| 1614227-97-2

• CAS: 1614227-97-2
• 化学式: C₂₅H₃₇O₆PRu
• 分子量: 565.609
• InChiKey: DCWCAQAEQLGLJF-UHFFFAOYSA-N

反应信息

• 作为产物：
  描述：

  在 aluminum oxide 作用下， 以 二氯甲烷 为溶剂， 反应 12.0h， 以74%的产率得到
  参考文献：
  名称：

  Ruthenium Hydroxycarbenes as Key Intermediates in Cycloisomerization and Decarbonylative Cyclization of Terminal Alkynals

  摘要：

  The complex [Ru(eta(5)-C5H5)(Co)(K-1-OCMe2)(PiPr(3))] BF4 (1) reacts with 3,3-bis(methoxycarbony1)-5-hexyn-1-al to give the alpha,beta-unsaturated cydopenteritylhydrolcarbene derivative [Ru(eta(5)-C5H5){=C (OH)C=CHCH2C(CO2CH3)(2)CH2}-(CO) (PiPr(3)) (2), which undergoes deprotonation with Al2O3 to afford Ru(eta(5)-C5H5){=C (OH)C=CHCH2C(CO2CH3)(2)CH2}-(CO) (PiPr(3)) (3). In the presence of P2O5, the reaction of 1 with the alkynal leads to the alkenylvinylidene Ru(eta(5)-C5H5) {=C= C-H=CH-C(CO2CH3)2-CH2}(CO)(PiPr(3))]BF4 (4), which yields the beta,gamma-unsaturated cydopentenylhydroxycarhene [Ru(eta(5)-C5H5){C(OH)CHCH=CHC(CO2CH3)(2)CH2}(CO)(PiPr(3))BF4 (5) by means of a 1,2-addition of water. Complex 5 slowly isomerizes into 2. The deprotonation of 5 with Al2O3 gives Ru(eta(5)-C5H5){C(O)CHCH= CHC(CO2CH3)(2)CH2}(CO)(PiPr(3)) (6). Solvate Ru complex 1 and Ru hydroxycarbene 2 catalyze the cyclization of 3,3-bis(methoxycarbonyl)-5-hexyn-1-al to give mixtures of the cydoisomerized aldehyde 1,1-bis(methoxycarbonyl)-3-formylcydopent-3-ene (7) and cydoalkene 1,1-bis(methoxycarbonyl)cyclopent-3-ene (8).

  DOI：

  10.1021/om5003864