September 2020 | Chiral nitrogen ligands

The important role of 33527-91-2

Chemical properties determine the actual use. Each compound has specific chemical properties and uses. We look forward to more synthetic routes in the future to expand reaction routes of Tris[2-(dimethylamino)ethyl]amine, 33527-91-2

33527-91-2, In the next few decades, the world population will flourish. As the population grows rapidly and people all over the world use more and more resources, all industries must consider their environmental impact.33527-91-2, Tris[2-(dimethylamino)ethyl]amine it is a common compound, a new synthetic route is introduced below.

To a mixture of Cu(NO3)22.5H2O (0.504 g, 2.17 mmol) in MeOH(15.0 mL), was added tris[2-(dimethylamino)ethyl]amine (L4)(0.500 g, 2.17 mmol) and stirred at RT. The blue solution was evaporatedunder reduced pressure to afford a yellow solid. The solidwas dissolved again in MeOH and diffused with diethyl ether. Suitableblue block-shaped crystals were obtained in 2 days. Yield(0.921 g, 98%).

Reference£º
Article; Sivanesan, Dharmalingam; Seo, Bongkuk; Lim, Choong-Sun; Kim, Hyeon-Gook; Journal of Catalysis; vol. 382; (2020); p. 121 – 128;,
Chiral nitrogen ligands in late transition metal-catalysed asymmetric synthesis¡ªI. Addressing the problem of ligand lability in rhodium-catalysed hydrosilations
Nitrogen-Containing Ligands for Asymmetric Homogeneous and Heterogeneous Catalysis

Analyzing the synthesis route of 110-70-3

110-70-3, In the next few decades, the world population will flourish. As the population grows rapidly and people all over the world use more and more resources, all industries must consider their environmental impact.110-70-3, N1,N2-Dimethylethane-1,2-diamine it is a common compound, a new synthetic route is introduced below.

To a solution of N,N?-dimethylethane-1,2-diamine (40.4 g) in DCM (300 mL) was added a solution of Boc2O (10 g, 10.6 mL, 45.8 mmol) in DCM (100 mL) dropwise at 0 C over 1 hr. The reaction mixture was stirred at room temperature for 18 hrs. The organic layer was washed with saturated aqueous NaHCO3 (50 mL), brine (50 mL), dried overNa2SO4 and concentrated in vacuo. The residue was purified by column chromatography toafford tert-butyl N-methyl-N- [2-(methylamino)ethyl]carbamate (6.8 g, Compound BC-i)as a yellow oil. 1H NMR (400MHz, CDCl3) 5 ppm: 3.34 (br. s., 2H), 2.89 (s, 3H), 2.74 (t, J= 6.7 Hz, 2H), 2.46 (s, 3H), 1.47 (s, 9H).

Reference£º
Patent; F. HOFFMANN-LA ROCHE AG; HOFFMANN-LA ROCHE INC.; POESCHINGER, Thomas; RIES, Carola; SHEN, Hong; YUN, Hongying; HOVES, Sabine; HAGE, Carina; (224 pag.)WO2019/166432; (2019); A1;,
Chiral nitrogen ligands in late transition metal-catalysed asymmetric synthesis¡ªI. Addressing the problem of ligand lability in rhodium-catalysed hydrosilations
Nitrogen-Containing Ligands for Asymmetric Homogeneous and Heterogeneous Catalysis

Some tips on N1,N2-Dimethylethane-1,2-diamine

To a solution of N,N’-dimethylethylenediamine (1.61 gram, 18.26 mmol) in methanol (20 mL) was added dropwise a solution of 2-pyridinecarboxaldehyde (1.96 gram, 18.29 mmol) in methanol (10 mL). The reaction mixture was stirred at room temperature for 1 hour forming an orange solution. NaCNBH3 (3.5 grams, 55.7 mmol) was added followed by addition of trifluoroacetic acid (5 mL), and the solution was stirred for additional 3 hours. After neutralization with NaOH 4M solution, the crude product was extracted with 3 portions of dichloromethane (30 mL). The collected organic layer was dried over Na2S04 and solvent was removed under vacuum yielding a yellow oil in 95 % yield. (0466) 1H NMR (CDC13, 500 MHz): delta 8.54 (ddd, 1H, J=4.85Hz, J=1.85Hz, J=0.85Hz, ArH), 7.65 (td, 1H, J=7.65Hz, J=1.82Hz, ArH), 7.40 (d, 1H, J=7.84Hz, ArH), 7.16 (ddd, 1H, J=7.65Hz, J=4.80Hz, J=1.0Hz, ArH), 3.67 (s, 2H, Ar-CH2), 2.70 (t, 2H, J=6.25Hz, CH2), 2.60 (t, 2H, J=6.16Hz, CH2), 2.42 (s, 3H, CH3), 2.28 (s, 3H, CH3). (0467) 13C NMR (CDC13, 125 MHz): delta 159.61 (C), 149.25 (CH), 136.60 (CH), 123.13 (CH), 122.14 (CH), 64.26 (CH2), 56.97 (CH2), 49.44 (CH2), 42.81 (CH3), 36.50 (CH3). (0468) MS (ESI): Calc for Ci0Hi7N3: 179.3, found: 180.3 (MH+).

Reference£º
Patent; RAMOT AT TEL-AVIV UNIVERSITY LTD.; KOL, Moshe; ROSEN, Tomer; POPOWSKI, Yanay; (87 pag.)WO2017/137990; (2017); A1;,
Chiral nitrogen ligands in late transition metal-catalysed asymmetric synthesis¡ªI. Addressing the problem of ligand lability in rhodium-catalysed hydrosilations
Nitrogen-Containing Ligands for Asymmetric Homogeneous and Heterogeneous Catalysis

The important role of 31886-58-5

31886-58-5, In the next few decades, the world population will flourish. As the population grows rapidly and people all over the world use more and more resources, all industries must consider their environmental impact.31886-58-5, (R)-(+)-N,N-Dimethyl-1-ferrocenylethylamine it is a common compound, a new synthetic route is introduced below.

15.4 ml of a cyclohexane solution of s-butyllithium (1.3 M, 22 mmol) are added to a solution of 5.14 g (20 mmol) of (R)-N, N-dimethyl-1 -ferrocenylethylamine [(R)-ugi- amine] in 30 ml of t-butyl methyl ether (TBME) at <20C over a period of 10 minutes. The mixture is then heated to 00C while stirring and maintained at this temperature for 1.5 hours. It is then cooled to <60C and 2.47 ml (20 mmol) of dichlororopropyl- phosphine are added over a period of 10 mintues. After stirring at -78C for30 minutes, the mixture is allowed to warm slowly to room temperature and is stirred at this temperature for 1.5 hours. Chemical properties determine the actual use. Each compound has specific chemical properties and uses. We look forward to more synthetic routes in the future to expand reaction routes of (R)-(+)-N,N-Dimethyl-1-ferrocenylethylamine, 31886-58-5 Reference£º
Patent; SOLVIAS AG; WO2008/55942; (2008); A1;,
Chiral nitrogen ligands in late transition metal-catalysed asymmetric synthesis¡ªI. Addressing the problem of ligand lability in rhodium-catalysed hydrosilations
Nitrogen-Containing Ligands for Asymmetric Homogeneous and Heterogeneous Catalysis

Some tips on (R)-(+)-N,N-Dimethyl-1-ferrocenylethylamine

(R)-(+)-N,N-Dimethyl-1-ferrocenylethylamine, A common heterocyclic compound, its traditional synthetic route has been very mature, but the traditional synthetic route has various shortcomings, such as complicated route, low yield, poor purity, etc., below Introduce a new synthetic route.”31886-58-5

To a degassed solution of (R)-1 (829 mg, 3.22 mmol) in THF (4.5 mL) at -78 C was added dropwise sec-BuLi (1.4 M in cyclohexane, 2.5 mL, 3.55 mmol). The resulting deep red solution was stirred for 1 h at -78 C and for 2 h at 0 C. A solution of ZnBr2 (1.3 M in THF, 3.2 mL, 4.19 mmol) was added and the reaction mixture was stirred for further 40 min at 0 C. A degassed solution of [Pd2(dba)3] (148 mg, 0.162 mmol) and tri-(2-furyl)phosphine (tfp) (299 mg, 1.29 mmol) in THF (6 mL) was prepared and stirred for 20 min at r.t. to give a dark green clear solution. To this catalyst solution were transferred a degassed solution of (R,SFc)-1-iodo-2-p-tolylsulfinylferrocene, (R,SFc)-2, (900 mg, 2.00 mmol) in THF (15 mL) and the freshly prepared ferrocenyl-zinc compound. The resulting red-brown solution was heated to reflux under argon at 75 C for 19 h. The reaction mixture was cooled to r.t., quenched with 5 M NaOH (6 mL), diluted with water and extracted with ethyl acetate (3 ¡Á 70 mL). The combined organic phases were washed with water (3 ¡Á 50 mL) and brine (2 ¡Á 50 mL) and dried over MgSO4. The mixture was filtered and the solvent was evaporated. The crude product was purified by column chromatography (silica, PE/EE/NEt3 = 10/10/1 ? 1/2/1). After a second chromatography (aluminium oxide, PE/EE/NEt3 = 1/1/1 ? 1/2/1) was the pure product obtained as an orange solid (yield: 55 mg, 5%). Single crystals suitable for X-ray structure determination were obtained from a solution of the product in EtOAc/PE by slow evaporation of the solvents. M.p.: 158-163 C. 1H NMR (600.1 MHz, CDCl3): delta 1.51 (d, J = 6.9 Hz, 3H, CH3CH), 1.72 (s, 6H, N(CH3)2), 2.42 (s, 3H, Ph-CH3), 3.59 (q, J = 6.9 Hz, 1H, CH3CH), 4.09 (m, 1H, H3?), 4.24 (s, 6H, Cp? + H3), 4.27 (s, 5H, Cp?), 4.39 (dd, J1 = J2 = 2.5 Hz, 1H, H4), 4.42 (dd, J1 = J2 = 2.5 Hz, 1H, H4?), 4.70 (m, 1H, H5?), 4.76 (m, 1H, H5), 7.31 (d, J = 8.0 Hz, 2H, Ph-meta), 7.67 (d, J = 8.0 Hz, 2H, Ph-ortho). 13C{1H} NMR (150.9 MHz, CDCl3): delta 18.9 (bs, CH3CH), 21.5 (Ph-CH3), 40.9 (2C, N(CH3)2), 55.5 (CH3CH), 66.9 (C4), 67.8 (2C, C3 + C3?), 68.8 (C4?), 69.8 (5C, Cp?), 70.7 (5C, Cp?), 71.8 (C5), 73.9 (C5?), 82.0 (C1), 88.6 (C1?/C2?), 89.5 (C2), 93.9 (C1?/C2?), 125.7 (2C, Ph-ortho), 129.4 (2C, Ph-meta), 141.0 (Ph-ipso), 141.4 (Ph para). HR-MS (ESI, MeOH/MeCN): m/z [M + H]+ calcd. 580.1060 for C31H34Fe2NOS; found: 580.1047. [alpha]lambda20 (nm): -739 (589), -843 (578), -1380 (546) (c 0.225, CHCl3).

Reference£º
Article; Gross, Manuela A.; Mereiter, Kurt; Wang, Yaping; Weissensteiner, Walter; Journal of Organometallic Chemistry; vol. 716; (2012); p. 32 – 38;,
Chiral nitrogen ligands in late transition metal-catalysed asymmetric synthesis¡ªI. Addressing the problem of ligand lability in rhodium-catalysed hydrosilations
Nitrogen-Containing Ligands for Asymmetric Homogeneous and Heterogeneous Catalysis

The important role of 110-70-3

N1,N2-Dimethylethane-1,2-diamine, A common heterocyclic compound, its traditional synthetic route has been very mature, but the traditional synthetic route has various shortcomings, such as complicated route, low yield, poor purity, etc., below Introduce a new synthetic route.”110-70-3

To a solution of compound 9-3 (10 g, 36.5 mmol) in EtOH was added dropwise compound 9-3-1 (39 mL, 365 mmol) under nitrogen atmosphere at 0 C., and then the reaction solution was stirred at 20 C. for 2 h, followed by concentration. The residue was purified by column chromatography to give the title compound 9-4 (yellow solid, 5.5 g, Yield 56%). 1H NMR (400 MHz, CDCl3): delta ppm 8.16 (d, J=8.8 Hz, 2H), 7.59 (d, J=8.8 Hz, 2H), 3.80 (s, 1H), 3.60-3.80 (m, 1H), 3.15-3.30 (m, 1H), 3.00-3.10 (m, 1H), 2.93 (s, 3H), 2.60-2.75 (m, 1H), 2.15 (s, 3H).

Reference£º
Patent; Hubei Bio-Pharmaceutical Industrial Technological Institute Inc.; Humanwell Healthcare (Group) Co., Ltd.; Wang, Xuehai; Wu, Chengde; Xu, Yong; Shen, Chunli; Li, Li’e; Hu, Guoping; Yue, Yang; Li, Jian; Guo, Diliang; Shi, Nengyang; Huang, Lu; Chen, Shuhui; Tu, Ronghua; Yang, Zhongwen; Zhang, Xuwen; Xiao, Qiang; Tian, Hua; Yu, Yanping; Chen, Hailiang; Sun, Wenjie; He, Zhenyu; Shen, Jie; Yang, Jing; Tang, Jing; Zhou, Wen; Yu, Jing; Zhang, Yi; Liu, Quan; (251 pag.)US2017/313683; (2017); A1;,
Chiral nitrogen ligands in late transition metal-catalysed asymmetric synthesis¡ªI. Addressing the problem of ligand lability in rhodium-catalysed hydrosilations
Nitrogen-Containing Ligands for Asymmetric Homogeneous and Heterogeneous Catalysis

Extracurricular laboratory: Synthetic route of 33527-91-2

Tris[2-(dimethylamino)ethyl]amine, A common heterocyclic compound, its traditional synthetic route has been very mature, but the traditional synthetic route has various shortcomings, such as complicated route, low yield, poor purity, etc., below Introduce a new synthetic route.”33527-91-2

To a solution of tris(2-dimethylaminoethyl)amine (0.436 g, 1.89 mmol) in acetonitrile (4 mL) was added 1-bromooctane (1.20 g, 6.22 mmol). The resulting mixture was heated at reflux with stirring for 18 hours, during which time a white solid was observed. After cooling, and the addition of a cold hexanes/acetone mixture (15 mL, 1:1), to the reaction flask, the precipitate was filtered with aBuchner funnel, and rinsed with a cold hexanes/acetone mixture (20 mL, 1:1), resulting in T-8,8,8 (1.45 g, 95%) as a yellow-white wax; ?H NMR (300 MI-Tz, CDC13) oe 4.02-3.94 (m, 6H), 3.63-3.54 (m, 6H), 3.42-3.30 (m, 24H), 1.79-1.67 (m, 6H), 1.41-1.19 (m, 30H), 0.90-0.83 (m, 9H); ?3C NMR (75 MHz, CD3OD) oe 65.3,61.0, 50.1, 46.8, 31.5, 28.9, 26.1, 22.4, 22.3, 13.1; high resolution mass spectrum(ESI) m/z 189.8823 ([Mj3 calculated for [C36H8,N4j3: 189.8815). See also Yoshimura et al., 2012, Langmuir 28:9322-933 1. ?H and ?3C NMR spectra of compound T-8,8,8 can be found in Figure 49.

Reference£º
Patent; TEMPLE UNIVERSITY-OF THE COMMONWEALTH SYSTEM OF HIGHER EDUCATION; VILLANOVA UNIVERSITY; WUEST, William, M.; MINBIOLE, Kevin, P.C.; BARBAY, Deanna, L.; (227 pag.)WO2016/172436; (2016); A1;,
Chiral nitrogen ligands in late transition metal-catalysed asymmetric synthesis¡ªI. Addressing the problem of ligand lability in rhodium-catalysed hydrosilations
Nitrogen-Containing Ligands for Asymmetric Homogeneous and Heterogeneous Catalysis

The important role of 31886-58-5

To a degassed solution of (R)-1 (662 mg, 2.57 mmol) in THF (3.2 mL) was added sec-BuLi (1.4 M in cyclohexane, 2 mL, 2.8 mmol) at 0 C. The resulting deep-red solution was stirred for an additional 3 h at the same temperature. To this reaction mixture was added a solution of ZnBr2 (1.3 M in THF, 2.38 mL, 3.09 mmol) at 0 C and stirring was continued at r.t. for 1 h. To a degassed solution of [Pd2dba3]¡¤CHCl3 (266 mg, 0.257 mmol) and tris(2,4-di-tert-butylphenyl)-phosphite (666 mg, 1.029 mmol) in THF (5.5 mL) was added a degassed solution of sulfide (S)- 4 (890 mg, 2.05 mmol) in THF (3 mL). The resulting dark purple solution was stirred for an additional 10 min at r.t. and was subsequently added dropwise to the previously prepared organozinc compound. The reaction mixture was heated to reflux under argon at 75 C for 18 h, and then cooled to r.t., quenched with H2O and extracted with ethyl acetate (3 ¡Á 200 mL). The combined organic layers were washed with brine (3 ¡Á 200 mL) and dried over MgSO4. The mixture was filtered, the solvent was evaporated and the crude product was purified by column chromatography (silica, PE/EE/NEt3 = 20/10/1). The product (R,SFc,RFc)- 5 was obtained as an orange foam (yield: 687 mg, 59%). M.p.: 58-61 C. 1H NMR (400 MHz, CDCl3): delta 1.37 (d, J = 6.8 Hz, 3H, CH3CH), 1.61 (s, 6H, N(CH3)2), 2.20 (s, 3H, Ph-CH3), 3.65 (q, J = 6.8 Hz, 1H, CH3CH), 4.11 (dd, J1 = 2.4 Hz, J2 = 1.4 Hz, 1H, H3), 4.27 (s, 5H, Cp?), 4.30 (dd, J1 = J2 = 2.4 Hz, 1H, H4), 4.35 (s, 5H, Cp?), 4.37 (dd, J1 = J2 = 2.5 Hz, 1H, H4?) 4.44 (dd, J1 = 2.5 Hz, J2 = 1.5 Hz, 1H, H3? 4.59 (dd, J1 = 2.5 Hz, J2 = 1.5 Hz, 1H, H5? 4.64 (dd, J1 = 2.4 Hz, J2 = 1.4 Hz, 1H, H5), 6.88 (d, J = 8.1 Hz, 2H, Ph-meta), 7.02 (d, J = 8.1 Hz, 2H, Ph-ortho). 13C{1H} NMR (100.6 MHz, CDCl3): delta 14.7 (CH3CH), 20.9 (Ph-CH3), 40.3 (2C, N(CH3)2), 55.4 (CH3CH), 66.1 (C4), 66.7 (C3), 67.9 (C4? 69.6 (5C, Cp’), 70.7 (5C, Cp?), 71.7 (C5? 72.4 (C5), 74.1 (C3? 89.8 (C2), 128.9 (2C, Ph-ortho), 129.1 (2C, Ph-meta), 135.1 (2C, Ph-ipso + Ph-para); 3 Cq (C1, C1? C2? were not observed. HR-MS (EI): m/z [M?]+ calcd. 563.1032 for C31H33Fe2NS; found: 563.1050. [alpha]lambda20 (nm): -660 (589), -746 (578), -1180 (546) (c 0.224, CHCl3).

Application of 6-Bromo-1,2,3,4-tetrahydroquinoline

beta-CD-OTs (500.0 mg, 0.388 mmol) was dissolved in 5 mL dry DMF with 100 mg NaI. N,N?-Dimethylethane-1,2-diamine (1.28 mL, 11.72 mmol) was then added under N2 and the reaction mixture was stirred overnight at 70 C. under N2. The next day the reaction mixture was cooled and precipitated in 50 mL acetone, giving a white precipitate. Unreacted tosylate was removed via the same ion-exchange methods as described above for beta-CD-NH2. Yield=374 mg (80.0%). 1H NMR (300 MHz, D2O, delta): 5.02-4.87 (s, 7H, C1H of CD), 3.93-3.64 (m, 29H, C2H, C3H, C4H, and C5H of CD and NH), 3.61-3.29 (m, 14H, C6H of CD), 3.01-2.36 (m, 10H, N1-CH2, N2-CH2, and N2-(CH3)2).

Reference£º
Patent; Thompson, David H.; Kulkarni, Aditya; Deng, Wei; US2015/202323; (2015); A1;,
Chiral nitrogen ligands in late transition metal-catalysed asymmetric synthesis¡ªI. Addressing the problem of ligand lability in rhodium-catalysed hydrosilations
Nitrogen-Containing Ligands for Asymmetric Homogeneous and Heterogeneous Catalysis

Analyzing the synthesis route of N1,N2-Dimethylethane-1,2-diamine

o-Anisaldehyde (10.0 g, 73.4 mmol, 1.0 equiv) was dissolved in EtOH (150 mL) at 25 CC, MAT-dimemylethylenediamine (8.70 mL, 80.8 mmol, 1.1 equiv) was added, and the reaction contents were stirred at 25 C for 24 h before being filtered through a pad of MgS04 and concentrated to afford the desired imidazolidine (15.0 g, 99% yield) as a white solid. Without any additional purification, this material (15.0 g, 72.8 mmol, 1.0 equiv) was dissolved in Et20 (250 mL) and cooled to -40 C. f-BuLi (1.7 M in pentane. 100 mL 170 mmol, 2.34 equiv) was then added dropwise over 1 h at -40 C. Upon completion, the resultant orange reaction contents were warmed slowly to -20 C. stirred for an additional 7 h, and then transferred by cannula over 5 min into a flask containing (CBrCl2)2 (55.3 g, 170 mmol, 2.34 equiv) in Et20 (250 mL) at 0 C. The reaction contents were then stirred for 12 h, during which time they were warmed to 25 C; upon completion, the solution was recooled to 0 C and 1 M HCI (500 mL) was added slowly. The resultant solution was stirred for 1 h at 0 C, quickly warmed to 25 C, and then quenched by the addition of water (500 mL). The reaction contents were then extracted with EtOAc (3 x 250 mL), and the combined organic extracts were washed with water (500 mL) and brine (250 mL). dried (MgSO-i), and 73 concentrated.’23’ The resultant crude yellow solid was purified by flash column chromatography (silica gel, hexanes EtOAc, 9/1) to give the desired brominated product 28 (8.12 g, 52% yield) as a white solid. This material (8.12 g, 37.8 mmol, 1.0 equiv) was suspended in MeOH (100 mL) at 25 C and cooled to 0 C. NaBHj (2.88g , 75.6 mmol, 2.0 equiv) was added portionwise and the reaction contents were stirred for 1 h at 0 C. Upon completion, the reaction contents were quenched with water (100 mL) and concentrated. The reaction contents were redissolved in EtOAc ( 100 mL), poured into water (100 mL), and extracted with EtOAc (3 x 50 mL). The combined organic extracts were washed with water ( 150 mL) and brine (50 mL), dried (MgSO- , and concentrated to afford the desired alcohol (7.83 g, 96%) as a white solid. Pressing forward without any additional purification, this newly prepared material (7.83 g, 36.1 mmol, 1.0 equiv) was dissolved in EtjO (180 mL) and pyridine (0.437 mL, 5.41 mmol, 0.15 equiv) and PBr^ (3.41 mL, 36.1 mmol, 1.0 equiv) were added sequentially at 25 C. The reaction contents were then stirred for 4 h at 25 C. Upon completion, the reaction contents were quenched by the addition of water (100 mL), poured into water ( 100 ml), and extracted with EtOAc (3 x 150 mL). The combined organic extracts were washed with water (200 mL) and brine (100 mL), dried (MgS04), and concentrated to give the desired bromide (10.0 g, 99%) as a white solid. [Note: This product quickly decomposes on standing once it is neat and should be carried forward immediately. | Finally, KHMDS (0.5 M in toluene, 129 mL, 64.5 mmol, 1.8 equiv) was added to a solution of diethyl phosphite (9.19 mL, 71.4 mmol, 2.0 equiv) in THF (100 mL) at 0 C and stirred for 15 min. To this solution was added dropwise a solution of the freshly prepared bromide (10.0 g, 35.7 mmol, 1.0 equiv) dissolved in THF (100 mL), and the reaction contents were stirred for 12 h with slow warming to 25 C. Upon completion, the reaction contents were quenched with saturated NH4CI (150 mL), poured into water (150 mL), and extracted with EtOAc (3 x 150 mL). The combined organic extracts were washed with water (100 mL) and brine (100 mL), dried (MgS04), and concentrated to give the phosphonate 31 (10.79 g, 90%) as a colorless oil. 31: R/ = 0.21 (silica gel, EtOAc); IR (film) vmax 2981, 1589, 1572, 1466, 1435, 1267, 1082, 965, 864, 771 ; NMR (400 MHz, CDCI3) delta 7.18 (d, / = 8.0 Hz, 1 H), 7.07 (app dt, J = 8.0, 2.4 Hz, 1 H), 6.81 (d, J = 8.4 Hz, 1 H), 4.05 (dq, J = 7.2, 7.2 Hz, 4 H), 3.85 (s, 3 H), 3.50 (d, J = 22.0 Hz, 2 H), 1.26 (t, J = 7.2 Hz, 6 H); l3C NMR (75 MHz, CDCI3) delta 158.4 (d, J = 5.4 Hz). 128.6 (d, J = 3.8 Hz), 125.8 (d, J = 7.5 Hz), 125.0 (d, J = 3.5 Hz), 121.6 (d, J = 10.6 Hz), 109.4 (d, J = 3.4 Hz), 61.9 (d, J = 6.5 Hz), 55.9, 28.3 (d, J = 139.0 Hz), 16.3 (d, J = 6.4 Hz); HRMS (MALDI-FTMS) calcd for Ci2H|9BrP04+ [M + H*] 337.0204, found 337.0189

Reference£º
Patent; THE TRUSTEES OF COLUMBIA UNIVERSITY IN THE CITY OF NEW YORK; SNYDER, Scott Alan; SHERWOOD, Trevor C.; ROSS, Audrey G.; OH, Hyunju; GHOSH, Sankar; WO2011/103442; (2011); A2;,
Chiral nitrogen ligands in late transition metal-catalysed asymmetric synthesis¡ªI. Addressing the problem of ligand lability in rhodium-catalysed hydrosilations
Nitrogen-Containing Ligands for Asymmetric Homogeneous and Heterogeneous Catalysis