| 129833-93-8

• CAS: 129833-93-8
• 化学式: CF₃O₃S*C₈H₉O₅PRe
• 分子量: 551.408
• InChiKey: TWNIHASZKHZITR-UHFFFAOYSA-M

反应信息

• 作为反应物：
  描述：

  在 CH₃MgBr 作用下， 以 四氢呋喃 、 甲苯 为溶剂， 以53%的产率得到cis-{(CO)4(PMe3)ReC(O)CH3}
  参考文献：
  名称：

  Reactivity studies on bimetallic μ-malonyl complexes: cleavage and alkylation chemistry of the malonyl ligand

  摘要：

  The bimetallic mu-malonyl complexes: {(eta-C5Me5)(NO)(PPh3)Re[mu-(COCH2CO)-C1:C3]Re(CO)4(Br)}-Li+ (1), {(eta5-C5Me5)(NO)(PPh3)Re[mu-(COCH2CO)-C1:C3]Re(CO)4(PMe3)} . Li+OSO2CF3- (2), and (eta5-C5Me5)(NO)(PPh3)Re[mu-COCH2CO)-C1,O3:C3]Re(CO)4 (3) undergo carbon-carbon bond cleavage reactions of the malonyl ligand upon exposure to HCl. Deprotonation of (eta5-C5Me5)Re(NO)(PPh3)(mu-eta1,eta2-COCH 2CO)Re(CO)4 (3), in THF solution and addition of CH3I leads to the C-alkylation product, (eta5-C5Me5)Re(NO)(PPh3)[mu-(COCH(CH3)CO)-C1,O3:C3]Re(CO)4 (11), isolated as a single diastereomer (85% yield). Deprotonation of 11 and alkylation with CD3I leads to (eta5-C5Me5)Re(NO)(PPh3)[mu-(COC(CH3)(CD3)CO)-C1,O3:C3]Re(CO),(12-d3) with >97% diastereoselectivity. Alkylation of the enolate anion derived from deprotonation of 11 with ethyl iodide led to isolation of (eta5-C5Me5)(NO)(PPh3)Re{mu-[COCCH3=C(OCH2CH3)]-C1,O3: C3}Re(CO)4 (21) in 84% yield. Quenching of the enolate anion of 3 with excess ethyl iodide led to formation of an 11 : 89 mixture of (eta5-C5Me5)(NO)(PPh3)Re[A-(COCHCH2CH3CO)-C1: C3,O3]Re(CO)4 (15) and (eta5-C5Me5)(NO)(PPh3)Re[mu-(COCH=COCH2CH3)-C1,O3:C3]Re(CO)4 (16) in 87% combined yield. When the enolate anion of 3 was treated with allyl bromide, both C and O alkylation products (eta5-C5Me5)(NO)(PPh3)Re{mu-[COCH(CH2CH=CH2)CO]-C1:C3,O1}Re(CO)4 (17) and (eta5-C5Me5)(NO)(PPh3)Re{mu-[COCH=C(OCH2CH=CH2)]-C1,O3:C3}Re(CO)4 (18) were formed in a 32:68 ratio (84% combined yield). Alkylation with benzyl bromide gave (eta5-C5Me5)(NO)(PPh3)Re[mu-(COCH=COCH2C6H5)-C1,O3:C3]Re(CO)4 (19) in 76% yield.

  DOI：

  10.1016/0022-328x(93)80393-p
• 作为产物：
  描述：

  [rhenium(I)(pentacarbonyl)(trifluoromethanesulfonate)] 、 三甲基膦 生成
  参考文献：
  名称：

  O'Connor, Joseph M.; Uhrhammer, Roger; Rheingold, Arnold L., Journal of the American Chemical Society, 1990, vol. 112, # 21, p. 7585 - 7598

  摘要：

  DOI：