[OsCl(CH(COOMe)2)(η6-p-cymene)((-)-(R)-(3,5-dioxa-4-phosphacyclohepta[2,1-a;3,4-a']dinaphthalen-4-yl)dimethylamine)] | 1068006-14-3

• 英文名称: [OsCl(CH(COOMe)2)(η6-p-cymene)((-)-(R)-(3,5-dioxa-4-phosphacyclohepta[2,1-a;3,4-a']dinaphthalen-4-yl)dimethylamine)]
• CAS: 1068006-14-3
• 化学式: C₃₇H₃₉ClNO₆OsP
• 分子量: 850.347
• InChiKey: FMUVUSMOUCDSMS-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
  None
• 可旋转键数：
  None
• 环数：
  None
• sp3杂化的碳原子比例：
  None
• 拓扑面积：
  None
• 氢给体数：
  None
• 氢受体数：
  None

反应信息

• 作为反应物：
  描述：

  [OsCl(CH(COOMe)2)(η6-p-cymene)((-)-(R)-(3,5-dioxa-4-phosphacyclohepta[2,1-a;3,4-a']dinaphthalen-4-yl)dimethylamine)] 、 sodiodimethylmalonate 以 四氢呋喃 为溶剂， 生成 Os(κ1-C(3)-[CH(CO2Me)2])(κ2-O,O-[CH(COOMe)2])(η6-p-cymene)
  参考文献：
  名称：

  Osmium-Catalyzed Allylic Alkylation

  摘要：

  Complex [OSCl2(eta(6)-p-cymene)](2) (1) reacts with (5,7-dioxa-6-phosphadibenzo[a,c]cyclohepten-6-yl)-dimethylamine (L-1) and (-)-(R)-(3,5-dioxa-4-phosphacyclohepta[2,1-a;3,4-a']dinaphthalen-4-yl)dimethylamine (L-2) to give OsCl2(eta(6)-p-eymene)L (L = L-1 (2), L-2 (3)). Complexes 1-3 and OsCl1(eta(6)-p-cymene) {P(OPh)3} (4) are efficient catalyst precursors for the alkylation of 1-phenylallyl methylcarbonate (5a), 1-phenylallyl acetate (5b), cinnamyl methylcarbonate (6a), and cinnamyl acetate (6b) with sodium dimethylmalonate to afford 1-phenylallyl dimethylmalonate (7) and cinnamyl dimethy1malonate (8) with branched:linear molar ratios between 97:3 and 67:33. In the absence of sodium dimethylmalonate, the reaction of 1 with 5a leads initially to {OsCl(eta(6) -p-cymene)}(2)(mu-OMe)(2) (9) and subsequently to [{Os(eta(6)- p-cymene)}(2)(mu-OMe)(3)][O2COMe] (10). In the absence of 5a, the reaction of 1 with sodium dimethylmalonate gives Os{kappa(1)-C-3-[CH(CO2Me)(2)]) {kappa(2)-O,O-[CH(CO2Me)(2)]}(eta(6)-p-cymene) (11). Complexes 9-11 are also efficient catalyst precursors for the alkylation of 5a with sodium dimethylmalonate. The activity of 9 and 10 is the same as that of 1. However, complex 11 is significantly less efficient than 1. In contrast to the latter, complexes 2 and 3 do not react with 5a in the absence of sodium dimethylmalonate. In the absence of the substrate, the reactions of 2 and 3 with sodium dimethylmalonate lead to Os{kappa(1)-C-3-[CH(CO2Me)(2)]}CI(eta(6)-p-cymene)L (L = L-1 (12), L-2 (13)), which further react with excess sodium dimethylmalonate to give 11. The catalytic behavior of 12 and 13 has been also studied. Their activities are the same as those of 2 and 3 and intermediate between those of 10 and 11. Complexes 3, 9, 11, and 12 have been characterized by X-ray diffraction analysis.

  DOI：

  10.1021/om800460h
• 作为产物：
  描述：

  [OsCl2(η6-p-cymene)((-)-(R)-(3,5-dioxa-4-phosphacyclohepta[2,1-a;3,4-a']dinaphthalen-4-yl)dimethylamine)] 、 sodiodimethylmalonate 以 四氢呋喃 为溶剂， 以63%的产率得到[OsCl(CH(COOMe)2)(η6-p-cymene)((-)-(R)-(3,5-dioxa-4-phosphacyclohepta[2,1-a;3,4-a']dinaphthalen-4-yl)dimethylamine)]
  参考文献：
  名称：

  Osmium-Catalyzed Allylic Alkylation

  摘要：

  Complex [OSCl2(eta(6)-p-cymene)](2) (1) reacts with (5,7-dioxa-6-phosphadibenzo[a,c]cyclohepten-6-yl)-dimethylamine (L-1) and (-)-(R)-(3,5-dioxa-4-phosphacyclohepta[2,1-a;3,4-a']dinaphthalen-4-yl)dimethylamine (L-2) to give OsCl2(eta(6)-p-eymene)L (L = L-1 (2), L-2 (3)). Complexes 1-3 and OsCl1(eta(6)-p-cymene) {P(OPh)3} (4) are efficient catalyst precursors for the alkylation of 1-phenylallyl methylcarbonate (5a), 1-phenylallyl acetate (5b), cinnamyl methylcarbonate (6a), and cinnamyl acetate (6b) with sodium dimethylmalonate to afford 1-phenylallyl dimethylmalonate (7) and cinnamyl dimethy1malonate (8) with branched:linear molar ratios between 97:3 and 67:33. In the absence of sodium dimethylmalonate, the reaction of 1 with 5a leads initially to {OsCl(eta(6) -p-cymene)}(2)(mu-OMe)(2) (9) and subsequently to [{Os(eta(6)- p-cymene)}(2)(mu-OMe)(3)][O2COMe] (10). In the absence of 5a, the reaction of 1 with sodium dimethylmalonate gives Os{kappa(1)-C-3-[CH(CO2Me)(2)]) {kappa(2)-O,O-[CH(CO2Me)(2)]}(eta(6)-p-cymene) (11). Complexes 9-11 are also efficient catalyst precursors for the alkylation of 5a with sodium dimethylmalonate. The activity of 9 and 10 is the same as that of 1. However, complex 11 is significantly less efficient than 1. In contrast to the latter, complexes 2 and 3 do not react with 5a in the absence of sodium dimethylmalonate. In the absence of the substrate, the reactions of 2 and 3 with sodium dimethylmalonate lead to Os{kappa(1)-C-3-[CH(CO2Me)(2)]}CI(eta(6)-p-cymene)L (L = L-1 (12), L-2 (13)), which further react with excess sodium dimethylmalonate to give 11. The catalytic behavior of 12 and 13 has been also studied. Their activities are the same as those of 2 and 3 and intermediate between those of 10 and 11. Complexes 3, 9, 11, and 12 have been characterized by X-ray diffraction analysis.

  DOI：

  10.1021/om800460h