ABSTRACT
Four furanoditerpenoids were isolated from roots of Croton jatrophoides (Euphorbiaceae) collected in Tanzania. In addition to the known compounds penduliflaworosin and teucvin (mallotucin A), a new teucvin isomer, which was named isoteucvin, and a furanoditerpenoid with a new skeleton, for which the name jatrophoidin was adopted, were isolated. Their structures were elucidated by spectroscopic methods such as ESI-MS and NMR, including (1)H-, (13)C-, and two-dimensional NMR. The crystal structures of isoteucvin and jatrophoidin were solved using single-crystal X-ray diffraction, by which we also established the absolute configuration of jatrophoidin. The refined crystal structure of isoteucvin has the same (absolute) configuration as jatrophoidin, although the X-ray diffraction data of isoteucvin were not conclusive with respect to the absolute configuration.
Subject(s)
Croton/chemistry , Diterpenes/isolation & purification , Plant Extracts/chemistry , Diterpenes/chemistry , Furans/chemistry , Furans/isolation & purification , Isomerism , Molecular Structure , Plant Roots , TanzaniaABSTRACT
The compact tricyclic substructure of solanoeclepin A containing the cyclobutanone ring was prepared by using as the key step a highly regioselective intramolecular [2 + 2]-photocycloaddition reaction between one of the [small pi]-bonds of an allene and the CC double bond of a butenolide.
Subject(s)
Bridged-Ring Compounds/chemical synthesis , Cyclobutanes/chemistry , Furans/chemistry , Hexanes/chemical synthesis , Ketones/chemistry , 4-Butyrolactone/analogs & derivatives , Bridged Bicyclo Compounds/chemical synthesis , Bridged Bicyclo Compounds/chemistry , Bridged-Ring Compounds/chemistry , Crystallography, X-Ray , Cyclization , Cyclobutanes/chemical synthesis , Furans/chemical synthesis , Hexanes/chemistry , Ketones/chemical synthesis , Models, Chemical , Molecular Structure , Photochemistry , StereoisomerismABSTRACT
The mechanism and kinetics of the solvolysis of complexes of the type [(L-L)Pd(C(O)CH(3))(S)](+)[CF(3)SO(3)](-) (L-L = diphosphine ligand, S = solvent, CO, or donor atom in the ligand backbone) was studied by NMR and UV-vis spectroscopy with the use of the ligands a-j: SPANphos (a), dtbpf (b), Xantphos (c), dippf (d), DPEphos (e), dtbpx (f), dppf (g), dppp (h), calix-6-diphosphite (j). Acetyl palladium complexes containing trans-coordinating ligands that resist cis coordination (SPANphos, dtbpf) showed no methanolysis. Trans complexes that can undergo isomerization to the cis analogue (Xantphos, dippf, DPEphos) showed methanolyis of the acyl group at a moderate rate. The reaction of [trans-(DPEphos)Pd(C(O)CH(3))](+)[CF(3)SO(3)](-) (2e) with methanol shows a large negative entropy of activation. Cis complexes underwent competing decarbonylation and methanolysis with the exception of 2j, [cis-(calix-diphosphite)Pd(C(O)CH(3))(CD(3)OD)](+)[CF(3)SO(3)](-). The calix-6-diphosphite complex showed a large positive entropy of activation. It is concluded that ester elimination from acylpalladium complexes with alcohols requires cis geometry of the acyl group and coordinating alcohol. The reductive elimination of methyl acetate is described as a migratory elimination or a 1,2-shift of the alkoxy group from palladium to the acyl carbon atom. Cis complexes with bulky ligands such as dtbpx undergo an extremely fast methanolysis. An increasing steric bulk of the ligand favors the formation of methyl propanoate relative to the insertion of ethene leading to formation of oligomers or polymers in the catalytic reaction of ethene, carbon monoxide, and methanol.
ABSTRACT
The title compound, C(11)H(17)N(2)O(3)PS(2), is a cyclic thiophosphoryl pyrimidine derivative exhibiting insecticidal properties. The crystal structure determination gives evidence for the presence of the thione isomer of the compound. The pyrimidine nucleus is planar and its substituents have small deviations from the least-squares plane. The dioxaphosphorinane ring adopts a chair conformation. The lack of classical hydrogen bonds and the weak intermolecular interactions lead to a 'loose' packing characterized by channels in the structure.
Subject(s)
Organophosphorus Compounds/chemistry , Organothiophosphorus Compounds/chemistry , Pyrimidines/chemistry , Crystallography, X-Ray , Indicators and Reagents , Models, Molecular , Molecular Conformation , Organophosphorus Compounds/chemical synthesis , Organothiophosphorus Compounds/chemical synthesis , Pyrimidines/chemical synthesisABSTRACT
Ru(SnPh(3))(2)(CO)(2)(iPr-DAB) was synthesized and characterized by UV-vis, IR, (1)H NMR, (13)C NMR, (119)Sn NMR, and mass (FAB(+)) spectroscopies and by single-crystal X-ray diffraction, which proved the presence of a nearly linear Sn-Ru-Sn unit. Crystals of Ru(SnPh(3))(2)(CO)(2)(iPr-DAB).3.5C(6)H(6) form in the triclinic space group P&onemacr; in a unit cell of dimensions a = 11.662(6) Å, b = 13.902(3) Å, c = 19.643(2) Å, alpha = 71.24(2) degrees, beta = 86.91(4) degrees, gamma = 77.89(3) degrees, and V = 2946(3) Å(3). One-electron reduction of Ru(SnPh(3))(2)(CO)(2)(iPr-DAB) produces the stable radical-anion [Ru(SnPh(3))(2)(CO)(2)(iPr-DAB)](*-) that was characterized by IR, and UV-vis spectroelectrochemistry. Its EPR spectrum shows a signal at g = 1.9960 with well resolved Sn, Ru, and iPr-DAB (H, N) hyperfine couplings. DFT-MO calculations on the model compound Ru(SnH(3))(2)(CO)(2)(H-DAB) reveal that the HOMO is mainly of sigma(Sn-Ru-Sn) character mixed strongly with the lowest pi orbital of the H-DAB ligand. The LUMO (SOMO in the reduced complex) should be viewed as predominantly pi(H-DAB) with an admixture of the sigma(Sn-Ru-Sn) orbital. Accordingly, the lowest-energy absorption band of the neutral species will mainly belong to the sigma(Sn-Ru-Sn)-->pi(iPr-DAB) charge transfer transition. The intrinsic strength of the Ru-Sn bond and the delocalized character of the three-center four-electron Sn-Ru-Sn sigma-bond account for the inherent stability of the radical anion.
