79803-33-1Relevant academic research and scientific papers
Enantioselective synthesis of rumphellaone A via epoxy nitrile cyclization
Hirokawa, Takafumi,Nagasawa, Tomohiro,Kuwahara, Shigefumi
, p. 705 - 706 (2012)
The first enantioselective synthesis of rumphellaone A, a cytotoxic 4,5-seco-caryophyllane derivative incorporating a γ-lactone ring as its structural feature, has been achieved by using base-induced intramolecular cyclization of an epoxy nitrile intermed
Synthesis of rumphellaone A via epoxy nitrile cyclization
Hirokawa, Takafumi,Kuwahara, Shigefumi
, p. 4581 - 4587 (2012)
The first enantioselective total synthesis of rumphellaone A, a cytotoxic 4,5-seco-caryophyllane isolated from the gorgonian coral Rumphella antipathies, has been achieved from a known olefinic alcohol by a 16-step sequence involving Stork's epoxy nitrile
An Investigation of the Thermal Decomposition of the Methohydroxides and Methodeuterio-oxides of Some 5-N,N-Dimethylaminopent-1-enes
Cocker, Wesley,Geraghty, Niall W. A.,McMurry, T. Brian H.,Shannon, Patrick V. R.
, p. 2245 - 2254 (2007/10/02)
The base-catalysed thermal decomposition of a number of quaternary bases of the type (R1)2C=CH(R2)2C(R3)2CH2N+Me3X- (R1 = H, Me; R2 = H, 2H; R3 = H, 2H, Me; X = OH, O2H) has been investigated.It is shown that the reaction is initiated by attack of base (OH-, O2H-, ylide) on an allylic proton or .A mechanism for the reaction is suggested.
Cyclometallation of Dialkylbis(triethylphosphine)platinum(II) Complexes: Formation of Pt,Pt-Bis(triethylphosphine)platinacycloalkanes
DiCosimo, Robert,Moore, Stephen S.,Sowinski, Allan F.,Whitesides, George M.
, p. 124 - 133 (2007/10/02)
The thermal decompositions of three analogues of bis(triethylphosphine)dineopentylplatinum(II) (L2Pt2 (1)) - L2Pt2 (3), L2Pt2 (5), and L2Pt2 (7) - have been examined.Compounds 3 and 7 decompose more rapidly than 1 by a factor of ca. 104 to give as products Pt,Pt-bis(triethylphosphine)-3,3-dimethylplatinacyclohexane (4) and Pt,Pt-bis(triethylphosphine)-3,3,5,5-tetramethylplatinacyclohexane (8), respectively, and 1 equiv of the corresponding alkane.Compound 5 decomposes at a rate ca. 50 times faster than 1 to yield Pt,Pt-bis(triethylphosphine)-2,4,4-trimethylplatinacyclopentane (6a), -3-methyl-3-n-propylplatinacyclobutane (6b), and -3,3-dimethylplatinacyclohexane (6c).The conversion of 3 to 4 and 5 to 6a proceeds by dissociation of triethylphosphine, intramolecular oxidative addition of a δ carbon-hydrogen bond of the alkyl groups to platinum, and reductive elimination of alkane.The decomposition of L2Pt2 (11) proceeds by β-hydride elimination rather than cleavage of a carbon-hydrogen bond and formation of platinacycloalkane.The difference in the free energies of activation for reactions which form four- and five-membered platinacycloalkanes is small (ΔΔG(excit.) ca./= 4 kcal mol-1); that for reactions wich form four- and six-membered rings is smaller (ΔΔG(excit.) ca./= 0 kcal mol-1).We identify these values of ΔΔG(excit.) with estimates of the strain energies of these rings, assuming the strain energy of the platinacyclohexane is small.The important conclusion from these studies is that the strain energy of the platinacyclobutane studied here is small (-1).
