Os3(CO)9(μ3-η3-C9H5(5-C(CH3)3)N)(μ-H) | 220076-16-4

• 英文名称: Os3(CO)9(μ3-η3-C9H5(5-C(CH3)3)N)(μ-H)
• CAS: 220076-16-4
• 化学式: C₂₂H₁₇NO₉Os₃
• 分子量: 1009.98
• InChiKey: OPQVTMWUMFBSQX-HHYDEXRCSA-N

反应信息

• 作为产物：
  描述：

  Os3(CO)9(μ3-η2-quinolin)(μ-H) 、 叔丁基锂 以 四氢呋喃 为溶剂， 以51.6%的产率得到Os3(CO)9(μ3-η3-C9H5(5-C(CH3)3)N)(μ-H)
  参考文献：
  名称：

  Functionalizing Heterocycles by Electron-Deficient Bonding to a Triosmium Cluster

  摘要：

  A new synthetic methodology for adding carbon-based nucleophiles to the carbocyclic ring of quinolines has been developed, based on the electron-deficient bonding of the C(8) carbon and the protective coordination of the nitrogen atom to the metal core in the complexes Os-3(CO)(9)(mu(3)-eta(2)-C9H5(R)N)(mu-H), 1a-1h. These compounds react with a wide range of carbanions (e.g., R'Li) to give the nucleophilic addition products Os-3(CO)(9)(mu(3)-eta(3)-C9H7(5-R')N)(mu-H), 2a-2l, and Os-3(CO)(9)(mu(3)-eta(3)-C9H6(3-, 4-, or 6-R)(5-R')N)(mu-H), 3b-3g, after quenching with trifluoroacetic acid, in isolated yields of 25-86%. ln the 6-substituted derivatives, this addition is stereoselective, forming only the cis-diastereomer. In the case the 6-chloro derivative, a second product is obtained, Os-3(CO)(9)(mu(3)-eta(2)-C9H5(6-Cl)(5-C(CH3)(2)CN)N)(mu-H)(2) 4, the result of protonation at the metal core and rearrangement of the carbocyclic ring. The trans-diastereomer of the 6-substituted derivatives can be obtained by quenching the intermediate anion of the unsubstituted complex with (CH3O)(2)SO2 or acetic anhydride. Nucleophilic addition to the 5-chloro complex occurs across the 3,4-bond to give OS3(CO)9(mu(3)-eta(2)-C9H6(5-Cl)(4-C(CH3)(2)CN)N)(mu-H), 5 The addition products, types 2 and 3, can be rearomatized by reaction with diazobicyclononane (DBU)/dichlorodicyanoquinone (DDQ) or by reaction of the intermediate anion with trityl cation or DDQ. The resulting rearomatized complexes can be cleanly cleaved from the cluster by heating in acetonitrile under a CO atmosphere, yielding the functionalized quinoline and Os-3(CO)(12) as the only two products. Solid structures of cis-3e, ti ans-3e, 4, and 5 are reported.

  DOI：

  10.1021/ja981445e