s, 6H), 1.11 (d, 3H). 31P-NMR (C6D6, 121 MHz): -11.0 (d), -16.5 (d).

Reference： [1]Current Patent Assignee: SOLVIAS AG - WO2008/815, 2008, A1 Location in patent: Page/Page column 36-37

29
[ 436-59-9 ]
[ 62336-24-7 ]
[ 1048641-05-9 ]

Yield	Reaction Conditions	Operation in experiment
81%	Stage #1: (2-bromophenyl)diphenylphosphane With n-butyllithium In diethyl ether; hexane at 0℃; for 0.5h; Stage #2: dimesitylfluoroborane In diethyl ether; hexane at -78 - 20℃;
74%	Stage #1: (2-bromophenyl)diphenylphosphane With n-butyllithium In diethyl ether; hexane at 20℃; for 0.166667h; Stage #2: dimesitylfluoroborane In diethyl ether; hexane at 20℃;

Reference： [1]Ito, Tatsuyoshi; Iwasawa, Nobuharu; Takaya, Jun [Angewandte Chemie - International Edition, 2020, vol. 59, # 29, p. 11913 - 11917][Angew. Chem., 2020, vol. 132, # 29, p. 12011 - 12015,5]
[2]Hudnall, Todd W.; Kim, Young-Min; Bebbington, Magnus W. P.; Bourissou, Didier; Gabbai, Francois P. [Journal of the American Chemical Society, 2008, vol. 130, # 33, p. 10890 - 10891]

30
[ 644-97-3 ]
[ 62336-24-7 ]
[ 1157917-50-4 ]

Yield	Reaction Conditions	Operation in experiment
73%	Stage #1: (2-bromophenyl)diphenylphosphane With n-butyllithium In tetrahydrofuran; hexane; tert-butyl methyl ether at -78℃; for 2h; Stage #2: Dichlorophenylphosphine In tetrahydrofuran; hexane; tert-butyl methyl ether at 0 - 20℃; for 1.5h; Stage #3: With water In tetrahydrofuran; hexane; tert-butyl methyl ether for 1.16667h;	B.5 To a solution of 2.6 g (7.6 mmol) of the compound o-bromophenyldiphenylphosphine in 6 ml of THF and 6 ml of TBME are added dropwise, at -78°C, 4.8 ml (7.6 mmol) of n-butyllithium (1.6 M in hexane). The mixture is stirred at -78°C for a further 2 hours. The reaction mixture is then transferred with the aid of a cannula using elevated argon pressure into a reaction vessel in which a solution of 1.03 ml (7.6 mmol) of P,P-di- chlorophenylphosphine in 6 ml of TBME is being stirred at 00C. The flask and the cannula are washed with a further 5 ml of THF. After 1.5 hours, the cooling is removed. 50 ml of water are then added. After stirring for 70 minutes, 20 ml of saturated aqueous NaCI are added, and the mixture is extracted first with 10:1 ethyl acetate / methylene chloride, then ethyl acetate, toluene and finally methylene chloride. The organic phases are collected and dried over sodium sulphate, and the solvent is distilled off on a rotary evaporator under reduced pressure. The white solid crude product is purified by chromatography (silica gel 60; eluent = ethyl acetate). The racemic ligand B5 is obtained as a white solid in a yield of 73%.

Reference： [1]Current Patent Assignee: SOLVIAS AG - WO2009/65783, 2009, A1 Location in patent: Page/Page column 37

31
[ 676-58-4 ]
[ 83021-21-0 ]
[ 62336-24-7 ]
C₂₉H₃₆P₂ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	Stage #1: (2-bromophenyl)diphenylphosphane With n-butyllithium In tetrahydrofuran; hexane; tert-butyl methyl ether at -78℃; for 1.5h; Stage #2: L-menthyldichlorophosphine In tetrahydrofuran; hexane; tert-butyl methyl ether at -78℃; for 2h; Stage #3: methylmagnesium chloride In tetrahydrofuran; hexane; tert-butyl methyl ether	B.6 To a solution of 0.92 g (2.7 mmol) of o-bromodiphenylphosphine in 2 ml of THF and 4 ml of TBME are added dropwise, at -78°C, 1.69 ml (2.7 mmol) of n-butyllithium (1.6 M in hexane). The resulting suspension is stirred at -78°C for a further 1.5 hour. Then the suspension is injected using elevated argon pressure with the aid of a cannula into a reaction vessel, in which a solution of 0.65 g (2.7 mmol) of (L)- menthyldichlorophosphine in 2 ml of TBME is being stirred at -78°C. It is rinsed with 4 ml of THF and the suspension is then stirred without cooling for a further 2 hours. Then 1.13 ml (3.2 mmol) of methylmagnesiunn chloride (3M in THF) are added and the reaction mixture is stirred overnight. Subsequently, it is extracted with water and TBME. The organic phases are collected and dried over sodium sulphate, and the solvent is distilled off under reduced pressure on a rotary evaporator. A 31P NMR of the almost solid crude product shows that predominantly one of the two possible diastereomeric P-chiral ligands has formed (diastereomer ratio about 9:1 ). The purification is effected by chromatography (silica gel 60; eluent = 2:1 heptane / toluene) and subsequent recrystallization of the main fraction in methanol. The main diastereomer, which is optically pure according to NMR, is obtained as a white crystalline solid.31P NMR of main diastereomer (C6D6, 121 MHz): δ -14.7 (d), -35.5 (d); 1H NMR of main diastereomer (C6D6, 300 MHz), characteristic signals: δ 7.43 - 6.9 (various m, 14H), 2.73 (m, 1 H), 2.11 (m, 1 H), 1.62 (m, 2H), 1.15 (d, 3H), 1.05 (d, 3H), 0.94 (d, 3H), 0.68 (s, 3H).

Reference： [1]Current Patent Assignee: SOLVIAS AG - WO2009/65784, 2009, A1 Location in patent: Page/Page column 41-42

32
[ 83021-21-0 ]
[ 62336-24-7 ]
C₂₈H₃₄OP₂ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
70%	Stage #1: (2-bromophenyl)diphenylphosphane With n-butyllithium In tetrahydrofuran; hexane; tert-butyl methyl ether at -78℃; for 1.5h; Stage #2: L-menthyldichlorophosphine In tetrahydrofuran; hexane; tert-butyl methyl ether at -78℃; for 1.5h; Stage #3: With sodium hydroxide; water In tetrahydrofuran; hexane; tert-butyl methyl ether	B.1 To a solution of 2.19 g (6.42 mmol) of o-bromophenyldiphenylphosphine in 7 ml of THF and 5 ml of TBME are added dropwise, at -78°C, 4.01 ml (6.42 mmol) of n-butyllithium (1.6 M in hexane). The resulting suspension is stirred at -78°C for a further 1.5 hour. Then the suspension is injected using elevated argon pressure with the aid of a cannula into a reaction vessel, in which a solution of 1.55 g (6.42 mmol) of (L)-menthyldichlorophosphine in 5 ml of TBME is being stirred at -78°C. After addition, 3 ml of THF are used to rinse it in and the suspension is then stirred without cooling for a further 1.5 hour. Then 5 ml of water and 0.5 ml of 1 N NaOH are added, and the reaction mixture is stirred until the phosphine chloride has been hydrolysed fully and finally extracted with TBME. The organic phases are collected and dried over sodium sulphate, and the solvent is distilled off under reduced pressure on a rotary evaporator. The crude yield is virtually quantitative. A 31P NMR of the white solid crude product shows that predominantly one of the two possible diastereomehc P-chiral ligands has formed (diastereomer ratio about 9:1 ). It is possible by chromatography (silica gel 60; eluent = 1 :1 heptane / ethyl acetate) to isolate the main stereoisomer in pure form, according to NMR analysis, as a white solid (yield 70%). 31P NMR of main diastereomer (C6D6, 121 MHz): δ 16.4 (d), -19.4 (d); 1H NMR of main diastereomer (C6D6, 300 MHz), characteristic signals: δ 8.64 (dd, J= 471 Hz, J= 5.1 Hz, 1 H), 8.63 - 8.56 (m, 1 H), 7.23 - 6.94 (various m, 13H), 2.77 - 0.3 (various m, 10H), 1.07 (d, 3H), 0.97 (d, 3H), 0.55 (d, 3H).
	Stage #1: (2-bromophenyl)diphenylphosphane With n-butyllithium In tetrahydrofuran; hexane; tert-butyl methyl ether at -78℃; for 1.5h; Stage #2: L-menthyldichlorophosphine In tetrahydrofuran; hexane; tert-butyl methyl ether at -78℃; for 1.5h; Stage #3: With formic acid; benzylamine more than 3 stages;	B.1' To a solution of 2.19 g (6.42 mmol) of o-bromophenyldiphenylphosphine in 7 ml of THF and 5 ml of TBME are added dropwise, at -78°C, 4.01 ml (6.42 mmol) of n- butyllithium (1.6 M in hexane). The resulting suspension is stirred at -78°C for a further 1.5 hour. Then the suspension is injected using elevated argon pressure with the aid of a cannula into a reaction vessel, in which a solution of 1.55 g (6.42 mmol) of (L)-menthyldichlorophosphine in 5 ml of TBME is being stirred at -78°C. After addition, 3 ml of THF are used to rinse it in and the suspension is then stirred without cooling for a further 1.5 hour. Then the solvent is distilled off under reduced pressure. 20 ml of toluene and 2 ml of benzylamine are added to the residue and the mixture is stirred overnight. This reaction mixture is then added to 20 ml of formic acid to give, according to 31P-NMR, an approx. 1 : 1 mixture of the product B1 and B1 '. The mixture is extracted with toluene, the organic phases are collected, washed with water, dired over Na2SO4 and the solvents distilled off under reduced pressure. Pure product B1 ' is obtained as a colorless oil by column chromatography (silicagel 60; eluent= heptane / ethylacetate 2 : 1 ).31P NMR (C6D6, 121 MHz): δ 30.95 (d), -17.13 (d); 1H NMR (C6D6, 300 MHz), characteristic signals: δ 8.03 (dd, J= 467 Hz, 1 H), 8.55 - 8.38 (m, 1 H), 7.4 - 6.7 (various m, 13H), 2.6 - 0.6 (various m, 10H), 0.95 (d, 3H), 0.80 (d, 3H), 0.35 (d, 3H).

Reference： [1]Current Patent Assignee: SOLVIAS AG - WO2009/65784, 2009, A1 Location in patent: Page/Page column 36
[2]Current Patent Assignee: SOLVIAS AG - WO2009/65784, 2009, A1 Location in patent: Page/Page column 37

33
[ 65654-60-6 ]
[ 62336-24-7 ]
[ 1215039-27-2 ]

Yield	Reaction Conditions	Operation in experiment
94%	Stage #1: (2-bromophenyl)diphenylphosphane With n-butyllithium In diethyl ether at -80℃; for 0.25h; Stage #2: (10-chloro-2,8-dimethyl-10H-phenoxaphosphine) In diethyl ether at -80 - 20℃;

Reference： [1]Location in patent: experimental part Zuidema, Erik; Elsbeth Goudriaan; Swennenhuis, Bert H. G.; Kamer, Paul C. J.; Van Leeuwen, Piet W. N. M.; Lutz, Martin; Spek, Anthony L. [Organometallics, 2010, vol. 29, # 5, p. 1210 - 1221]

34
[ 1257322-37-4 ]
[ 62336-24-7 ]

Yield	Reaction Conditions	Operation in experiment
88%	In tetrahydrofuran; methanol for 96h; Inert atmosphere; Molecular sieve; Reflux;
79%	With 1,4-diaza-bicyclo[2.2.2]octane In toluene at 20℃; Inert atmosphere;

Reference： [1]Location in patent: experimental part Li, Jie; Lutz, Martin; Spek, Anthony L.; Van Klink, Gerard P.M.; Van Koten, Gerard; Klein Gebbink, Robertus J.M. [Journal of Organometallic Chemistry, 2010, vol. 695, # 24, p. 2618 - 2628]
[2]Location in patent: experimental part Bayardon, Jerome; Laureano, Hugo; Diemer, Vincent; Dutartre, Mathieu; Das, Utpal; Rousselin, Yoann; Henry, Jean-Christophe; Colobert, Francoise; Leroux, Frederic R.; Juge, Sylvain [Journal of Organic Chemistry, 2012, vol. 77, # 13, p. 5759 - 5769]

35
[ 62336-24-7 ]
ortho-lithio-diphenylphosphinobenzene [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
90%	With n-butyllithium In diethyl ether; hexane at -78 - 20℃; for 2h; Inert atmosphere; Schlenk technique;
87%	With n-butyllithium In diethyl ether; hexane at -40 - 20℃; for 1h; Inert atmosphere;
	With n-butyllithium In diethyl ether; hexane at 20℃; for 0.333333h; Inert atmosphere; Schlenk technique;

Reference： [1]Herrmann, Roy; Braun, Thomas; Mebs, Stefan [European Journal of Inorganic Chemistry, 2014, vol. 2014, # 28, p. 4826 - 4835]
[2]Gualco, Pauline; Ladeira, Sonia; Miqueu, Karinne; Amgoune, Abderrahmane; Bourissou, Didier [Angewandte Chemie - International Edition, 2011, vol. 50, # 36, p. 8320 - 8324]
[3]Nol-Duchesneau, Ludovik; Lugan, Nol; Lavigne, Guy; Labande, Agns; Csar, Vincent [Organometallics, 2014, vol. 33, # 19, p. 5085 - 5088]

36
[ 110-85-0 ]
[ 62336-24-7 ]
[ 453559-77-8 ]
[ 603-35-0 ]

Yield	Reaction Conditions	Operation in experiment
1: 72% 2: 23%	With tris-(dibenzylideneacetone)dipalladium⁽⁰⁾; tris(2-morpholinophenyl)phosphine; sodium t-butanolate In toluene at 100℃; for 24h;	4.4.1. 1-(2-(Diphenylphosphino)phenyl)piperazine (L3) General procedure: BDPP (341 mg, 1 mmol), NaOtBu (114 mg, 1.5 mmol), piperazine (129 mg, 1.5 mmol), Pd2(dba)3 (9 mg, 0.01 mmol), L7 (31 mg, 0.06 mmol), and toluene (2.5 mL) were mixed in a Schlenk reactor. After the reaction mixture was placed in a pre-heated oil bath at 100 °C for 24 h, H2O (20 mL) was added at room temperature. The product was extracted with ether (10 mL × 3) and was dried over Na2SO4. The solvent was evaporated in vacuo. The remaining solid was purified by chromatography (5:100 methanol/dichloromethane) to give L3 (249 mg, 72% yield) as a yellow crystal along with a debrominated product (PPh3, 25%). 1H NMR (400 MHz, CDCl3) δ 7.34-7.28 (m, 11H), 7.18-7.15 (m, 1H), 7.04 (t, J = 7.5 Hz, 1H), 6.72-6.69 (m, 1H), 2.82 (t, J = 4.5 Hz, 4H), 2.69-2.68 (m, 4H).; 13C NMR (101 MHz, CDCl3): δ 156.0, 155.8, 138.1, 138.0, 136.84, 136.76, 134.1, 133.9, 133.0, 129.7, 128.5, 128.4, 128.3, 125.3, 121.8, 53.4, 45.9.; 31P NMR (162 MHz, CDCl3): δ -11.72; IR (KBr) 3281, 3052, 2942, 2817, 1580, 1466, 1434, 1371, 1219, 1316, 1220, 937, 909, 767, 739, 742, 697 cm-1; HRMS (EI) calcd. for C22H23N2P: 346.1599 [M]+; found: 346.1610; m.p.: 98-100 °C.

Reference： [1]Location in patent: experimental part Dai, Yao; Feng, Xiujuan; Wang, Bin; He, Ren; Bao, Ming [Journal of Organometallic Chemistry, 2012, vol. 696, # 26, p. 4309 - 4314]

37
[ 109-01-3 ]
[ 62336-24-7 ]
[ 1350654-30-6 ]

Yield	Reaction Conditions	Operation in experiment
94%	With tris-(dibenzylideneacetone)dipalladium⁽⁰⁾; tris(2-morpholinophenyl)phosphine; sodium t-butanolate In toluene at 100℃; for 24h;	4.4.1. 1-(2-(Diphenylphosphino)phenyl)piperazine (L3) General procedure: BDPP (341 mg, 1 mmol), NaOtBu (114 mg, 1.5 mmol), piperazine (129 mg, 1.5 mmol), Pd2(dba)3 (9 mg, 0.01 mmol), L7 (31 mg, 0.06 mmol), and toluene (2.5 mL) were mixed in a Schlenk reactor. After the reaction mixture was placed in a pre-heated oil bath at 100 °C for 24 h, H2O (20 mL) was added at room temperature. The product was extracted with ether (10 mL × 3) and was dried over Na2SO4. The solvent was evaporated in vacuo. The remaining solid was purified by chromatography (5:100 methanol/dichloromethane) to give L3 (249 mg, 72% yield) as a yellow crystal along with a debrominated product (PPh3, 25%).

Reference： [1]Location in patent: experimental part Dai, Yao; Feng, Xiujuan; Wang, Bin; He, Ren; Bao, Ming [Journal of Organometallic Chemistry, 2012, vol. 696, # 26, p. 4309 - 4314]

38
[ 5735-53-5 ]
[ 62336-24-7 ]
[ 1350654-31-7 ]

Yield	Reaction Conditions	Operation in experiment
44%	With tris-(dibenzylideneacetone)dipalladium(0); 2,2'-bis-(diphenylphosphino)-1,1'-binaphthyl; sodium t-butanolate; In toluene; at 100℃; for 24h;	General procedure: BDPP (341 mg, 1 mmol), NaOtBu (114 mg, 1.5 mmol), piperazine (129 mg, 1.5 mmol), Pd2(dba)3 (9 mg, 0.01 mmol), L7 (31 mg, 0.06 mmol), and toluene (2.5 mL) were mixed in a Schlenk reactor. After the reaction mixture was placed in a pre-heated oil bath at 100 C for 24 h, H2O (20 mL) was added at room temperature. The product was extracted with ether (10 mL × 3) and was dried over Na2SO4. The solvent was evaporated in vacuo. The remaining solid was purified by chromatography (5:100 methanol/dichloromethane) to give L3 (249 mg, 72% yield) as a yellow crystal along with a debrominated product (PPh3, 25%).

Reference： [1]Journal of Organometallic Chemistry,2012,vol. 696,p. 4309 - 4314

39
[ 50777-76-9 ]
[ 62336-24-7 ]
C₃₇H₃₀OP₂ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
90%	Stage #1: (2-bromophenyl)diphenylphosphane With n-butyllithium In diethyl ether; hexane at 0℃; for 0.5h; Inert atmosphere; Stage #2: (2-formylphenyl)(diphenyl)phosphine In diethyl ether; hexane at 0℃; for 1.16667h;

Reference： [1]Nakamura, Yuki; Yoshikai, Naohiko; Ilies, Laurean; Nakamura, Eiichi [Organic Letters, 2012, vol. 14, # 13, p. 3316 - 3319]

40
[ 80-10-4 ]
[ 62336-24-7 ]
[ 1401614-87-6 ]

Yield	Reaction Conditions	Operation in experiment
87%	Stage #1: (2-bromophenyl)diphenylphosphane With n-butyllithium In diethyl ether; hexane; toluene at 20℃; for 0.416667h; Inert atmosphere; Stage #2: diphenylsilyl dichloride In diethyl ether; hexane; toluene at 20℃; Inert atmosphere;
29%	Stage #1: (2-bromophenyl)diphenylphosphane With n-butyllithium In diethyl ether; hexane at -50℃; for 3h; Inert atmosphere; Stage #2: diphenylsilyl dichloride In diethyl ether; hexane at 20℃;	1.2 Synthesis of Compound 2: Subsequently, Compound 1 (0.500 g, 1.47 mmol) was placed in a 100 ml two-neck eggplant-shaped flask,Under a nitrogen atmosphere, diethyl ether (7.5 ml) was added and the mixture was cooled to -50 ° C. Further, 1.0 ml (1.55 M, 1.55 mmol) of n-BuLi hexane solution was added dropwise, and the mixture was stirred for 3 hours.Thereafter, diphenyldichlorosilane (4.51 g, 17.8 mmol) was added and the temperature was raised to room temperature with stirring.After the reaction, the solution was diluted with hexane, and the by-produced salt was removed by filtration.After distilling off the solvent under reduced pressure, recrystallization from hexane solvent was carried out to isolate Compound 2. Yield 0.204 g, yield 29%.

Reference： [1]Sanji, Takanobu; Naito, Keigo; Kashiwabara, Taigo; Tanaka, Masato [Heteroatom Chemistry, 2012, vol. 23, # 6, p. 520 - 524]
[2]Current Patent Assignee: NATIONAL INSTITUTE OF ADVANCED INDUSTRIAL SCIENCE AND TECHNOLOGY - JP5791040, 2015, B2 Location in patent: Paragraph 0018

41
[ 62336-24-7 ]
[ 84783-64-2 ]

Yield	Reaction Conditions	Operation in experiment
48%	Stage #1: (2-bromophenyl)diphenylphosphane With n-butyllithium In tetrahydrofuran; hexane at -78℃; for 1h; Inert atmosphere; Stage #2: With iron(III) acetylacetonate In tetrahydrofuran at -78℃; for 1h; Inert atmosphere;	2.2.2. Synthesis of 2,2′-bis(diphenylphosphino)biphenyl (bpbp) This compound was synthesized from a modified protocol of the literature [36]. To a solutionof (2-bromophenyl)diphenylphosphine (0.41 g, 1.20 mmol) in THF (5 mL) was added at -78 °Cunder nitrogen n-BuLi (1.6 M in hexane) (0.75 mL, 1.20 mmol) and the resulting solution wasstirred at this temperature during one hour. A solution of Fe(acac)3 (0.51 g, 1.44 mmol) inTHF (7 mL) was then added and the stirring was maintained for one hour at -78 °C. The solution was quenched with water (2 mL) and extracted with dichloromethane (3 × 10 mL).The organic phases were dried over MgSO4 and the solvent evaporated under vacuum togive a residue which was purified by chromatographic column on silica gel using petroleumether/dichloromethane (2/1) as eluent. The titled compound was obtained as white solid(0.15 g, 48%). 1H NMR (600 MHz, CDCl3): δ 7.32-7.13 (m, 24H), 7.07 (d, J = 6 Hz, 2H), 6.90(d, J = 6 Hz, 2H).
46%	Stage #1: (2-bromophenyl)diphenylphosphane With n-butyllithium In tetrahydrofuran; hexane at -78℃; for 1h; Inert atmosphere; Stage #2: With iron(III)-acetylacetonate In tetrahydrofuran; hexane at -78℃; for 1h;	J.1 J.1. bis-2,2'-(diphenylphosphino)biphenyl 49a J.l. bis-2,2 '-(Diphenylphosphino)biphenyle 49aTo a solution of (2-bromophenyl)-diphenylphosphine (Il-a) (0.41 g, 1.20 mmol) in THF (5 mL) was added at -78°C under argon w-BuLi (1.6 M in hexane) (0.75 mL, 1.20 mmol) and the resulting solution was stirred at this temperature during one hour. A solution of Fe(acac)3 (0.52 g, 1.44 mmol) in THF (7 mL) was then added and the stirring was maintained during one hour at -78°C. The solution was quenched with water (2 mL) and extracted with methylene chloride (3x10 mL). The organic phases were dried over MgS04 and the solvent evaporated under vacuo to give a residue which was purified by chromatographic column on silica gel using petroleum ether/methylene chloride (2/1) as eluent. The titled compound was obtained as white solid. Yield: 46%; Rf 0.32 (petroleum ether/CH2Cl2 2/1); 1H NMR (300MHz, CDC13) δ 6.80-6.84 (m, 2H, Harom), 6.98-7.01 (m, 2H, Harom), 7.04-7.22 (m, 24H, H arom); 31P NMR (121 MHz, CDC13) δ -14.4. Noteworthy, the coupling of (Il-a) was also carried out with FeCl3 or Cu(OAc)2 and the diphosphine 49a was obtained in satisfactory yields (30-45%).

Reference： [1]Chen, Bu-Lin; Liu, Li; Zhong, Xin-Xin; Asiri, Abdullah M.; Alamry, Khalid A.; Li, Guang-Hua; Li, Fa-Bao; Zhu, Nian-Yong; Wong, Wai-Yeung; Qin, Hai-Mei [Journal of Coordination Chemistry, 2017, vol. 70, # 23, p. 3907 - 3919]
[2]Current Patent Assignee: CENTRE NATIONAL DE LA RECHERCHE SCIENTIFIQUE; UNIVERSITY OF STRASBOURG; SYNTHELOR SAS; UNIVERSITY OF BURGUNDY - WO2013/7724, 2013, A1 Location in patent: Page/Page column 80

42
[ 3282-30-2 ]
[ 62336-24-7 ]
[ 1417911-85-3 ]

Yield	Reaction Conditions	Operation in experiment
78%	Stage #1: (2-bromophenyl)diphenylphosphane With n-butyllithium In tetrahydrofuran at -78℃; for 1h; Inert atmosphere; Stage #2: pivaloyl chloride In tetrahydrofuran at 20℃;	G G. SYNTHESIS OF o-ACYLARYL PHOSPHINE DERIVATIVES (I-46) G. SYNTHESIS OF o-ACYLARYL PHOSPHINE DERIVATIVES (1-46)o-( t-butylcarbonyl)phenyl]diphenylphosphine (1-46)To a solution of (2-bromophenyl)diphenylphosphine (Il-a) (0.50 mmol) in dry THF (2 mL) was added dropwise under argon at -78°C w-BuLi (0.55 mmol). The resulting solution was stirred at this temperature during one hour and pivaloyl chloride (0.80 mmol) was then added dropwise. After stirring at room temperature overnight, the reaction mixture was quenched with water (10 mL) and extracted with methylene chloride (3x10 mL). The organic phases were dried over MgS04, filtered and the solvent evaporated giving a residue which was purified by column chromatography on silica gel using petroleum ether/ethyl acetate 3: 1 as eluent. White solid; Yield 78%; Rf 0.43 (petroleum ether/ethyl acetate 3: 1); IR (neat) 3049, 2967, 2928, 2867, 1686, 1585, 1477, 1458, 1431, 1389, 1361, 1283, 1192, 967, 947, 778, 741, 691 cm"1; 1H NMR (300MHz, CDC13) δ 1.35 (s, 9H, CH3), 7.18-7.22 (m, 1H, Harom), 7.25-7.40 (m, 13H, Harom); 13C NMR (75.5 MHz, CDC13) δ27.7 (d, J = 3.3 Hz, CH3), 44.7 (C(CH3)3), 124.8 (d, J = 8.6 Hz, Carom), 128.3 (Carom), 128.5 (d, J = 4.9 Hz, Carom), 128.7 (Carom), 133.3 (Carom), 133.5 (Carom), 134.6 (d, J =15.8 Hz, Carom), 134.8 (d, J = 2.2 Hz, Carom), 137.0 (d, J = 10.4 Hz, Carom), 148.0 (d, J = 35.8 Hz, Carom); 31P NMR (121 MHz, CDC13) δ -10.4; HRMS calcd for C23H23PONa [M+Na]+ 369.1379, found 369.1382.

Reference： [1]Current Patent Assignee: CENTRE NATIONAL DE LA RECHERCHE SCIENTIFIQUE; UNIVERSITY OF STRASBOURG; SYNTHELOR SAS; UNIVERSITY OF BURGUNDY - WO2013/7724, 2013, A1 Location in patent: Page/Page column 65; 66

43
[ 75-78-5 ]
[ 62336-24-7 ]
[ 1417911-87-5 ]

Yield	Reaction Conditions	Operation in experiment
52%	Stage #1: (2-bromophenyl)diphenylphosphane With n-butyllithium In tetrahydrofuran at -78℃; for 1h; Inert atmosphere; Stage #2: dimethylsilicon dichloride In tetrahydrofuran at 20℃;	H.2.1 H.2. Synthesis of diphosphine 47b,c with a silano group as bridge General procedure: H.2. Synthesis of diphosphine 47b,c with a silano group as bridgeGeneral procedure: To a solution of obromophosphine (II) (0.50 mmol) in dry THF (3 mL) was added dropwise under argon at -78°C w-BuLi (0.55 mmol). The resulting solution was stirred at this temperature during one hour and dichlorodimethylsilane (0.23 mmol) was then added dropwise. After stirring at room temperature overnight, the reaction mixture was quenched with water (10 mL) and extracted with methylene chloride (3x10 mL). The organic phases were dried over MgS04, filtered and the solvent evaporated giving a residue which was purified by column chromatography on silica gel and/or recristallisation.H.2.1. Diphosphine 47b:Purification: column chromatography (elution with 3: 1 methylene chloride/petroleum ether) and recristallisation in methyl alcohol/methylene chloride. White solid; Yield: 52%; Rf 0.28 (methylene chloride/petroleum ether 3: 1); IR (neat) 3045, 2966, 1583, 1478, 1431, 1251, 1108, 831, 809, 737, 694 cm"1; 1H NMR (300MHz, CDC13) δ 0.63 (t, J = 1.5 Hz, 6H, SiCH3), 6.90-6.95 (m, 8H, Harom), 7.06-7.21 (m, 18H, Harom), 7.64-7.68 (m, 2H, Harom); 13C NMR (75.5 MHz, CDC13) δ 2.58 (t, J = 10.1 Hz, SiCH3), 127.9 (Carom), 128.1 (d, J = 6.1 Hz, Carom), 128.2 (Carom), 129.1 (Carom), 133.2 (d, J = 18.8 Hz, Carom), 135.2 (Carom), 136.3 (dd, J = 2.8, 16.0 Hz, Carom), 138.4 (d, J = 13.3 Hz, Carom), 143.0 (d, J = 12.0 Hz, Carom), 148.0 (dd, J = 3.3, 47.5 Hz, Carom); 31P NMR (121 MHz, CDC13) δ -11.2; HRMS calcd for C38H34P2SiNa [M+Na]+ 603.1797, found 603.1778.

Reference： [1]Current Patent Assignee: CENTRE NATIONAL DE LA RECHERCHE SCIENTIFIQUE; UNIVERSITY OF STRASBOURG; SYNTHELOR SAS; UNIVERSITY OF BURGUNDY - WO2013/7724, 2013, A1 Location in patent: Page/Page column 67; 68; 69

44
[ 1417912-02-7 ]
[ 62336-24-7 ]
[ 1417911-99-9 ]

Yield	Reaction Conditions	Operation in experiment
54%	Stage #1: (2-bromophenyl)diphenylphosphane With n-butyllithium In tetrahydrofuran; hexane at -78℃; for 1h; Inert atmosphere; Stage #2: (R)-phenyl-o-tolylphenylphosphinite In tetrahydrofuran; hexane at -78 - 20℃;	I.2.1 I.2.1. (Sp)-1-diphenylphosphino-2-(o-tolylphenylphosphino)benzene 48i 1.2.1. (Sp)-l -diphenylphosphino-2-( o-tolylphenylphosphino )benzene 48iTo a solution of obromodiphenylphosphine (Il-a) (0.20 g, 0.59 mmol) in THF (3 mL) was added at -78°C under argon w-BuLi (1.6 M in hexane) (0.41 mL, 0.65 mmol) and the resulting solution was stirred at this temperature during one hour. At this time, a solution of (R)-phenyl-otolylphenylphosphinite (0.17 g, 0.59 mmol) in THF (2 mL) was added drop wise at -78°C and the mixture was stirred at room temperature overnight. After quenching with water, the mixture was extracted with methylene chloride (3x5 mL) and the organic phases were dried over MgS04. The solvent was evaporated under vacuo to give a residue which was purified by chromatographic column on silica gel using toluene/petroleum ether (1/1) as eluent.Colorless sticky solid; Yield: 54%; Enantiomeric excess: 99% by HPLC analysis (Lux 5u Cellulose 2, 0.2 mL.min"1, hexane/2-propanol 98:2, tR (S)= 19.5 min, tR (R)= 20.8 min; Rf 0.43 (petroleum ether/toluene 1: 1); [D +33.0 (c 0.3 CHC13); IR (neat) 3051, 1584, 1477, 1433, 1269, 1068, 998, 739, 693 cm"1; 1H NMR (300MHz, C6D6) δ 2.45 (d, J = 0.8 Hz, 3H, CH3), 7.00-7.07 (m, 3H, Harom), 7.08-7.19 (m, 12H, Harom), 7.30-7.32 (m, 1H, Harom), 7.36-7.38 (m, 1H, Harom), 7.43-7.48 m, 6H, Harom); 13C NMR (75.5 MHz, C6D6) δ 21.2 (d, J = 22.6 Hz, CH3), 126.0 (Carom), 128.3 (Carom), 128.4 (m, Carom), 128.5 (Carom), 128.6 (d, J = 7.3 Hz, Carom), 129.2 (d, J = 6.2 Hz, Carom), 130.2 (d, J = 4.5 Hz, Carom), 133.7 (Carom), 133.8 (Carom), 134.0 (Carom), 134.1 (Carom), 134.2 (d, J = 18.7 Hz, Carom), 134.3 (Carom), 134.4 (Carom), 134.5 (Carom), 136.7 (dd, J = 5.6, 13.3 Hz, Carom), 137.0 (dd, J = 5.6, 13.3 Hz, Carom), 137.7 (dd, J = 6.1, 12.8 Hz, Carom), 138.0 (dd, J = 6.1, 12.8 Hz, Carom), 142.4 (d, J = 26.2 Hz, Carom), 143.8 (dd, J = 11.7, 32.9 Hz, Carom), 144.4 (dd, J = 12.2, 33.2 Hz, Carom); 31P NMR (121 MHz, C6D6) δ - 12.7 (d, J = 154.0 Hz), -19.8 (d, J = 154.0 Hz); HRMS calcd for C31H26P2Na [M+Na]+ 483.1402, found 483.1423.

Reference： [1]Current Patent Assignee: CENTRE NATIONAL DE LA RECHERCHE SCIENTIFIQUE; UNIVERSITY OF STRASBOURG; SYNTHELOR SAS; UNIVERSITY OF BURGUNDY - WO2013/7724, 2013, A1 Location in patent: Page/Page column 76; 77

45
[ 1066-35-9 ]
[ 62336-24-7 ]
[ 1435872-01-7 ]

Yield	Reaction Conditions	Operation in experiment
90%	Stage #1: (2-bromophenyl)diphenylphosphane With n-butyllithium In tetrahydrofuran; hexane at -78℃; for 0.5h; Inert atmosphere; Stage #2: dimethylmonochlorosilane at -78℃; for 0.5h;
87%	Stage #1: (2-bromophenyl)diphenylphosphane With n-butyllithium In tetrahydrofuran at -78℃; for 0.5h; Stage #2: dimethylmonochlorosilane In tetrahydrofuran at -78 - 20℃;

Reference： [1]Zhang, Fushi; Wang, Liduo; Chang, Shih-Han; Huang, Kuan-Lin; Chi, Yun; Hung, Wen-Yi; Chen, Chih-Ming; Lee, Gene-Hsiang; Chou, Pi-Tai [Dalton Transactions, 2013, vol. 42, # 19, p. 7111 - 7119]
[2]Ren, Shishuai; Xie, Shangqing; Zheng, Tingting; Wang, Yangyang; Xu, Shilu; Xue, Benjing; Li, Xiaoyan; Sun, Hongjian; Fuhr, Olaf; Fenske, Dieter [Dalton Transactions, 2018, vol. 47, # 12, p. 4352 - 4359]

46
[ 145240-28-4 ]
[ 62336-24-7 ]
2-diphenylphosphino-4'-butylbiphenyl [ No CAS ]

Reference： [1]Angewandte Chemie - International Edition,2013,vol. 52,p. 11892 - 11895
Angew. Chem.,2013

47
[ 5720-07-0 ]
[ 62336-24-7 ]
(4'-methoxy-[1,1'-biphenyl]-2-yl)diphenylphosphine [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
68%	With palladium diacetate; potassium carbonate In toluene at 80℃; for 72h;
39%	With potassium phosphate; dichloro(1,1'-bis(diphenylphosphanyl)ferrocene)palladium(II)*CH₂Cl₂ In 1,4-dioxane at 100℃;

Reference： [1]An, Jiangzhen; Jia, Chunqi; Li, Gang; Wang, Junjie; Yan, Bingxu; Yang, Suling; Zhong, Lei [Organic Letters, 2020, vol. 22, # 24, p. 9450 - 9455]
[2]Baba, Katsuaki; Tobisu, Mamoru; Chatani, Naoto [Angewandte Chemie - International Edition, 2013, vol. 52, # 45, p. 11892 - 11895][Angew. Chem., 2013]

48
[ 32316-92-0 ]
[ 62336-24-7 ]
(2-(naphthalen-2-yl)phenyl)diphenylphosphine [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
58%	With palladium diacetate; potassium carbonate In toluene at 80℃; for 72h;
	With potassium phosphate; dichloro(1,1'-bis(diphenylphosphanyl)ferrocene)palladium(II)*CH₂Cl₂ In 1,4-dioxane at 100℃;

Reference： [1]An, Jiangzhen; Jia, Chunqi; Li, Gang; Wang, Junjie; Yan, Bingxu; Yang, Suling; Zhong, Lei [Organic Letters, 2020, vol. 22, # 24, p. 9450 - 9455]
[2]Baba, Katsuaki; Tobisu, Mamoru; Chatani, Naoto [Angewandte Chemie - International Edition, 2013, vol. 52, # 45, p. 11892 - 11895][Angew. Chem., 2013]

49
[ 75-77-4 ]
[ 62336-24-7 ]
[ 885702-66-9 ]

Yield	Reaction Conditions	Operation in experiment
82%	Stage #1: (2-bromophenyl)diphenylphosphane With n-butyllithium In diethyl ether; hexane at 20℃; for 2h; Inert atmosphere; Stage #2: chloro-trimethyl-silane In diethyl ether; hexane at 0 - 20℃; for 3h; Inert atmosphere;
82%	Stage #1: (2-bromophenyl)diphenylphosphane With n-butyllithium In diethyl ether; hexane at 0 - 20℃; for 2h; Inert atmosphere; Schlenk technique; Stage #2: chloro-trimethyl-silane In diethyl ether; hexane at 0 - 20℃; for 3h; Inert atmosphere; Schlenk technique;
80%	Stage #1: (2-bromophenyl)diphenylphosphane With n-butyllithium In diethyl ether; hexane at 0 - 23℃; for 2h; Inert atmosphere; Stage #2: chloro-trimethyl-silane In diethyl ether; hexane at 0 - 23℃; for 3h; Inert atmosphere;

Reference： [1]Xue, Mei; Li, Jiayun; Peng, Jiajian; Bai, Ying; Zhang, Guodong; Xiao, Wenjun; Lai, Guoqiao [Applied Organometallic Chemistry, 2014, vol. 28, # 2, p. 120 - 126]
[2]Li, Jiayun; Xue, Mei; Bai, Ying; Peng, Jiajian; Xiao, Wenjun [Applied Organometallic Chemistry, 2016, vol. 30, # 11, p. 905 - 910]
[3]Pei, Xiao-Li; Pereira, Ana; Smirnova, Ekaterina S.; Echavarren, Antonio M. [Chemistry - A European Journal, 2020, vol. 26, # 32, p. 7309 - 7313]

50
(2S_P,4R,5S)-(-)-3,4-dimethyl-2,5-diphenyl-1,3,2-oxazaphospholidine borane [ No CAS ]
[ 62336-24-7 ]
(R_P)-(2-diphenylphosphinophenyl)[(1S,2R)-(N-ephedrino)](phenyl)phosphine-P-borane [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
92%	Stage #1: (2-bromophenyl)diphenylphosphane With sec.-butyllithium In diethyl ether; hexane; cyclohexane at 0℃; for 1h; Inert atmosphere; Stage #2: (2S_P,4R,5S)-(-)-3,4-dimethyl-2,5-diphenyl-1,3,2-oxazaphospholidine borane In tetrahydrofuran; diethyl ether; hexane; cyclohexane at -15 - 0℃; for 2h; Inert atmosphere;

Reference： [1]Rast, Slavko; Stephan, Michel; Mohar, Barbara [European Journal of Organic Chemistry, 2015, vol. 2015, # 10, p. 2214 - 2225]

51
[ 62336-24-7 ]
2-(diphenylphosphanyl)benzeneselenol [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
93%	Stage #1: (2-bromophenyl)diphenylphosphane With magnesium In tetrahydrofuran at 90℃; for 1h; Schlenk technique; Inert atmosphere; Stage #2: With selenium at 0 - 20℃; Inert atmosphere;

Reference： [1]Zhou, Hongwei; Sun, Hongjian; Zheng, Tingting; Zhang, Shumiao; Li, Xiaoyan [European Journal of Inorganic Chemistry, 2015, vol. 2015, # 19, p. 3139 - 3145]

52
[ 88284-48-4 ]
[ 62336-24-7 ]
[ 1088-00-2 ]

Reference： [1]Organic Letters,2015,vol. 17,p. 70 - 73

53
[ 644-97-3 ]
[ 62336-24-7 ]
[ 53103-03-0 ]

Yield	Reaction Conditions	Operation in experiment
86%	Stage #1: (2-bromophenyl)diphenylphosphane With n-butyllithium In tetrahydrofuran at -78℃; for 1h; Stage #2: Dichlorophenylphosphine In tetrahydrofuran at -70 - 20℃; for 4h;
86%	Stage #1: Dichlorophenylphosphine; (2-bromophenyl)diphenylphosphane With n-butyllithium In tetrahydrofuran at -78℃; for 0.166667h; Inert atmosphere; Stage #2: In tetrahydrofuran at -70 - 20℃; for 6h; Inert atmosphere;
81%	Stage #1: (2-bromophenyl)diphenylphosphane With n-butyllithium In tetrahydrofuran; hexane at -78 - 20℃; for 1.5h; Inert atmosphere; Stage #2: Dichlorophenylphosphine In tetrahydrofuran; hexane at -78 - 20℃; Inert atmosphere;

36%

Stage #1: (2-bromophenyl)diphenylphosphane With n-butyllithium In diethyl ether; hexane at -40 - 20℃; for 2.16667h; Stage #2: Dichlorophenylphosphine In diethyl ether; hexane at 20℃;

Reference： [1]Chakkaradhari, Gomathy; Chen, Yi-Ting; Karttunen, Antti J.; Dau, Minh Thuy; Jänis, Janne; Tunik, Sergey P.; Chou, Pi-Tai; Ho, Mei-Lin; Koshevoy, Igor O. [Inorganic Chemistry, 2016, vol. 55, # 5, p. 2174 - 2184]
[2]Chakkaradhari, Gomathy; Belyaev, Andrey A.; Karttunen, Antti J.; Sivchik, Vasily; Tunik, Sergey P.; Koshevoy, Igor O. [Dalton Transactions, 2015, vol. 44, # 29, p. 13294 - 13304]
[3]Shang, Rui; Ilies, Laurean; Nakamura, Eiichi [Journal of the American Chemical Society, 2016, vol. 138, # 32, p. 10132 - 10135]
[4]Li, Ping; De Bruin, Bas; Reek, Joost N. H.; Dzik, Wojciech I. [Organometallics, 2015, vol. 34, # 20, p. 5009 - 5014]

54
[ 1417912-03-8 ]
[ 62336-24-7 ]
[ 1417911-91-1 ]

Yield	Reaction Conditions	Operation in experiment
65%	Stage #1: (2-bromophenyl)diphenylphosphane With n-butyllithium In tetrahydrofuran; hexane at -78℃; for 1h; Inert atmosphere; Stage #2: (R)-phenyl-o-anisylphenylphosphinite In tetrahydrofuran; hexane at -78 - 20℃; Inert atmosphere; stereoselective reaction;

Reference： [1]Bayardon, Jérôme; Rousselin, Yoann; Jugé, Sylvain [Organic Letters, 2016, vol. 18, # 12, p. 2930 - 2933]

55
[ 1417912-02-7 ]
[ 62336-24-7 ]
(S)-1-(phenyl-o-tolylphosphino)-1-(diphenylphosphino)benzene [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
54%	Stage #1: (2-bromophenyl)diphenylphosphane With n-butyllithium In tetrahydrofuran; hexane at -78℃; for 1h; Inert atmosphere; Stage #2: (R)-phenyl-o-tolylphenylphosphinite In tetrahydrofuran; hexane at -78 - 20℃; Inert atmosphere; stereoselective reaction;

Reference： [1]Bayardon, Jérôme; Rousselin, Yoann; Jugé, Sylvain [Organic Letters, 2016, vol. 18, # 12, p. 2930 - 2933]

56
(R)-phenyl-(3,5-di-tert-butylphenyl)phenylphosphinite [ No CAS ]
[ 62336-24-7 ]
(S)-1-(di-(3,5-di-tert-butylphenyl)phosphino)-2-(diphenylphosphino)benzene [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
45%	Stage #1: (2-bromophenyl)diphenylphosphane With n-butyllithium In tetrahydrofuran; hexane at -78℃; for 1h; Inert atmosphere; Stage #2: (R)-phenyl-(3,5-di-tert-butylphenyl)phenylphosphinite In tetrahydrofuran; hexane at -78 - 20℃; Inert atmosphere; stereoselective reaction;

Reference： [1]Bayardon, Jérôme; Rousselin, Yoann; Jugé, Sylvain [Organic Letters, 2016, vol. 18, # 12, p. 2930 - 2933]

57
(S)-methyl-o-anisylphenylphosphinite [ No CAS ]
[ 62336-24-7 ]
(R<SUB>P</SUB>)-(2-anisyl)(2-diphenylphosphinophenyl)(phenyl)phosphine [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
55%	Stage #1: (2-bromophenyl)diphenylphosphane With n-butyllithium In tetrahydrofuran; hexane at -78℃; for 1h; Inert atmosphere; Stage #2: (S)-methyl-o-anisylphenylphosphinite In tetrahydrofuran; hexane at -78 - 20℃; Inert atmosphere; stereoselective reaction;

Reference： [1]Bayardon, Jérôme; Rousselin, Yoann; Jugé, Sylvain [Organic Letters, 2016, vol. 18, # 12, p. 2930 - 2933]

58
(4-bromophenyl)(4,6-diphenyl-1,3,5-triazin-2-yl)methanone [ No CAS ]
[ 62336-24-7 ]
(4-bromophenyl)(4,6-diphenyl-1,3,5-triazin-2-yl)(2-(diphenylphosphanyl)phenyl)methanol [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	Stage #1: (2-bromophenyl)diphenylphosphane With n-butyllithium In tetrahydrofuran; hexane at -78℃; for 35h; Stage #2: (4-bromophenyl)(4,6-diphenyl-1,3,5-triazin-2-yl)methanone In tetrahydrofuran; hexane at -78 - 20℃; for 3.08333h;	3 (4-bromophenyl)(4,6-diphenyl-1,3,5-triazin-2-yl)(2-(diphenylphospha nyl)phenyl)methanol A 50 mL three neck round bottom flask is charged with (2- bromophenyl)diphenylphosphine (0.5 g, 1.47 mmol) and anhydrous THF (20 mL) and is cooled to -78°C. 1.6M n-butyllithium in hexanes (1 mL, 1.6 mmol) is added over 5 minutes and the reaction stirred at -78°C for 30 mm. Ketone (0.555 g, 1.33 mmol) in THF (10 mL) is added to the lithiated species forming a dark mixture. After 5 mm at -78°C the ice bath is removed and the reaction stirred at room temperature for 3 h. The reaction is partitioned between dichloromethane and water. The organic layer is dried over magnesium sulfate, filtered, and concentrated giving a sticky oil. The material is taken into the next reaction without further purification.

Reference： [1]Current Patent Assignee: DOW INC - WO2016/109274, 2016, A1 Location in patent: Paragraph 00151

59
[ 62336-24-7 ]
C₁₈H₁₄BrF₂P [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
96%	With xenon difluoride In dichloromethane at -35℃; for 1h;

Reference： [1]Firth, Kelly F.; Möbus, Juri; Stephan, Douglas W. [Chemical Communications, 2016, vol. 52, # 97, p. 13967 - 13970]

60
[ 365999-78-6 ]
[ 62336-24-7 ]
1,1'-[2-(diphenylphosphaneyl)phenyl]phosphanediyl}bis(1H-pyrrole) [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
67%	Stage #1: (2-bromophenyl)diphenylphosphane With n-butyllithium In tetrahydrofuran; hexane at -78℃; for 1h; Inert atmosphere; Stage #2: 1,1′-(chlorophosphinediyl)bis(1H-pyrrole) In tetrahydrofuran; hexane at -78 - 20℃; Inert atmosphere;
65%	Stage #1: (2-bromophenyl)diphenylphosphane With n-butyllithium In tetrahydrofuran; hexane at -78℃; for 1h; Inert atmosphere; Schlenk technique; Stage #2: 1,1′-(chlorophosphinediyl)bis(1H-pyrrole) In tetrahydrofuran; hexane at -78 - 20℃; Inert atmosphere; Schlenk technique; regioselective reaction;

Reference： [1]Alcarazo, Manuel; Golz, Christopher; Kpante, Malkaye; Marset, Xavier; Recort-Fornals, Martí; Wolf, Lawrence M.; Zieliński, Adam [Advanced Synthesis and Catalysis, 2021, vol. 363, # 14, p. 3546 - 3553]
[2]Gu, Lianghu; Wolf, Lawrence M.; Zieliński, Adam; Thiel, Walter; Alcarazo, Manuel [Journal of the American Chemical Society, 2017, vol. 139, # 13, p. 4948 - 4953]

61
[ 75-50-3 ]
[ 62336-24-7 ]
C₂₁H₂₃N₂P [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
31%	With copper(l) iodide In N,N-dimethyl-formamide at 80℃; for 12h; Inert atmosphere; Schlenk technique;	31.1 O-(diphenylphosphino)bromobenzene (20 mmol), N,N-dimethyl methylamine (50 mmol), N,N-dimethyl methanamide solvent (40 mL), and CuI catalyst (0.5 g) are added into a Schlenk bottle (100 mL) in N2 atmosphere. The mixed liquid is heated to 80° C. and kept for 12 hours at such a temperature. After completion of the reaction, the liquid is cooled to room temperature. Insoluble substances are removed through filtration. The residual solution is separated by a chromatographic column, and is eluted by n-hexane. All solution is collected, and all solvent and volatile compositions are removed through a vacuum decompression method so as to obtain a white solid product. A productivity of the product is 31%. The elemental analysis results are shown as follows. Calculation values: N, 8.38; C, 75.43; H, 6.93. Measured values: N, 8.35; C, 75.50; H, 6.95.

Reference： [1]Current Patent Assignee: CHINA PETROCHEMICAL CORPORATION; SHANGHAI HUAYI (GROUP) COMPANY; XIAMEN UNIVERSITY - US2017/106358, 2017, A1 Location in patent: Paragraph 0141-0144

62
[ 598-56-1 ]
[ 62336-24-7 ]
[ 858135-33-8 ]

Yield	Reaction Conditions	Operation in experiment
37%	With copper(l) iodide In N,N-dimethyl-formamide at 80℃; for 12h; Inert atmosphere; Schlenk technique;	32.1 O-(diphenylphosphino)bromobenzene (20 mmol), N,N-dimethyl ethylamine (50 mmol), N,N-dimethyl methanamide solvent (40 mL), and CuI catalyst (0.5 g) are added into a Schlenk bottle (100 mL) in N2 atmosphere. The mixed liquid is heated to 80° C. and kept for 12 hours at such a temperature. After completion of the reaction, the liquid is cooled to room temperature. Insoluble substances are removed through filtration. The residual solution is separated by a chromatographic column, and is eluted by n-hexane. All solution is collected, and all solvent and volatile compositions are removed through a vacuum decompression method so as to obtain a white solid product. A productivity of the product is 37%. The elemental analysis results are shown as follows. Calculation values: N, 8.04; C, 75.84; H, 7.23. Measured values: N, 8.05; C, 75.69; H, 7.27.

Reference： [1]Current Patent Assignee: CHINA PETROCHEMICAL CORPORATION; SHANGHAI HUAYI (GROUP) COMPANY; XIAMEN UNIVERSITY - US2017/106358, 2017, A1 Location in patent: Paragraph 0153-0156

63
(diphenylphosphino)methylamine [ No CAS ]
[ 62336-24-7 ]
[ 473250-02-1 ]

Yield	Reaction Conditions	Operation in experiment
28%	With copper(l) iodide; triethylamine In N,N-dimethyl-formamide at 80℃; for 12h; Inert atmosphere; Schlenk technique;	33.1 O-(diphenylphosphino)bromobenzene (20 mmol), diphenylphosphino methylamine (20 mmol), triethylamine (50 mmol), N,N-dimethyl methanamide solvent (40 mL), and CuI catalyst (0.5 g) are added into a Schlenk bottle (100 mL) in N2 atmosphere. The mixed liquid is heated to 80° C. and kept for 12 hours at such a temperature. After completion of the reaction, the liquid is cooled to room temperature. Insoluble substances are removed through filtration. The residual solution is separated by a chromatographic column, and is eluted by n-hexane. All solution is collected, and all solvent and volatile compositions are removed through a vacuum decompression method. Solid product obtained therein is recrystallized so as to obtain a light yellow crystalline product. A productivity of the product is 28%. The elemental analysis results are shown as follows. Calculation values: N, 2.95; C, 78.30; H, 5.72. Measured values: N, 2.87; C, 78.41; H, 5.76.

Reference： [1]Current Patent Assignee: CHINA PETROCHEMICAL CORPORATION; SHANGHAI HUAYI (GROUP) COMPANY; XIAMEN UNIVERSITY - US2017/106358, 2017, A1 Location in patent: Paragraph 0164-0167

64
[ 4848-43-5 ]
[ 62336-24-7 ]
C₃₂H₂₉NP₂ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
46%	With copper(l) iodide; triethylamine; In N,N-dimethyl-formamide; at 80℃; for 12h;Inert atmosphere; Schlenk technique;	O-(diphenylphosphino)bromobenzene (20 mmol), diphenylphosphino ethylamine (20 mmol), triethylamine (50 mmol), N,N-dimethyl methanamide solvent (40 mL), and CuI catalyst (0.5 g) are added into a Schlenk bottle (100 mL) in N2 atmosphere. The mixed liquid is heated to 80 C. and kept for 12 hours at such a temperature. After completion of the reaction, the liquid is cooled to room temperature. Insoluble substances are removed through filtration. The residual solution is separated by a chromatographic column, and is eluted by n-hexane. All solution is collected, and all solvent and volatile compositions are removed through a vacuum decompression method so as to obtain a white solid product. A productivity of the product is 46%. The elemental analysis results are shown as follows. Calculation values: N, 2.86; C, 78.51; H, 5.97. Measured values: N, 2.89; C, 78.49; H, 5.96.

Reference： [1]Patent: US2017/106358,2017,A1 .Location in patent: Paragraph 0175-0178

65
[ 22086-34-6 ]
[ 62336-24-7 ]
2-(9-borabicyclo[3.3.1]nonanyl)phenyl(diphenyl)phosphine [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
53%	Stage #1: (2-bromophenyl)diphenylphosphane With n-butyllithium In tetrahydrofuran; hexane at -30℃; for 1h; Sealed tube; Inert atmosphere; Stage #2: 9-chloro-9-bora-bicyclo[3.3.1]nonane In tetrahydrofuran; hexane at 20℃; for 20h; Sealed tube; Inert atmosphere;

Reference： [1]Hirata, Goki; Satomura, Hideaki; Kumagae, Hidenobu; Shimizu, Aika; Onodera, Gen; Kimura, Masanari [Organic Letters, 2017, vol. 19, # 22, p. 6148 - 6151]

66
[ 62336-24-7 ]
bis-(2-diphenylphosphino)phosphine oxide [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
66%	Stage #1: (2-bromophenyl)diphenylphosphane With n-butyllithium In tetrahydrofuran; hexane at -70℃; for 1h; Stage #2: With phosphorus trichloride In tetrahydrofuran; hexane at 20℃; for 1h;
	Stage #1: (2-bromophenyl)diphenylphosphane With n-butyllithium In diethyl ether; hexane at -40 - 20℃; for 1h; Stage #2: With diethylphosphoramidous dichloride In diethyl ether; hexane at -40 - 20℃; Stage #3: With hydrogenchloride In diethyl ether; hexane; water at 0℃; for 3h;	1 Tridentate phosphine ligands were synthesized as follows (2-Bromophenyl) diphenylphosphine (1.71 g, 5 mmol) was dissolved in 20 mL of ether and cooled to -40 ° C.To the above solution was added dropwise a hexane solution of n-butyllithium (3.75 mL, 6 mmol)The mixture was stirred at room temperature for 1 hour, then cooled again to -40 ° C,A solution of 1,1-dichloro-N, N-diethylphosphonamide (0.435 g, 2.5 mmol) in ether (5 mL)The solution was stirred at the same temperature for 1 hour. The mixture was slowly warmed to room temperature and stirred overnight,After cooling to 0 ° C, 2 mL of concentrated hydrochloric acid was added and the reaction mixture was stirred for 3 hours,Saturated sodium bicarbonate (50 mL) was added and the reaction mixture was extracted with ethyl acetate (30 mL x 3 times), the organic phases were combined,Drying over sodium sulfate, concentration of the solvent and purification of the crude product by column chromatography (hexane / ethyl acetate = 3: 1) gave the product.
	Stage #1: (2-bromophenyl)diphenylphosphane With n-butyllithium In diethyl ether; hexane at -40 - 20℃; for 1h; Stage #2: With diethylphosphoramidous dichloride In diethyl ether; hexane at -40 - 20℃; Stage #3: With hydrogenchloride In diethyl ether; hexane at 0℃; for 3h;

Reference： [1]Beliaeva, Mariia; Belyaev, Andrey; Grachova, Elena V.; Steffen, Andreas; Koshevoy, Igor O. [Journal of the American Chemical Society, 2021, vol. 143, # 37, p. 15045 - 15055]
[2]Current Patent Assignee: SOUTHERN UNIVERSITY OF SCIENCE AND TECHNOLOGY OF CHINA - CN107417724, 2017, A Location in patent: Paragraph 0026; 0028; 0030
[3]Tan, Xuefeng; Zeng, Weijun; Zhang, Xiaoyong; Chung, Lung Wa; Zhang, Xumu [Chemical Communications, 2018, vol. 54, # 5, p. 535 - 538]

67
[ 314730-64-8 ]
[ 62336-24-7 ]
C₃₈H₄₀N₂P₂ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
40%	Stage #1: (2-bromophenyl)diphenylphosphane With n-butyllithium In diethyl ether; hexane at -30 - 20℃; for 1h; Inert atmosphere; Glovebox; Stage #2: 2-chloro-1,3-bis-(2,4,6-trimethylphenyl)[1,3,2]diazaphospholidine In toluene at 20℃; for 48h; Inert atmosphere; Glovebox;

Reference： [1]Gatien, Alexandre V.; Lavoie, Christopher M.; Bennett, Raymond N.; Ferguson, Michael J.; McDonald, Robert; Johnson, Erin R.; Speed, Alexander W. H.; Stradiotto, Mark [ACS Catalysis, 2018, vol. 8, # 6, p. 5328 - 5339]

68
2-bromo-1,3-di-mesityl-2,3-dihydro-1H-1,3,2-diazaphosphole [ No CAS ]
[ 62336-24-7 ]
C₃₈H₃₈N₂P₂ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
38%	Stage #1: (2-bromophenyl)diphenylphosphane With n-butyllithium In diethyl ether; hexane at -30 - 20℃; for 1h; Inert atmosphere; Glovebox; Stage #2: 2-bromo-1,3-di-mesityl-2,3-dihydro-1H-1,3,2-diazaphosphole In toluene at 20℃; for 48h; Inert atmosphere; Glovebox;

Reference： [1]Gatien, Alexandre V.; Lavoie, Christopher M.; Bennett, Raymond N.; Ferguson, Michael J.; McDonald, Robert; Johnson, Erin R.; Speed, Alexander W. H.; Stradiotto, Mark [ACS Catalysis, 2018, vol. 8, # 6, p. 5328 - 5339]

69
[ 67-56-1 ]
[ 55124-35-1 ]
[ 62336-24-7 ]
[ 1187936-76-0 ]

Yield	Reaction Conditions	Operation in experiment
70%	Stage #1: diisopropylamine borane With magnesium; phenylmagnesium bromide In tetrahydrofuran at 20℃; for 0.166667h; Stage #2: (2-bromophenyl)diphenylphosphane In tetrahydrofuran at 70℃; Stage #3: methanol Further stages;	PhMgBr dehydrogenation followed by the addition under Barbier conditions (procedure B) General procedure: To a solution in THF (4 mL) of DIPAB (863 mg, 7.5 mmol) and Mg (182 mg, 7.5 mmol) were added a PhMgBr 1M THF solution (375 μL, 375μmol) at room temperature. After 10 min, 30 mL of anhydrous THF were added followed by the arylbromide (5 mmol). The reaction mixture was cooled down to 0 °C and quenched slowly with 7 mL of MeOH. After 1h, volatile were removed under reduced pressure and the resulting solid was dissolved in 1N HCl/MeOH (7/3). After 1h at room temperature, 100 mL of AcOEt were added, the organic phase was washed with 1N HCl (30 mL) and brine (3×30 mL). Organic phases were concentrated under reduced pressure yielding a solid which was recrystallized from H2O.

Reference： [1]Marciasini, Ludovic D.; Richard, Jimmy; Cacciuttolo, Bastien; Sartori, Guillaume; Birepinte, Melodie; Chabaud, Laurent; Pinet, Sandra; Pucheault, Mathieu [Tetrahedron, 2019, vol. 75, # 2, p. 164 - 171]

70
[ 5570-18-3 ]
[ 62336-24-7 ]
2'-diphenylphosphino-2-amino-1,1'-biphenyl [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
86%	With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; potassium phosphate; In 1,4-dioxane; at 100 - 105℃; for 16h;Sealed tube; Glovebox; Inert atmosphere;	Add in a dry, clean 100mL sealed tube with a magnetic stir bar(2-bromophenyl)-diphenylphosphine 37a (1.2 g, 3.5 mmol),<strong>[5570-18-3]2-aminophenylboronic acid</strong> (480 mg, 3.5 mmol),[1,1'-bis(diphenylphosphino)ferrocene]palladium dichloride (143 mg, 0.18 mmol),Anhydrous potassium phosphate (2.3 g, 11.5 mmol). Transfer the sealed tube to a glove box with an argon atmosphere.Add 30 mL of anhydrous 1,4-dioxane, seal the sealed tube with a cock, and take it out.The oil bath was heated at 100-105 C for 16 hours. Stop heating,After cooling to room temperature, the reaction was quenched by the addition of 20 mL of water.The aqueous phase was extracted with ethyl acetate (20 mL×3), and the organic phase was washed once with brine.Dry over anhydrous sodium sulfate. The desiccant was removed by suction filtration, and the filtrate was removed by a rotary evaporator.The residue was 1.1g to give 27a as a white solid was purified by silica gel column chromatography (petroleum ether / ethyl acetate = 5),Yield 86%, melting point: 103-105 C.

Reference： [1]Patent: CN109956970,2019,A .Location in patent: Paragraph 0041; 0043; 0044; 0045

71
[ 4073-31-8 ]
[ 62336-24-7 ]
C₂₈H₂₉NP₂ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	Stage #1: (2-bromophenyl)diphenylphosphane With n-butyllithium In tetrahydrofuran; hexane at -78 - -65℃; for 2.5h; Stage #2: (diethylamino)phenylchlorophosphine In tetrahydrofuran; hexane at -65 - 20℃; for 18h;	General Procedure for Obtaining Chloroarylphosphinesand Chloroaryldiphosphines by the Case of [2-(Diphenylphosphino)phenyl]chlorophenylphosphine A 1.15 mL of a 1.6 M n-BuLi solution inhexane was slowly added to a solution of 0.6 g(1.76 mmol) of 1-bromo-2-diphenylphosphinobenzenein 8 mL of absolute tetrahydrofuran at -78°C.The solution turned bright orange. The reaction mixturewas stirred for 2.5 h at -65°C, and then a solutionof 0.38 g of diethylaminophenylchlorophosphine in1.5 mL of absolute tetrahydrofuran was slowly addedat this temperature. The mixture was allowed to warmup to room temperature upon stirring, and then themixture was stirred at this temperature for additional18 h, the solvent was evaporated, and the residue wasdissolved in 4 mL of toluene and filtered. Then dryHCl obtained by slow dropwise addition of concentratedsulfuric acid to ammonium chloride upon stirring(HCl was dried by passing the gas through a columnwith P2O5) was bubbled through the obtained filtrate(it was red) for 3 h. Immediate precipitation ofwhite diethylammonium hydrochloride and change inthe color of the solution to pale yellow were observed.The mixture was stirred for 18 h in an argon atmosphere.The pale yellow solution was filtered from thewhite precipitate in an argon flow, and the solvent wasevaporated. The residue (yellow oil) was dried in vacuum.The yield of [2-(diphenylphosphino)phenyl]chlorophenylphosphinewas 87%. 1H NMR spectrum(400 MHz, CDCl3): δ (ppm) 6.72-7.82 (m, 19H, Ar-H).31P{1H} spectrum (161.98 MHz, CDCl3): δ (ppm)73.40 (d, 3JPP = 282 Hz, P(Ph)Cl), -19.60 (d, 3JPP =282 Hz, PPh2)
	Stage #1: (2-bromophenyl)diphenylphosphane With n-butyllithium In tetrahydrofuran; hexane at -78 - -65℃; for 2.5h; Inert atmosphere; Schlenk technique; Stage #2: (diethylamino)phenylchlorophosphine In tetrahydrofuran; hexane at -78 - 20℃; for 18h; Inert atmosphere; Schlenk technique;	1.15 mL of a 1.6 M n-BuLi solution in hexane was slowly added to a solution of 0.6 g(1.76 mmol) of 1-bromo-2-diphenylphosphinobenzenein 8 mL of absolute tetrahydrofuran at -78°C.The solution turned bright orange. The reaction mixture was stirred for 2.5 h at -65°C, and then a solution of 0.38 g of diethylaminophenylchlorophosphine in 1.5 mL of absolute tetrahydrofuran was slowly added at this temperature. The mixture was allowed to warmup to room temperature with stirring. The mixture was stirred at this temperature for additional 18 h, the solvent was evaporated, and the residue was dissolved in 4 mL of toluene and filtered. Then dry HCl (HCl was obtained by the slow dropwise addition of concentrated sulfuric acid to ammonium chloride upon stirring; hydrogen chloride was dried by passing the formed gas through a column with P2O5) was bubbled through the obtained red filtrate for 3 h. Immediate formation of a white precipitate of diethylammonium hydrochloride and a change in the color of the solution to pale yellow were observed. The mixture was stirred for 18 h in an argon atmosphere. The pale yellow solution was filtered from the white precipitate under argon, and the solvent was evaporated. The residue (yellow oil) was dried in a vacuum.

Reference： [1]Cheredilin; Sheloumov; Senin; Kozlova; Afanas’ev; Bespalova [Petroleum Chemistry, 2019, vol. 59, p. S72 - S87][Neftekhimiya]
[2]Afanas’ev, V. V.; Bespalova, N. B.; Cheredilin, D. N.; Kozlova, G. A.; Senin, A. A.; Sheloumov, A. M. [Petroleum Chemistry, 2020, vol. 60, # 1, p. 55 - 68][Neftekhimiya, 2020, vol. 60, # 1, p. 61 - 75,15]

72
2-(methoxy)naphthylchlorophenylphosphine [ No CAS ]
[ 62336-24-7 ]
[2-(diphenylphosphino)phenyl][2-(methoxy)naphthyl]phenylphosphine [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
59.4%	Stage #1: (2-bromophenyl)diphenylphosphane With n-butyllithium In tetrahydrofuran; hexane at -80 - -78℃; for 0.5h; Schlenk technique; Inert atmosphere; Stage #2: 2-(methoxy)naphthylchlorophenylphosphine In tetrahydrofuran at -78℃; for 0.5h; Schlenk technique; Inert atmosphere;	Synthesis of [2-(Diphenylphosphino)phenyl][2-(methoxy)naphthyl]phenylphosphine (7) and [2-(Diphenylphosphino)-5-isopropylphenyl][2-(methoxy)naphthyl]phenylphosphine (8) A 0.44 g (1.30 mmol) of 1-bromo-2-diphenylphosphinobenzenewas charged into a Schlenk flask,6 mL of tetrahydrofuran was added, and the obtainedsolution was cooled to -78°C. 0.94 mL (1.50 mmol) ofa 1.6 M n-BuLi solution in hexane was slowly addedto the solution. The yellow-red solution was stirred at-78 to -80°C for 30 min. A solution of 0.44 g(1.45 mmol) of 2-[(methoxy)naphthyl]chlorophenylphosphinein 6 mL of tetrahydrofuran was preparedseparately. The obtained solution was added to thestirred and cooled solution in such a way that the temperatureof the mixture did not exceed -78°C. Thesolution was stirred at -78°C for 30 min. The coolingwas removed, and the mixture was allowed to warm upto room temperature. The solvent was evaporatedunder reduced pressure, and 10 mL of methylenechloride and 10 mL of a saturated aqueous solution ofsodium chloride were poured to the residue. The aqueous and organic phases were separated. Theaqueous phase was washed with 5 mL of methylenechloride, and the organic phase, with 10 mL of a saturatedaqueous solution of sodium chloride. The phaseswere separated. The organic phases were combinedand dried over anhydrous sodium sulfate. The solutionwas evaporated to dryness. The residue was a yellowishoil, from which a white precipitate was formed uponthe addition of methanol. The precipitate was dried invacuum. The yield of [2-(diphenylphosphino)phenyl][2-(methoxy)naphthyl]phenylphosphine (7) was 0.68 g(59.4%). 1H NMR spectrum (300 MHz, C6D6): δ(ppm) 9.40 (t, J = 7 Hz, 1H, Ar-H), 7.77 (m, J =4 Hz, 1H, Ar-H), 7.60-6.75 (m, 22H, Ar-H), 6.51(d, J = 9 Hz, 1H, Ar-H), 2.84 (s, 3H, CH3). 31P{1H}NMR spectrum (121.5 MHz, C6D6): δ (ppm) -13.77(d, J = 141 Hz, 1P, P(C10H6OCH3)Ph), -28.02 (d, J =141 Hz, 1P, PPh2).

Reference： [1]Cheredilin; Sheloumov; Senin; Kozlova; Afanas’ev; Bespalova [Petroleum Chemistry, 2019, vol. 59, p. S72 - S87][Neftekhimiya]

73
[ 486-25-9 ]
[ 62336-24-7 ]
C₃₁H₂₃OP [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	With n-butyllithium In tetrahydrofuran at -90 - -70℃; for 2.5h;	1 Example 1: Synthesis of compound 1aa: 2-Bromophenyldiphenylphosphine 3 (2.0mmol, 0.68g)Dissolved in tetrahydrofuran,Add 1mL of n-butyl lithium (2.0mmol, 2.0M) toIn a solution of 2-bromophenyldiphenylphosphine 3 in tetrahydrofuran,Then 9-fluorenone 7a (2.0mmol, 0.36g)THF solution was added to the reaction bottle,React at -70 to -90 ° C for 2.5 hours,Compound 8a is obtained;

Reference： [1]Current Patent Assignee: XINYANG NORMAL UNIVERSITY - CN110845537, 2020, A Location in patent: Paragraph 0047; 0048; 0049

74
[ 2227-29-4 ]
[ 62336-24-7 ]
(2-(diisopropylsilyl)phenyl)diphenylphosphane [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
100%	Stage #1: (2-bromophenyl)diphenylphosphane With n-butyllithium In diethyl ether; hexane at -78 - 20℃; for 1h; Inert atmosphere; Stage #2: chlorodiisopropylsilane In diethyl ether; hexane at -78 - 20℃; for 6h;

Reference： [1]Bischof, Daniel; Breuer, Tobias; Grell, Yvonne; Hofmann, Philipp E.; Ivlev, Sergei I.; Koert, Ulrich; Schiller, Anna L. C.; Tripp, Matthias W.; Witte, Gregor [Angewandte Chemie - International Edition, 2020, vol. 59, # 38, p. 16501 - 16505][Angewandte Chemie, 2020, vol. 132, # 38, p. 16644 - 16648,5]

75
[ 123324-71-0 ]
[ 62336-24-7 ]
(4'-(tert-butyl)-[1,1'-biphenyl]-2-yl)diphenylphosphine [ No CAS ]