6057-79-0|tert-butyl(Phenyl)phosphine oxide| Ambeed (2024)

*All experimental methods are cited from the reference, please refer to the original source for details. We do not guarantee the accuracy of the content in the reference.

[ 6057-79-0 ] Synthesis Path-Downstream 1~46

1
[ 6057-79-0 ]
[ 6002-45-5 ]

Yield	Reaction Conditions	Operation in experiment
93%	With sulfur In toluene for 10h; Heating;
	With sulfur In benzene
	With sulfur In toluene

2
[ 6057-79-0 ]
[ 100-44-7 ]
[ 156146-40-6 ]

Yield	Reaction Conditions	Operation in experiment
89%	Stage #1: tert-Butylphenylphosphine oxide With sodium hydride In tetrahydrofuran; mineral oil at 20℃; Inert atmosphere; Stage #2: benzyl chloride In tetrahydrofuran; mineral oil Inert atmosphere;	4.2. General procedure for the synthesis of phosphine oxides 1b-f,i-k General procedure: Into a flame-dried two-necked flask equipped with magnetic stirrer and argon inlet was placed secondary phosphine oxide (3 mmol) in dry and degassed THF (15 mL). The mixture was cooled to 0 °C and sodium hydride (3.3 mmol, 60% dispersion in mineral oil) was added in one portion. After the evolution of hydrogen ceased, the appropriate alkyl halide (3.3 mmol) was added in one portion and the reaction was allowed to reach room temperature and stirred for overnight under argon. The reaction was quenched by addition of saturated NH4Cl solution (10 mL), the mixture was extracted with DCM (3×30 mL), the organic layers were collected, dried over MgSO4, filtered, and evaporated. The residue was purified by flash chromatography using chloroform/methanol 15:1 as eluent.

Reference： [1]Location in patent: experimental partStankevič, Marek; Włodarczyk, Adam; Jaklińska, Magdalena; Parcheta, Renata; Pietrusiewicz, K. Michał[Tetrahedron, 2011, vol. 67, # 45, p. 8671 - 8678]
[2]Hoffmann,H.; Schellenbeck,P.[Chemische Berichte, 1966, vol. 99, p. 1134 - 1142]

3
[ 50-00-0 ]
[ 6057-79-0 ]
[ 106649-33-6 ]

Yield	Reaction Conditions	Operation in experiment
83%	With sodium ethanolate In ethanol at 50 - 60℃; for 1h;
78%	With sodium In ethanol for 24h; Inert atmosphere; Schlenk technique; Reflux;
78%	With 1,8-diazabicyclo[5.4.0]undec-7-ene In tetrahydrofuran at 60℃; for 24h; Inert atmosphere; Schlenk technique;	α-Hydroxyphosphine Oxides; General Procedure To a solution of respective secondary phosphine oxide (2.0 mmol) inanhyd THF was added DBU (29 μL, 0.2 mmol) followed by paraformaldehyde (180 mg, 6 mmol). The reaction mixture was heated at 60 °C for 24 h. The mixture was then evaporated to dryness and the residue was dissolved in CH2Cl2 (10 mL) and quenched with sat. aq NH4Cl (5 mL). The resulting mixture was extracted with CH2Cl2 (5 × 30 mL), the combined organic phases were dried (anhyd Na2SO4), and evaporated. The residue was purified by column chromatography on silica gel usingCHCl3/EtOAc/MeOH (30:5:1, v/v/v) as eluent. tert-Butyl(hydroxymethyl)phenylphosphine Oxide. tert-Butylphenylphosphine oxide (0.364 g, 2.0 mmol) was reacted according to the general procedure to afford the title compound (0.33 g,1.56 mmol, 78%) as a beige solid; mp 153.7-154.7 °C; Rf = 0.47(EtOAc-MeOH 10:1). IR (film, ATR): 3161, 2948, 2868, 1475, 1436, 1361, 1218, 1140, 1105,1049, 839, 816, 753, 742, 694, 631, 507, 471, 439 cm-1. 1H NMR (500 MHz, CDCl3): δ = 7.66-7.69 (m, 2 H), 7.40-7.44 (m, 2 H),7.48-7.50 (m, 1 H), 5.47 (br s, 1 H), 4.44 (dd, JP,H = 14.5 Hz, JH,H = 6.94Hz, 1 H), 4.24 (dd, JP,H = 14.19 Hz, JH,H = 6.31 Hz, 1 H), 1.18 (d, JH,P =14.19 Hz, 9 H). 13C NMR (125 MHz, CDCl3): δ = 131.6 (d, JP,C = 2.73 Hz), 131.5 (d, JP,C =7.3 Hz), 128.7 (d, JP,C = 85.4 Hz), 128.2 (d, JP,C = 10.9 Hz), 57.4 (d, JP,C =71.8 Hz), 32.5 (d, JP,C = 64.5 Hz), 24.6. 31P NMR (202 MHz, CDCl3): δ = 46.39 (s). HRMS (ESI-TOF): m/z [M + H]+ calcd for C11H17O2P: 213.1039; found:213.1039.Anal. Calcd for C11H17O2P: C, 62.25; H, 8.07. Found: C, 62.40; H, 8.11.

Reference： [1]Patsanovskii, I. I.; Ishmaeva, E. A.; Sundukova, E. N.; Yarkevich, A. N.; Tsvetkov, E. N.[Journal of general chemistry of the USSR, 1986, vol. 56, # 3, p. 501 - 509][Zhurnal Obshchei Khimii, 1986, vol. 56, # 3, p. 567 - 576]
[2]Sowa, Sylwia; Stankeviç, Marek; Szmigielska, Anna; Małuszyńska, Hanna; Kozioł, Anna E.; Pietrusiewicz, K. Michał[Journal of Organic Chemistry, 2015, vol. 80, # 3, p. 1672 - 1688]
[3]Sowa, Sylwia; Stankevič, Marek; Flis, Anna; Pietrusiewicz, K. Michał[Synthesis, 2018, vol. 50, # 10, p. 2106 - 2118]
[4]Tsvetkov, E. N.; Tkachenko, S. E.; Yarkevich, A. N.[Bulletin de la Societe Chimique de France, 1988, # 2, p. 339 - 341]

4
[ 54100-47-9 ]
[ 6057-79-0 ]

Yield	Reaction Conditions	Operation in experiment
87%	With nickel In ethanol at 15℃; for 3h; ultrasonic irradiation;
87%	With nickel In ethanol at 15 - 20℃; for 3h; Irradiation;
82%	With nickel In ethanol for 10h; Heating;

79%	With nickel In ethanol at 15 - 20℃; for 3h; Irradiation;
	With nickel

Reference： [1]Haynes, Richard K.; Au-Yeung, Tin-Lok; Chan, Wai-Kuen; Lam, Wai-Lun; Li, Zhi-Yi; Yeung, Lam-Lung; Chan, Albert S. C.; Li, Pauline; Koen, Mark; Mitchell, Craig R.; Vonwiller, Simone C.[European Journal of Organic Chemistry, 2000, # 18, p. 3205 - 3216]
[2]Haynes, Richard K.; Freeman, Richard N.; Mitchell, Craig R.; Vonwiller, Simone C.[Journal of Organic Chemistry, 1994, vol. 59, # 11, p. 2919 - 2921]
[3]Kopusinski, A.; Kuczak, L.; Michalski, J.; Kabachnik, M. M.; Moriyama, M.[Tetrahedron, 1981, vol. 37, p. 2011 - 2020]
[4]Haynes, Richard K.; Freeman, Richard N.; Mitchell, Craig R.; Vonwiller, Simone C.[Journal of Organic Chemistry, 1994, vol. 59, # 11, p. 2919 - 2921]
[5]Omelanczuk, Jan; Mikolajczyk, Marian[Journal of the Chemical Society. Chemical communications, 1994, # 19, p. 2223 - 2224]

5
[ 629-09-4 ]
[ 6057-79-0 ]
C₂₆H₄₀O₂P₂ [ No CAS ]

Reference： [1]Tetrahedron Letters,1996,vol. 37,p. 4733 - 4736

6
[ 6057-79-0 ]
[ 128014-09-5 ]

Yield	Reaction Conditions	Operation in experiment
78%	With ethylene dibromide; lithium diisopropyl amide In tetrahydrofuran; hexane at -78℃; for 1h;
69%	With ethylene dibromide; lithium diisopropyl amide In tetrahydrofuran at -78℃; Inert atmosphere;
	With ethylene dibromide; lithium diisopropyl amide In tetrahydrofuran at -78℃; for 3h; Inert atmosphere;

Reference： [1]Haynes, Richard K.; Au-Yeung, Tin-Lok; Chan, Wai-Kuen; Lam, Wai-Lun; Li, Zhi-Yi; Yeung, Lam-Lung; Chan, Albert S. C.; Li, Pauline; Koen, Mark; Mitchell, Craig R.; Vonwiller, Simone C.[European Journal of Organic Chemistry, 2000, # 18, p. 3205 - 3216]
[2]Location in patent: scheme or tableFrancesco, Irene Notar; Wagner, Alain; Colobert, Francoise[Chemical Communications, 2010, vol. 46, # 12, p. 2139 - 2141]
[3]Location in patent: scheme or tableNotar Francesco, Irene; Egloff, Coraline; Wagner, Alain; Colobert, Francoise[European Journal of Organic Chemistry, 2011, # 20-21, p. 4037 - 4045]

7
[ 6057-79-0 ]
[ 6002-31-9 ]

Yield	Reaction Conditions	Operation in experiment
86%	With diisobutylaluminium hydride In tetrahydrofuran at 50℃; for 4h;
86%	With diisobutylaluminium hydride In tert-butyl methyl ether; cyclohexane at 50℃; for 4h; Inert atmosphere; chemoselective reaction;
	With phenylsilane In 1,3,5-trimethyl-benzene at 70℃;

8
[ 2511-09-3 ]
[ 677-22-5 ]
[ 6057-79-0 ]

Yield	Reaction Conditions	Operation in experiment
78%	In tetrahydrofuran at 23℃; for 1h;
78%	In tetrahydrofuran at -10 - 20℃; for 1.66667h; Inert atmosphere;
73%	In tetrahydrofuran at -10℃; Inert atmosphere;

1.7 g	In tetrahydrofuran; 2-methyltetrahydrofuran at 0 - 20℃; for 2.5h; Inert atmosphere;
1.56 g	In tetrahydrofuran at 0 - 20℃; for 2.5h; Inert atmosphere;

Reference： [1]Busacca, Carl A.; Lorenz, Jon C.; Grinberg, Nelu; Haddad, Nizar; Hrapchak, Matt; Latli, Bachir; Lee, Heewon; Sabila, Paul; Saha, Anjan; Sarvestani, Max; Shen, Sherry; Varsolona, Richard; Wei, Xudong; Senanayake, Chris H.[Organic Letters, 2005, vol. 7, # 19, p. 4277 - 4280]
[2]Kumaraswamy, Gullapalli; Raju, Ragam[Advanced Synthesis and Catalysis, 2014, vol. 356, # 11-12, p. 2591 - 2598]
[3]Location in patent: scheme or tableAchard, Thierry; Giordano, Laurent; Tenaglia, Alphonse; Gimbert, Yves; Buono, Gerard[Organometallics, 2010, vol. 29, # 17, p. 3936 - 3950]
[4]Beaud, Rodolphe; Phipps, Robert J.; Gaunt, Matthew J.[Journal of the American Chemical Society, 2016, vol. 138, # 40, p. 13183 - 13186]
[5]Trost, Barry M.; Spohr, Simon M.; Rolka, Alessa B.; Kalnmals, Christopher A.[Journal of the American Chemical Society, 2019, vol. 141, # 36, p. 14098 - 14103]

9
[ 6002-45-5 ]
[ 6057-79-0 ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 2 steps1: 72 percent2: 87 percent / Raney Ni / ethanol / 3 h / 15 °C / ultrasonic irradiation

10
[ 6002-45-5 ]
[ 6057-79-0 ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 2 steps1: 79 percent2: 79 percent / Raney Ni / ethanol / 3 h / 15 °C / Irradiation

11
[ 6057-79-0 ]
[ 54100-47-9 ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 2 steps1: 93 percent / S / toluene / 10 h / Heating2: 72 percent
	Stage #1: tert-Butylphenylphosphine oxide With sulfur; (<i>S</i>)-1-phenyl-ethylamine In diethyl ether at 0℃; Inert atmosphere; Stage #2: With hydrogenchloride; sodium hydroxide In chloroform; water Inert atmosphere;

12
[ 6057-79-0 ]
[ 54100-47-9 ]

Yield	Reaction Conditions	Operation in experiment
82%	With sulfur In tetrahydrofuran at 67℃; for 1.5h;

Reference： [1]Location in patent: experimental partXu, Qing; Zhao, Chang-Qiu; Han, Li-Biao[Journal of the American Chemical Society, 2008, vol. 130, # 38, p. 12648 - 12655]

13
[ 594-19-4 ]
[ 31352-60-0 ]
[ 6057-79-0 ]

Yield	Reaction Conditions	Operation in experiment
95%	In pentane at -80℃; for 14h; Inert atmosphere; optical yield given as %ee;
80%	Stage #1: tert.-butyl lithium; (1R,2S,5R)-2-isopropyl-5-methylcyclohexyl phenylphosphinate In tetrahydrofuran at -78℃; for 2h; Inert atmosphere; Stage #2: With water; ammonium chloride In tetrahydrofuran; diethyl ether at -20℃; Inert atmosphere; optical yield given as %ee; enantioselective reaction;

Reference： [1]Xu, Qing; Zhao, Chang-Qiu; Han, Li-Biao[Journal of the American Chemical Society, 2008, vol. 130, # 38, p. 12648 - 12655]
[2]Gatineau, David; Giordano, Laurent; Buono, Gerard[Journal of the American Chemical Society, 2011, vol. 133, # 28, p. 10728 - 10731]

14
[ 6057-79-0 ]
[ 180208-48-4 ]
[ 1269811-32-6 ]

Yield	Reaction Conditions	Operation in experiment
63%	In tetrahydrofuran at 60℃; for 16h; Inert atmosphere; chemoselective reaction;	Synthesis of 3a, 3b and 3g General procedure: 2b (5 mmol) in THF (100 mL) was added to the solution of 1a or 1b (5 mmol), respectively, in THF (25 mL) at room temperature. After complete addition the reaction mixture was heated at 60 °C for 16 h. Next, a sample of the reaction mixture was taken, DMSO-d6 was added, and the 31P{1H} NMR spectrum was recorded. Subsequently dry air was passed through the reaction mixture at room temperature, for 1a. The volatiles were evaporated and the residue was purified by chromatography and crystallisation.

Reference： [1]Location in patent: experimental partNycz, Jacek E.; Malecki, Grzegorz; Ponikiewski, Lukasz; Leboschka, Markus; Nowak, Maria; Kusz, Joachim[Journal of Molecular Structure, 2011, vol. 986, # 1-3, p. 39 - 48]

15
[ 7136-58-5 ]
[ 6057-79-0 ]
[ 1445236-19-0 ]

Yield	Reaction Conditions	Operation in experiment
85%	Stage #1: tert-Butylphenylphosphine oxide With sodium hydride In tetrahydrofuran; mineral oil at 0℃; for 1h; Inert atmosphere; Stage #2: 2-(3'-thienyl)ethyl chloride In tetrahydrofuran; mineral oil at 0 - 20℃; for 24h;
84.9%	Stage #1: tert-Butylphenylphosphine oxide With sodium hydride In tetrahydrofuran; mineral oil at 0℃; Inert atmosphere; Stage #2: 2-(3'-thienyl)ethyl chloride In tetrahydrofuran; mineral oil at 0 - 20℃; for 24h;	I Example I. Example I. To obtain racemic t-butyl-2-(3'-thienyl)ethyl-phenyl phosphine oxide of Formula 1, the following procedure was used: To a suspension of 50% sodium hydride (0.763 g, 15.90 mmol) in 50 ml of tetrahydrofuran at a temperature of 0 °C in argon atmosphere, a solution of secondary t-butyl-phenyl phosphine oxide (2.633 g, 14.45 mmol) of Formula 2 in 50 ml of tetrahydrofuran was slowly added dropwise and it was left stirring until gaseous hydrogen ceased to evolve. Subsequently, previously distilled off 2-(3'-thienyl)ethyl chloride (2.120 g, 14.45 mmol) was slowly added dropwise to the solution of the resulting sodium salt of t -butyl-phenyl phosphine oxide and the reaction solution was stirred for 3 h at a temperature of 0 °C; subsequently, the reaction mixture was left to reach room temperature and it was stirred for further 21 h. Reaction progress was monitored using 31P NMR spectroscopy. After 24 h, no presence of the sodium salt of the substrate of Formula 2 in the reaction mixture was found. 50 ml of saturated aqueous NH4Cl solution and 50 ml CH2Cl2 was added to the reaction mixture and the liquid was transferred to the separation funnel. The aqueous solution was extracted with three 40 ml portions of dichloromethane. Merged organic layers were washed with brine (1x50 ml) and after separation they were dried over magnesium sulphate. Subsequently, the desiccant was filtered off and the filtrate was evaporated in vacuum. The crude product (3.690 g) was purified by washing with cold hexane, obtaining 3.584 g (yield: 84.9 %) of racemic t-butyl-2-(3'-thienyl)ethyl-phenyl phosphine oxide in the form of white solid.

Reference： [1]Fenyk, Anna; Krasowska, Dorota; Urbaniak, Pawel; Drabowicz, Jozef[Phosphorus, Sulfur and Silicon and the Related Elements, 2013, vol. 188, # 4, p. 473 - 482]
[2]Current Patent Assignee: POLISH ACADEMY OF SCIENCES - EP2639233, 2013, A1Location in patent: Paragraph 0012; 0013; 0014

16
[ 6057-79-0 ]
[ 29949-69-7 ]

Yield	Reaction Conditions	Operation in experiment
94%	With acetyl chloride In tetrahydrofuran at 25℃; Inert atmosphere;	2.1 General procedure A for the synthesis of chlorophosphines 2a to 2e General procedure: To an 10mL oven-dried Schlenk tube under argon atmosphere were added R1R2P(O)H (1.0 mmol) and THF (2.0 mL), stirring the solution until all the solid was totally dissolved, and then MeC(O)Cl (2.0 mmol) was added to the solution and the mixture was stirred at room temperature or 50oC for overnight. After reaction, the excessive MeC(O)Cl, byproduct AcOH and solvent THF were removed under vacuum to afford pure R1R2PCl.
	With phosphorus trichloride In dichloromethane at 20℃; for 1.5h; Inert atmosphere; Schlenk technique;

Reference： [1]Zhang, Jian-Qiu; Yang, Shangdong; Han, Li-Biao[Tetrahedron Letters, 2020, vol. 61, # 10]
[2]Stankevic, Marek; Wlodarczyk, Adam; Nieckarz, Damian[European Journal of Organic Chemistry, 2013, # 20, p. 4351 - 4371]

17
[ 57070-76-5 ]
[ 6057-79-0 ]
[ 1445236-19-0 ]

Yield	Reaction Conditions	Operation in experiment
45%	Stage #1: tert-Butylphenylphosphine oxide With n-butyllithium In tetrahydrofuran; hexane at -78℃; for 1h; Inert atmosphere; Stage #2: 2-(3'-thiophenyl)-1-bromoethane In tetrahydrofuran; hexane at -30 - 20℃; for 24h;	II Example II. Example II. To a stirred solution of secondary t-butyl-phenyl phosphine oxide (0.330 g, 1.81 mmol) in freshly distilled tetrahydrofuran (15 ml) in argon atmosphere, cooled to a temperature of -78°C, a solution of n-butyl lithium in hexane (1.66 ml; C=1.2 mol/l) was added dropwise. The reaction solution was stirred at that temperature for further 1 h; subsequently, it was left to reach a temperature of -30°C and then 2-(3'-thienyl)ethyl bromide (0.346 g, 1.81 mmol) was slowly added dropwise. The reaction mixture was left to reach ambient temperature. Reaction progress was monitored using 31P NMR spectroscopy. The reaction was confirmed to be completed after 24 hours. 50 ml of saturated aqueous NH4Cl solution was added to the reaction mixture which was additionally diluted with a 50 ml portion of CH2Cl2 and the liquid was transferred to the separation funnel and extracted. The organic layer was separated and the aqueous phase left was additionally washed twice with dichloromethane (50 mL each). Merged organic layers were dried over anhydrous MgSO4, filtered and evaporated in vacuum. The crude product (0.299 g) was purified using column chromatography [silica gel, Et2OgCH2Cl2:MeOH (20:1)], to obtain 0.240 g of the product (yield: 45%). The spectroscopic properties of the resulting compound of Formula 1 are as follows: 1H NMR [ppm] (200 MHz, CDCl3) δ = 1.14 (d, 3JP-H=14.50 Hz, 9H, Me3C), 2.23-2.43 (m, 2H, CH2-C3'C3'Thioph), 2.48-2.72 (m, 1H, CH2-P), 2.97-3.16 (m, 1H, CH2-P), 6.91-6.95 (m, 2H, ArC3'Thioph), 7.21-7.24 (m, 1H, ArC3' Thioph), 7.45-7.58 (m, 3H, Ar), 7.69-7.78 (m, 2H, Ar); 31P NMR [ppm] (81 MHz, CDCl3) δ = 48.93; 13C NMR [ppm] (50 MHz, CDCl3) δ = 20.99 (d, J=3.22 Hz, CH2-C3'Tioph), 23.05 (d, J=62.02 Hz, CH2-P), 23.19 (s, CH3C), 31.46 (d, J=68.90 Hz, CH 3C), 119.30 (s, C2'Tioph), 124.52 (s, C5'Tioph), 126.50 (s, C4'Tioph), 127.03 (d, J=10.56 Hz, o-CArx2), 128.51 (d, J=86.05 Hz, ipso-CAr), 130.19 (s, p-CAr), 130.56 (d, J=7.8 Hz, m-CArx2), 140.62 (d, J=14.44 Hz, C3'Tioph ). MS (CI/isobutane): m/z (%): 293.2 (100) [M+1], 585.3 (72.5) [2M+1] HRMS (EI) for C16H21OPS: calc.: 292.10507, determined: 292.10488 Elemental analysis: for C16H21OPS: calc.: C(65.73%), H(7.24%), S(10.97%); determined: C(65.82%), H(7.08%), S(10.95%), IR (KBr) [cm-1]: 3074, 3048 (C-Haryl); 2979, 2933, 2911.2865 (C-Haliph), 1464, 1435 (C-C aliph), 1169.1156 (P=O)strong

Reference： [1]Current Patent Assignee: POLISH ACADEMY OF SCIENCES - EP2639233, 2013, A1Location in patent: Paragraph 0015-0025

18
tert-Butylphenylphosphine oxide [ No CAS ]
[ 501-65-5 ]
1-(tert-butyl)-2,3-diphenyl-1H-phosphindole 1-oxide [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
80%	With silver(l) oxide In acetonitrile at 100℃; for 2h; Inert atmosphere; Microwave irradiation;	4.2. General procedure for the synthesis of 1-alkyl-1H-phoshindole 1-oxides (1-3) or 1-alkoxy-1H-phoshindole 1-oxides (4-16) General procedure: To the mixture of 0.3 mmol of >P(O)H derivatives (diphenylphosphineoxide: 0.061 g, t-butylphenilphosphine oxide: 0.055 g, ethyl phenyl-H-phosphinate: 0.051 g, n-propyl phenyl-H-phosphinate: 0.055 g, i-propyl phenyl-H-phosphinate: 0.055 g, n-butylphenyl-H-phosphinate: 0.059 g, i-butyl phenyl-H-phosphinate: 0.059 g, n-pentyl phenyl-H-phosphinate: 0.064 g, n-octyl phenyl-H-phosphinate: 0.076 g, or adamantyl phenyl-H-phosphinate: 0.083 g) and 0.2 mmol of acetylene (diphenylacetylene: 0.036 g or ethyl phenylpropiolate: 0.033 mL), 0.4 mmol (0.093 g) silver oxide was added 3 mL of acetonitrile and stirred under nitrogen atmosphereat 100-120 °C for 1e3 h in a CEM Microwave reactor (CEM Microwave Technology Ltd., Buckingham, UK) equipped with a pressure controller. The volatile components were removed in vacuum, and the residue was purified by column chromatography using silica gel as the absorbent and hexan:ethylacetate (3:1) as the eluent. The following products were thus prepared:
76%	With silver(l) oxide In N,N-dimethyl-formamide at 100℃; for 12h; Sealed tube; Inert atmosphere;
75%	With 1-ethoxy-2-methylpyridin-1-ium tetrafluoroborate; sodium hydrogencarbonate In N,N-dimethyl-formamide at 20℃; for 24h; Irradiation;

72%	With 1-ethoxy-2-methylpyridin-1-ium tetrafluoroborate; sodium hydrogencarbonate; eosin y In N,N-dimethyl-formamide at 35℃; for 48h; Irradiation; Schlenk technique; Inert atmosphere;
66%	With silver(I) acetate In N,N-dimethyl-formamide at 100℃; for 4h; Inert atmosphere;
55%	With silver(I) acetate In dimethyl sulfoxide at 120℃; for 12h; Inert atmosphere;	1-Ethoxy-2,3-diphenylphosphindole 1-Oxide (3aa); TypicalProcedure General procedure: A suspension of phosphinate 1a (85 mg, 0.50 mmol), diphenylacetylene(2a; 178 mg, 1.00 mmol), AgOAc (167.0 mg, 1.00 mmol) inDMSO (2.0 mL) was stirred under N2 atmosphere at r.t., and then at 120 C for 12 h. At r.t., the reaction mixture was diluted with H2O(10 mL) and extracted with EtOAc (3 ~ 25 mL). The combined organiclayers were dried (Na2SO4). After filtration and evaporationof the solvents in vacuo, the crude product was purified by columnchromatography on silica gel (n-hexane.EtOAc, 5:1 2:1) to afford3aa as an off-white oil; yield: 104 mg (60%).

Reference： [1]Bálint, Erika; Kovács, Botond Dániel; Perdih, Franc; Popovics-Tóth, Nóra; Tajti, Ádám[Tetrahedron, 2021, vol. 102]
[2]Chen, Yun-Rong; Duan, Wei-Liang[Journal of the American Chemical Society, 2013, vol. 135, # 45, p. 16754 - 16757]
[3]Huang, Wei; Byun, Jeehye; Rörich, Irina; Ramanan, Charusheela; Blom, Paul W. M.; Lu, Hao; Wang, Di; Caire da Silva, Lucas; Li, Run; Wang, Lei; Landfester, Katharina; Zhang, Kai A. I.[Angewandte Chemie - International Edition, 2018, vol. 57, # 27, p. 8316 - 8320][Angew. Chem., 2018, vol. 130, # 27, p. 8449 - 8453,5]
[4]Quint, Valentin; Morlet-Savary, Fabrice; Lohier, Jean-François; Lalevée, Jacques; Gaumont, Annie-Claude; Lakhdar, Sami[Journal of the American Chemical Society, 2016, vol. 138, # 23, p. 7436 - 7441]
[5]Unoh, Yuto; Hirano, Koji; Satoh, Tetsuya; Miura, Masahiro[Angewandte Chemie - International Edition, 2013, vol. 52, # 49, p. 12975 - 12979][Angew. Chem., 2013, vol. 52-125, # 49, p. 13213 - 13217]
[6]Ma, Wenbo; Ackermann, Lutz[Synthesis, 2014, vol. 46, # 17, p. 2297 - 2304]

19
[ 533-58-4 ]
[ 6057-79-0 ]
[ 1592979-99-1 ]

Yield	Reaction Conditions	Operation in experiment
94%	With copper(l) iodide; caesium carbonate In toluene at 80℃; for 14h; Inert atmosphere;

Reference： [1]Xiong, Biquan; Li, Mei; Liu, Yanxi; Zhou, Yongbo; Zhao, Changqiu; Goto, Midori; Yin, Shuang-Feng; Han, Li-Biao[Advanced Synthesis and Catalysis, 2014, vol. 356, # 4, p. 781 - 794]

20
[ 4645-32-3 ]
[ 6057-79-0 ]
[ 1803449-84-4 ]

Yield	Reaction Conditions	Operation in experiment
64%	With trimethylphosphane In tetrahydrofuran at 0 - 25℃; for 20.5h; Schlenk technique;	General procedure for PMe₃ catalyzed additionof P(O)-H compounds to vinylphosphorus compounds General procedure: A glass schlenk tube was charged with P(O)-H compounds (1.0 mmol), vinylphosphorus compounds(1.0 mmol) and 1.0 mL solvent. After the tube was cooled in an ice bath, PMe3/THF(1.0mol/L, 0.05 L) was injected into it with a syringe. Stirring the mixture for30 minutes, the ice bath was removed and stirring continued for 20 h at room temperature.The reaction was monitored by 31P NMR. Removal of the solvent andPMe3 under reduce pressure gave a crude product which were purifiedby GPC to get the analytically pure samples

Reference： [1]Saga, Yuta; Han, Daoqing; Kawaguchi, Shin-Ichi; Ogawa, Akiya; Han, Li-Biao[Tetrahedron Letters, 2015, vol. 56, # 38, p. 5303 - 5305]

21
[ 31599-61-8 ]
tert-Butylphenylphosphine oxide [ No CAS ]
t-butylphenyl(3,4-dimethylphenyl)phosphine oxide [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
94%	With copper(l) iodide; potassium carbonate; rac-methylbenzylamine In toluene for 24h; Inert atmosphere; Schlenk technique; Reflux;	4.3. The synthesis of 15b and 15e through copper-catalyzed coupling with aryl iodides General procedure: In the flame-dried Schlenk flask (50 mL), equipped with magnetic stirrer and inert gas inlet secondary phosphine oxide 18 (0.546 g, 0.003 mol) was dissolved in toluene (5 mL). Then, aryl iodide (3,4-dimethyliodobenzene (0.696 g, 0.426 mL, 0.003 mol) or 4-iodotoluene (0.655 g, 0.003 mol)) was added, followed by CuI (0.057 g, 0.300 mmol), α-phenylethylamine (0.073 g, 0.077 mL, 0.600 mmol) and K2CO3 (0.829 g, 0.006 mmol). The mixture was heated at reflux for 24 h, then cooled to room temperature. Saturated NH4Cl solution (15 mL) was then added and the mixture was extracted with CHCl3 (3×40 mL). The organic phase was dried over MgSO4 and evaporated and the residue was purified by flash chromatography using CHCl3:MeOH 50:1 as eluent yielding 15b (0.808 g, 94%) as white solid or 15e (0.727 g, 89%) as pale yellow solid.

Reference： [1]Stankevič, Marek; Pisklak, Jolanta; Włodarczyk, Katarzyna[Tetrahedron, 2016, vol. 72, # 6, p. 810 - 824]

22
[ 624-31-7 ]
[ 6057-79-0 ]
[ 1852544-17-2 ]

Yield	Reaction Conditions	Operation in experiment
89%	With copper(l) iodide; potassium carbonate; rac-methylbenzylamine In toluene for 24h; Inert atmosphere; Schlenk technique; Reflux;	4.3. The synthesis of 15b and 15e through copper-catalyzed coupling with aryl iodides General procedure: In the flame-dried Schlenk flask (50 mL), equipped with magnetic stirrer and inert gas inlet secondary phosphine oxide 18 (0.546 g, 0.003 mol) was dissolved in toluene (5 mL). Then, aryl iodide (3,4-dimethyliodobenzene (0.696 g, 0.426 mL, 0.003 mol) or 4-iodotoluene (0.655 g, 0.003 mol)) was added, followed by CuI (0.057 g, 0.300 mmol), α-phenylethylamine (0.073 g, 0.077 mL, 0.600 mmol) and K2CO3 (0.829 g, 0.006 mmol). The mixture was heated at reflux for 24 h, then cooled to room temperature. Saturated NH4Cl solution (15 mL) was then added and the mixture was extracted with CHCl3 (3×40 mL). The organic phase was dried over MgSO4 and evaporated and the residue was purified by flash chromatography using CHCl3:MeOH 50:1 as eluent yielding 15b (0.808 g, 94%) as white solid or 15e (0.727 g, 89%) as pale yellow solid.

Reference： [1]Stankevič, Marek; Pisklak, Jolanta; Włodarczyk, Katarzyna[Tetrahedron, 2016, vol. 72, # 6, p. 810 - 824]

23
[ 2398-37-0 ]
[ 6057-79-0 ]
[ 1852544-18-3 ]

Yield	Reaction Conditions	Operation in experiment
99%	With bis-triphenylphosphine-palladium(II) chloride; caesium carbonate In toluene for 24h; Inert atmosphere; Schlenk technique; Reflux;	4.4. The synthesis of 15f and 15g through palladium-catalyzed coupling with 3-bromoanizole General procedure: In the flame-dried Schlenk flask (50 mL), equipped with magnetic stirrer and inert gas inlet secondary phosphine oxide 18 (0.546 g, 0.003 mol) or 19 (0.589 g, 0.003 mol) was dissolved in toluene (5 mL). Then, 3-bromoanizole (0.561 g, 0.380 mL, 0.003 mol) was added, followed by (Ph3P)2PdCl2 (0.105 g, 0.150 mmol) and Cs2CO3 (1.955 g, 0.006 mmol). The mixture was heated at reflux for 24 h, then cooled to room temperature. Saturated NH4Cl solution (15 mL) was then added and the mixture was extracted with CHCl3 (3×40 mL). The organic phase was dried over MgSO4 and evaporated and the residue was purified by flash chromatography using CHCl3:MeOH 50:1 as eluent yielding 15f (0.856 g, 99%) as yellow oil or 15g (0.535 g, 59%) as yellow oil.

Reference： [1]Stankevič, Marek; Pisklak, Jolanta; Włodarczyk, Katarzyna[Tetrahedron, 2016, vol. 72, # 6, p. 810 - 824]

24
[ 17763-67-6 ]
tert-Butylphenylphosphine oxide [ No CAS ]
[ 56598-35-7 ]

Yield	Reaction Conditions	Operation in experiment
78%	With 1,1'-bis-(diphenylphosphino)ferrocene; bis(1,5-cyclooctadiene)nickel ⁽⁰⁾; sodium carbonate In 1,4-dioxane at 100℃; for 20h; Inert atmosphere;	h 4.3. Typical procedure for the nickel-catalyzed phosphorylation of aryl triflates with P(O)-H compounds General procedure: Under a N2 atmosphere, 0.2 mmol aryl triflate 1a, 0.2 mmol Ph2P(O)H 2a,10 mol% Ni(COD)2, 10 mol% dppf,1.0 equiv Na2CO3 and 2 mL dioxane were charged into a 10 mL schlenck tube. The mixturewas stirred at 80 °C for 20 h. After removal of the volatile, the residues were passed through a short silica chromatography (particlesize 37-54 mm, petroleum ether/ethyl acetate as eluent) toafford analytically pure organophosphorus compounds 3. Purification by chromatography (petroleum ether/EtOAc = 1:2) afforded 3m (40.2 mg, 78%) as a white solid. Rf = 0.60 (EtOAc); 1H NMR (400 MHz CDCl3): δ 7.96 (dd, J = 8.4 Hz, J = 8.4 Hz, 4H), 7.55-7.46 (m, 6H), 1.25 (d, J = 14.8 Hz, 9H). 13C NMR (100 MHz CDCl3): δ 132.20 (d, JC-P = 8.1 Hz), 131.49 (d, JC-P = 2.7 Hz), 131.17 (d, JC-P = 89.9 Hz), 128.28 (d, JC-P = 10.9 Hz), 33.97 (d, JC-P = 70.4 Hz), 25.21. 31P NMR (162 MHz CDCl3): δ 38.77 ppm.

Reference： [1]Yang, Jia; Xiao, Jing; Chen, Tieqiao; Han, Li-Biao[Journal of Organometallic Chemistry, 2016, vol. 820, p. 120 - 124]

25
[ 4645-32-3 ]
[ 6057-79-0 ]
[ 2052590-97-1 ]

Yield	Reaction Conditions	Operation in experiment
55%	With trimethylphosphane In tetrahydrofuran at 20℃; Schlenk technique; Cooling with ice; stereoselective reaction;	1 General procedure for the PMe3-catalyzed addition of P(O)H compounds to vinylphosphorus compounds General procedure: A glass schlenk tube was charged with P(O)H compounds(0.5 mmol), vinylphosphorus compounds (0.5 mmol), and 0.5 mLof solvent. After the tube was cooled in an ice bath, PMe3/THF(1.0 mol/L, 25 lL) was injected into the system with a syringe.After the mixture was stirred for 30 min, the ice bath was removed.Stirring was then continued for 20 h at room temperature. Thereaction was monitored by 31P NMR. Removal of the solvent and PMe3 under reduced pressure gave a crude product. The adductswere isolated by GPC to afford analytically pure samples.

Reference： [1]Saga, Yuta; Mino, Yuka; Kawaguchi, Shin-ichi; Han, Daoqing; Ogawa, Akiya; Han, Li-Biao[Tetrahedron Asymmetry, 2017, vol. 28, # 1, p. 84 - 89]

26
[ 6057-79-0 ]
[ 29176-55-4 ]
[ CAS Unavailable ]
[ CAS Unavailable ]

Yield	Reaction Conditions	Operation in experiment
71%	With 1,1'-bis-(diphenylphosphino)ferrocene; palladium diacetate; potassium carbonate In N,N-dimethyl-formamide at 80℃; for 7h; Schlenk technique; Inert atmosphere;	General Procedure for preparative synthesis of 3a-3d. General procedure: Oven-dried Schlenk flask was evacuated and backfilled with argon three times. In the stream of argon heteroaryl dichloride (1 eq), K2CO3 (3 eq) were placed thereto. Secondary phosphine oxide (2.4 eq) was dissolved in DMF (15 ml/mmol) and the solution was added to the flask. The solution was bubbled with argon for 10 min and Pd(OAc)2 (0.02 eq) and dppf (0.04 eq) were added to the flask simultaneously. The resulting mixture was heated at 80oC for 7 h and then poured into fourfold excess of brine. The mixture was extracted with CH2Cl2 three times (40 ml/mmol each). Combined organic extracts were washed with brine to remove traces of DMF, dried over anhydrous Na2SO4 and then evaporated to dryness. The residue was purified by column chromatography on silica gel 40-60 using CH2Cl2-MeOH mixture as eluent.

Reference： [1]Zakirova, Gladis G.; Mladentsev, Dmitrii Yu.; Borisova, Nataliya E.[Tetrahedron Letters, 2017, vol. 58, # 35, p. 3415 - 3417]

27
[ 98976-30-8 ]
[ 53344-72-2 ]
[2,2'-bipyridine]-6,6'-diylbis(tert-butyl(phenyl)phosphine oxide) [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
77%	With 1,1'-bis-(diphenylphosphino)ferrocene; palladium diacetate; potassium carbonate; In N,N-dimethyl-formamide; at 80℃; for 7h;Schlenk technique; Inert atmosphere;	General procedure: Oven-dried Schlenk flask was evacuated and backfilled with argon three times. In the stream of argon heteroaryl dichloride (1 eq), K2CO3 (3 eq) were placed thereto. Secondary phosphine oxide (2.4 eq) was dissolved in DMF (15 ml/mmol) and the solution was added to the flask. The solution was bubbled with argon for 10 min and Pd(OAc)2 (0.02 eq) and dppf (0.04 eq) were added to the flask simultaneously. The resulting mixture was heated at 80oC for 7 h and then poured into fourfold excess of brine. The mixture was extracted with CH2Cl2 three times (40 ml/mmol each). Combined organic extracts were washed with brine to remove traces of DMF, dried over anhydrous Na2SO4 and then evaporated to dryness. The residue was purified by column chromatography on silica gel 40-60 using CH2Cl2-MeOH mixture as eluent.

Reference： [1]Tetrahedron Letters,2017,vol. 58,p. 3415 - 3417

28
[ 2402-78-0 ]
[ 6057-79-0 ]
[ 2098084-81-0 ]

Yield	Reaction Conditions	Operation in experiment
72%	With 1,1'-bis-(diphenylphosphino)ferrocene; palladium diacetate; potassium carbonate In N,N-dimethyl-formamide at 120℃; for 7h; Schlenk technique; Inert atmosphere;	General Procedure for preparative synthesis of 3a-3d. General procedure: Oven-dried Schlenk flask was evacuated and backfilled with argon three times. In the stream of argon heteroaryl dichloride (1 eq), K2CO3 (3 eq) were placed thereto. Secondary phosphine oxide (2.4 eq) was dissolved in DMF (15 ml/mmol) and the solution was added to the flask. The solution was bubbled with argon for 10 min and Pd(OAc)2 (0.02 eq) and dppf (0.04 eq) were added to the flask simultaneously. The resulting mixture was heated at 80oC for 7 h and then poured into fourfold excess of brine. The mixture was extracted with CH2Cl2 three times (40 ml/mmol each). Combined organic extracts were washed with brine to remove traces of DMF, dried over anhydrous Na2SO4 and then evaporated to dryness. The residue was purified by column chromatography on silica gel 40-60 using CH2Cl2-MeOH mixture as eluent.

Reference： [1]Zakirova, Gladis G.; Mladentsev, Dmitrii Yu.; Borisova, Nataliya E.[Tetrahedron Letters, 2017, vol. 58, # 35, p. 3415 - 3417]

29
[ 6057-79-0 ]
[ 536-74-3 ]
[ 2486250-95-5 ]

Yield	Reaction Conditions	Operation in experiment
75%	With tris-(dibenzylideneacetone)dipalladium⁽⁰⁾; water; C₃₆H₄₄NOPS In 1,2-dichloro-ethane at 35℃; for 12h; Sealed tube; Inert atmosphere; enantioselective reaction;

Reference： [1]Dai, Qiang; Li, Wenbo; Liu, Lu; Qian, Yanyan; Zhang, Junliang[Angewandte Chemie - International Edition, 2020, vol. 59, # 46, p. 20645 - 20650][Angew. Chem., 2020, vol. 132, # 46, p. 20826 - 20831,6]

30
[ 772-38-3 ]
[ 6057-79-0 ]
[ 2486251-00-5 ]

Yield	Reaction Conditions	Operation in experiment
81%	With tris-(dibenzylideneacetone)dipalladium⁽⁰⁾; water; C₃₆H₄₄NOPS In 1,2-dichloro-ethane at 35℃; for 12h; Sealed tube; Inert atmosphere; enantioselective reaction;

31
[ 14235-81-5 ]
[ 6057-79-0 ]
[ 2486251-02-7 ]

Yield	Reaction Conditions	Operation in experiment
77%	With tris-(dibenzylideneacetone)dipalladium⁽⁰⁾; water; C₃₆H₄₄NOPS In 1,2-dichloro-ethane at 35℃; for 12h; Sealed tube; Inert atmosphere; enantioselective reaction;

32
[ 705-31-7 ]
[ 6057-79-0 ]
[ 2486251-07-2 ]

Yield	Reaction Conditions	Operation in experiment
78%	With tris-(dibenzylideneacetone)dipalladium⁽⁰⁾; water; C₃₆H₄₄NOPS In 1,2-dichloro-ethane at 35℃; for 12h; Sealed tube; Inert atmosphere; enantioselective reaction;

33
[ 10401-11-3 ]
[ 6057-79-0 ]
[ 2486251-11-8 ]

Yield	Reaction Conditions	Operation in experiment
76%	With tris-(dibenzylideneacetone)dipalladium⁽⁰⁾; water; C₃₆H₄₄NOPS In 1,2-dichloro-ethane at 35℃; for 12h; Sealed tube; Inert atmosphere; enantioselective reaction;

34
[ 766-83-6 ]
[ 6057-79-0 ]
[ 2486251-12-9 ]

Yield	Reaction Conditions	Operation in experiment
76%	With tris-(dibenzylideneacetone)dipalladium⁽⁰⁾; water; C₃₆H₄₄NOPS In 1,2-dichloro-ethane at 35℃; for 12h; Sealed tube; Inert atmosphere; enantioselective reaction;

35
[ 1945-84-2 ]
[ 6057-79-0 ]
[ 2486251-18-5 ]

Yield	Reaction Conditions	Operation in experiment
80%	With tris-(dibenzylideneacetone)dipalladium⁽⁰⁾; water; C₃₆H₄₄NOPS In 1,2-dichloro-ethane at 35℃; for 12h; Sealed tube; Inert atmosphere; enantioselective reaction;

36
[ 2510-23-8 ]
[ 6057-79-0 ]
[ 2486251-19-6 ]

Yield	Reaction Conditions	Operation in experiment
76%	With tris-(dibenzylideneacetone)dipalladium⁽⁰⁾; water; C₃₆H₄₄NOPS In 1,2-dichloro-ethane at 35℃; for 12h; Sealed tube; Inert atmosphere; enantioselective reaction;

37
[ 1271-47-2 ]
[ 6057-79-0 ]
[ CAS Unavailable ]

Yield	Reaction Conditions	Operation in experiment
75%	With tris-(dibenzylideneacetone)dipalladium⁽⁰⁾; water; C₃₆H₄₄NOPS In 1,2-dichloro-ethane at 35℃; for 12h; Sealed tube; Inert atmosphere; enantioselective reaction;

38
[ 6057-79-0 ]
[ 79-11-8 ]
[ 1448512-65-9 ]

Yield	Reaction Conditions	Operation in experiment
76%	With potassium hydroxide In water; dimethyl sulfoxide at 40 - 60℃; for 1h;	Phosphinoylacetic Acids 2a-d; General Procedure General procedure: To a stirred solution of the secondary phosphine oxide 1a-d (22 mmol) and chloroacetic acid (2.27 g, 24 mmol) in DMSO (12 mL) was added dropwise a 56% aq KOH solution (5.6 ml, 57 mmol) at r.t. After heating for 1 h at 40-60 °C, the mixture was diluted with H2O. The aqueous solution was acidified with dil HCl and the crude mixture was extracted with CHCl3. The combined CHCl3 extracts were dried (MgSO4), filtered, and evaporated under vacuum. The residue was crystallized from MeCN.

Reference： [1]Dziuba, Kamil; Frynas, Sławomir; Szwaczko, Katarzyna[Synthesis, 2021, vol. 53, # 12, p. 2142 - 2154]

39
[ 6057-79-0 ]
[ CAS Unavailable ]
[ CAS Unavailable ]

Yield	Reaction Conditions	Operation in experiment
53%	With (1,2-dimethoxyethane)dichloronickel(II); tetra-(n-butyl)ammonium iodide; tris<3,5-bis(trifluoromethyl)phenyl>phosphane; N,N,N',N'-tetramethylguanidine In N,N-dimethyl acetamide at 110℃; for 12h; Electrolysis; Inert atmosphere;	1.2.2 General procedure for nickela-electro-catalyzed C-H phosphorylation General procedure: The electrolysis was carried out in an undivided cell, with a graphite felt (GF) anode (10 mm × 15 mm × 6 mm) and a nickel foam (Ni) cathode (10 mm × 15 mm × 1.4 mm). Amide 1 or 1’ (0.25 mmol, 1.0 equiv), Ni(DME)Cl2 (5.5 mg, 0.025 mmol, 10 mol %), [3,5-(CF3)2C6H3]3P (33.5 mg, 0.050 mmol, 20 mol %), 1,1,3,3-Tetramethylguanidine (TMG) (28.8 mg, 0.25 mmol, 1.0 equiv), nBu4NI (0.125 mmol) and phosphonating reagents 2 were dissolved in DMA (3.0 mL). Electrolysis was conducted with a constant current of 8.0 mA which was maintained at 110 °C for 12 h under N2. At ambient temperature, the mixture was transferred to a separating funnel and the electrodes were rinsed with EtOAc (10 mL). Subsequently, H2O (10 mL) was added to the mixture and the organic layer was collected. The aqueous layer was extracted with EtOAc (2 × 5.0 mL). Evaporation of the combined organic layers and subsequent column chromatography on silica gel (eluent: nhexane/EtOAc) yielded the desired product.

Reference： [1]Zhang, Shou-Kun; Del Vecchio, Antonio; Kuniyil, Rositha; Messinis, Antonis M.; Lin, Zhipeng; Ackermann, Lutz[Chem, 2021, vol. 7, # 5, p. 1379 - 1392]

40
[ 6057-79-0 ]
[ 97802-65-8 ]
[ 6057-79-0 ]
[ 6057-79-0 ]
[ 2756612-22-1 ]

Yield	Reaction Conditions	Operation in experiment
1: 50%2: 43%	With rubidium carbonate; tris-(dibenzylideneacetone)dipalladium⁽⁰⁾; C₃₆H₄₄NOPS In acetonitrile at 55℃; for 14h; Inert atmosphere;	17 Experimental procedure General procedure: In a sealed tube with a volume of 15mL, put in: (dibenzylideneacetone)palladium (0.01mmol, 5mol%), (S,RS)-X6 (0,03mmol, 15mol%). Connect a double-row tube, pump three times under argon, and add racemic secondary phosphine I-1 (0.4 mmol), alkylating reagent II-2 (0.2 mmol), carbonic acid while maintaining ventilation Rubidium (0.44 mmol) and acetonitrile (2.0 mL). The reaction system was closed, and the reaction solution was reacted at 55°C. After the reaction is completed, the reaction system is filtered through a small amount of silica gel and concentrated, and the obtained concentrate can be separated and purified to obtain the target compound III-1 and the target compound IV-1, respectively.
1: 43%2: 69 % ee	With rubidium carbonate; tris-(dibenzylideneacetone)dipalladium⁽⁰⁾; C₃₆H₄₄NOPS In acetonitrile at 55℃; for 14h; Sealed tube; Inert atmosphere; enantioselective reaction;

Reference： [1]Current Patent Assignee: FUDAN UNIVERSITY; EAST CHINA NORMAL UNIVERSITY - CN113861238, 2021, ALocation in patent: Paragraph 0040-0044; 0082-0090
[2]Dai, Qiang; Liu, Lu; Zhang, Junliang[Angewandte Chemie - International Edition, 2021, vol. 60, # 52, p. 27247 - 27252][Angew. Chem., 2021, vol. 133, # 52, p. 27453 - 27458]

41
[ 7145-06-4 ]
[ 6057-79-0 ]
[ 6057-79-0 ]
[ 2756612-23-2 ]

Yield	Reaction Conditions	Operation in experiment
1: 42%2: 38%	With rubidium carbonate; tris-(dibenzylideneacetone)dipalladium⁽⁰⁾; C₃₆H₄₄NOPS In acetonitrile at 55℃; for 40h; Sealed tube; Inert atmosphere; enantioselective reaction;
1: 38%2: 42%	With rubidium carbonate; tris-(dibenzylideneacetone)dipalladium⁽⁰⁾; C₃₆H₄₄NOPS In acetonitrile at 55℃; for 40h; Inert atmosphere;	18 Experimental procedure General procedure: In a sealed tube with a volume of 15mL, put in: (dibenzylideneacetone)palladium (0.01mmol, 5mol%), (S,RS)-X6 (0,03mmol, 15mol%). Connect a double-row tube, pump three times under argon, and add racemic secondary phosphine I-1 (0.4 mmol), alkylating reagent II-2 (0.2 mmol), carbonic acid while maintaining ventilation Rubidium (0.44 mmol) and acetonitrile (2.0 mL). The reaction system was closed, and the reaction solution was reacted at 55°C. After the reaction is completed, the reaction system is filtered through a small amount of silica gel and concentrated, and the obtained concentrate can be separated and purified to obtain the target compound III-1 and the target compound IV-1, respectively.

Reference： [1]Dai, Qiang; Liu, Lu; Zhang, Junliang[Angewandte Chemie - International Edition, 2021, vol. 60, # 52, p. 27247 - 27252][Angew. Chem., 2021, vol. 133, # 52, p. 27453 - 27458]
[2]Current Patent Assignee: FUDAN UNIVERSITY; EAST CHINA NORMAL UNIVERSITY - CN113861238, 2021, ALocation in patent: Paragraph 0040-0044; 0082-0090

42
[ 6057-79-0 ]
[ 49640-94-0 ]
[ 6057-79-0 ]
[ 2756612-24-3 ]

Yield	Reaction Conditions	Operation in experiment
1: 43%2: 39%	With rubidium carbonate; tris-(dibenzylideneacetone)dipalladium⁽⁰⁾; C₃₆H₄₄NOPS In acetonitrile at 55℃; for 46h; Sealed tube; Inert atmosphere; enantioselective reaction;
1: 39%2: 43%	With rubidium carbonate; tris-(dibenzylideneacetone)dipalladium⁽⁰⁾; C₃₆H₄₄NOPS In acetonitrile at 55℃; for 46h; Inert atmosphere;	19 Experimental procedure General procedure: In a sealed tube with a volume of 15mL, put in: (dibenzylideneacetone)palladium (0.01mmol, 5mol%), (S,RS)-X6 (0,03mmol, 15mol%). Connect a double-row tube, pump three times under argon, and add racemic secondary phosphine I-1 (0.4 mmol), alkylating reagent II-2 (0.2 mmol), carbonic acid while maintaining ventilation Rubidium (0.44 mmol) and acetonitrile (2.0 mL). The reaction system was closed, and the reaction solution was reacted at 55°C. After the reaction is completed, the reaction system is filtered through a small amount of silica gel and concentrated, and the obtained concentrate can be separated and purified to obtain the target compound III-1 and the target compound IV-1, respectively.

43
[ 1640017-45-3 ]
[ 6057-79-0 ]
[ 6057-79-0 ]
[ 2756612-25-4 ]

Yield	Reaction Conditions	Operation in experiment
1: 45%2: 36%	With rubidium carbonate; tris-(dibenzylideneacetone)dipalladium⁽⁰⁾; C₃₆H₄₄NOPS In acetonitrile at 55℃; for 26h; Sealed tube; Inert atmosphere; enantioselective reaction;
1: 36%2: 45%	With rubidium carbonate; tris-(dibenzylideneacetone)dipalladium⁽⁰⁾; C₃₆H₄₄NOPS In acetonitrile at 55℃; for 26h; Inert atmosphere;	20 Experimental procedure General procedure: In a sealed tube with a volume of 15mL, put in: (dibenzylideneacetone)palladium (0.01mmol, 5mol%), (S,RS)-X6 (0,03mmol, 15mol%). Connect a double-row tube, pump three times under argon, and add racemic secondary phosphine I-1 (0.4 mmol), alkylating reagent II-2 (0.2 mmol), carbonic acid while maintaining ventilation Rubidium (0.44 mmol) and acetonitrile (2.0 mL). The reaction system was closed, and the reaction solution was reacted at 55°C. After the reaction is completed, the reaction system is filtered through a small amount of silica gel and concentrated, and the obtained concentrate can be separated and purified to obtain the target compound III-1 and the target compound IV-1, respectively.

44
[ 6057-79-0 ]
[ 1805782-92-6 ]
[ 6057-79-0 ]
[ CAS Unavailable ]

Yield	Reaction Conditions	Operation in experiment
1: 42%2: 40%	With rubidium carbonate; tris-(dibenzylideneacetone)dipalladium⁽⁰⁾; C₃₆H₄₄NOPS In acetonitrile at 55℃; for 22h; Sealed tube; Inert atmosphere; enantioselective reaction;
1: 40%2: 42%	With rubidium carbonate; tris-(dibenzylideneacetone)dipalladium⁽⁰⁾; C₃₆H₄₄NOPS In acetonitrile at 55℃; for 22h; Inert atmosphere;	21 Experimental procedure General procedure: In a sealed tube with a volume of 15mL, put in: (dibenzylideneacetone)palladium (0.01mmol, 5mol%), (S,RS)-X6 (0,03mmol, 15mol%). Connect a double-row tube, pump three times under argon, and add racemic secondary phosphine I-1 (0.4 mmol), alkylating reagent II-2 (0.2 mmol), carbonic acid while maintaining ventilation Rubidium (0.44 mmol) and acetonitrile (2.0 mL). The reaction system was closed, and the reaction solution was reacted at 55°C. After the reaction is completed, the reaction system is filtered through a small amount of silica gel and concentrated, and the obtained concentrate can be separated and purified to obtain the target compound III-1 and the target compound IV-1, respectively.

45
[ 6057-79-0 ]
[ 128732-38-7 ]
[ 6057-79-0 ]
[ 6057-79-0 ]
[ 2756612-27-6 ]

Yield	Reaction Conditions	Operation in experiment
1: 42%2: 83 % ee	With rubidium carbonate; tris-(dibenzylideneacetone)dipalladium⁽⁰⁾; C₃₆H₄₄NOPS In acetonitrile at 55℃; for 14h; Sealed tube; Inert atmosphere; enantioselective reaction;
1: 42%2: 42%	With rubidium carbonate; tris-(dibenzylideneacetone)dipalladium⁽⁰⁾; C₃₆H₄₄NOPS In acetonitrile at 55℃; for 14h; Inert atmosphere;	22 Experimental procedure General procedure: In a sealed tube with a volume of 15mL, put in: (dibenzylideneacetone)palladium (0.01mmol, 5mol%), (S,RS)-X6 (0,03mmol, 15mol%). Connect a double-row tube, pump three times under argon, and add racemic secondary phosphine I-1 (0.4 mmol), alkylating reagent II-2 (0.2 mmol), carbonic acid while maintaining ventilation Rubidium (0.44 mmol) and acetonitrile (2.0 mL). The reaction system was closed, and the reaction solution was reacted at 55°C. After the reaction is completed, the reaction system is filtered through a small amount of silica gel and concentrated, and the obtained concentrate can be separated and purified to obtain the target compound III-1 and the target compound IV-1, respectively.

46
[ 6057-79-0 ]
[ 169172-48-9 ]
[ 6057-79-0 ]
[ 2756612-28-7 ]

Yield	Reaction Conditions	Operation in experiment
1: 93%2: 36%	With rubidium carbonate; tris-(dibenzylideneacetone)dipalladium⁽⁰⁾; C₃₉H₅₀NOPS In acetonitrile at 55℃; for 114h; Inert atmosphere;	23 Experimental procedure General procedure: In a sealed tube with a volume of 15mL, put in: (dibenzylideneacetone)palladium (0.01mmol, 5mol%), (S,RS)-X6 (0,03mmol, 15mol%). Connect a double-row tube, pump three times under argon, and add racemic secondary phosphine I-1 (0.4 mmol), alkylating reagent II-2 (0.2 mmol), carbonic acid while maintaining ventilation Rubidium (0.44 mmol) and acetonitrile (2.0 mL). The reaction system was closed, and the reaction solution was reacted at 55°C. After the reaction is completed, the reaction system is filtered through a small amount of silica gel and concentrated, and the obtained concentrate can be separated and purified to obtain the target compound III-1 and the target compound IV-1, respectively.
1: 36%2: 36%	With rubidium carbonate; tris-(dibenzylideneacetone)dipalladium⁽⁰⁾; C₃₉H₅₀NOPS In acetonitrile at 55℃; for 114h; Sealed tube; Inert atmosphere; enantioselective reaction;