With the rapid development and complex challenges of chemical substances, new drug synthesis pathways are usually the most effective.29841-69-8,(1S,2S)-(-)-1,2-Diphenylethylenediamine,as a common compound, the synthetic route is as follows.
trans-RuH(eta1-BH4)[(s)-xylbinap][(S,S)-dpen] was synthesized. First, trans-RuCl2[(S)-xylbinap][(S,S)-dpen] was synthesized. That is, [RuCl2(benzene)]2 (62.5 mg; 0.125 mmol) (made by Aldrich Inc.) and (R)-XylBINAP (183.5 mg; 0.25 mmol) were weighed and placed in a 75 mL Schlenk reaction tube equipped with a stirrer coated with polytetrafluoroethylene, and after depressurizing the interior of the vessel to eliminate air, argon was introduced. After then adding DMF (3 mL) with a syringe, heating in an oil bath set to 100 C. was performed for 10 minutes under an argon atmosphere. After cooling the reaction solution to room temperature, DMF was distilled off under reduced pressure(1 mmHg). (S, S)-DPEN (53.0 mg; 0.25 mmol) (made by Kankyo Kagaku Center Co., Ltd.) and methylene chloride (3 mL) were then added under an argon gas flow to the reddish-brown RuCl2[(S)-xylbinap] (dmf)n solution thus obtained and stirring at 25 C. was performed for 1 hour. A green-colored crude product obtained by distilling off the methylene chloride under reduced pressure (1 mmHg) was dissolved in a 1:1 volume ratio methylene chloride/diethyl ether mixed solvent (2 mL) and this was passed through a column packed with silica gel (5 g) using a 1:1 volume ratio diethyl ether-hexane solution as an eluate to remove impurities. A yellow solution obtained as a precursor was then concentrated until a complex precipitated and solids were separated by filtration and dried under reduced pressure (1 mmHg) to obtain trans-RuCl2[(S)-xylbinap][(S,S)-dpen] (214.8 mg; 0.192 mmol; yield: 77%) as a yellow powder. [XylBINAP] and [xylbinap] are abbreviations for 2,2′-bis(di-3,5-xylylphosphino)-1,1′-binaphthyl. [00032] The abovementioned trans-RuCl2[(S)-xylbinap] [(S,S)-dpen] (89.5 mg; 0.08 mmol) and sodium borohydride (75.6 mg; 2.0 mmol) (made by Nacalai Tesque, Inc.) were then weighed and placed in a 20 mL Schlenk reaction tube equipped with a stirrer coated with polytetrafluoroethylene, and after depressurizing the interior of the vessel to eliminate air, argon was introduced. After then adding a 1:1 volume ratio mixed solvent of benzene/ethanol (6 mL) with a syringe, heating in an oil bath set to 65 C. was performed for 5 minutes under an argon atmosphere. The reaction solution was thereafter stirred for 30 minutes at room temperature. After then drying and solidifying the crude product by distilling off the solvent under reduced pressure (1 mmHg), hexane (5 mL) was added under an argon gas flow to dissolve as much of a yellow product as possible and then the excess sodium borohydride was eliminated by filtration by celite (0.5 g). A yellow filtrate thus obtained was concentrated to approximately 1 ml by depressurization (1 mm Hg) and yellow solids thus precipitated were separated by filtration through a glass filter and dried under reduced pressure (1 mmHg) to obtain trans-RuH(eta1-BH4)[(S)-xylbinap][(S,S)-dpen] (38.3 mg; yield: 45%; see formula (4) below) as a yellow powder. Decomposition temperature: 220 C.; 1HNMR(400 MHz, C6D6) delta-13.67(t, 1, J=23.2 Hz, RuH), -0.48(brs, 4, BH4), 1.59(brs, 12, 4 CH3), 1.78(s, 6, 2CH3), 2.00(s, 6, 2CH3), 2.28-2.35(m, 2, 2NHH), 3.62-3.67(m, 1, CHNH2), 3.76-3.81(m, 2,2CHNH2), 4.09 (dd, 1, J=9.6 and 18.2 Hz, CHNH2), 5.77-8.38(m, 34, aromatics); 31PNMR(161.7 MHz, C6D6) delta73.1(d, J=41.4 Hz), 76.8(d, J=41.4 Hz); IR(toluene)2319(s), 1850(s), 1125(s)cm-1; ESI-MS m/z1063.33([M-H]+), theoretical value (C66H68BN2P2Ru): 1063.40.
29841-69-8, 29841-69-8 (1S,2S)-(-)-1,2-Diphenylethylenediamine 6931238, acatalyst-ligand compound, is more and more widely used in various fields.
Reference£º
Patent; Nagoya Industrial Science Research Institute; US6720439; (2004); B1;,
Metal catalyst and ligand design
Ligand Template Strategies for Catalyst Encapsulation – NCBI