bluuebunny/crossref_metadata_2025_split huggingface dataset:
Synthesis of 2-Amino-2,5,6-trideoxy-5-phenylphosphinyl-l-galactopyranose. The P-in-the-Ring Analogue of l-Fucosamine
Authors: Hanaya Tadashi , Yamamoto Hiroshi , Kawamoto Heizan , Armour Margaret-Ann , Hogg Alan M , Yamamoto Hiroshi 
Published: August 2006

Abstract
3-O-Benzyl-1,2-O-isopropylidene-6-O-tosyl-α-d-allofuranose was led to methyl (5R and 5S)-3-O-benzyl-5,6-dideoxy-5-[(methoxy)phenylphosphinyl]-d-ribo-hexofuranoside (9) in a 4 step sequence (55% overall yield). Methyl (5R and 5S)-2-acetamido-2,5,6-trideoxy-5-[(methoxy)phenylphosphinyl]-d-arabino-hexofuranoside (12) was prepared from 9 in 4 steps involving a C-2 inversion (62% overall yield). Compound 12 was then converted, in 2 steps, into the title compound, which was characterized as the peracetyl derivatives.
Knoevenagel Reaction of Malononitrile with Acetone Followed by Double Cyclization Catalyzed by KF-Coated Alumina in Aqueous Solution
Authors: Nakano Yoshiharu , Niki Seiji , Kinouchi Shigetoshi , Miyamae Hiroshi , Igarashi Minoru 
Published: August 2006

Abstract
The condensation reaction of malononitrile with acetone was catalyzed by variously pretreated alumina (1/4 equiv based on the amount of KF) to give a 2-azabicyclo[2.2.2]octane derivative in water (in more than 90% yield). With more catalyst (1 equiv), a potassium salt of the product was formed unexpectedly. Both products released isobutylene to give the corresponding pyridine derivatives.
The Total Synthesis of Herbimycin A
Authors: Nakata Masaya , Osumi Tomomasa , Ueno Ari , Kimura Takenori , Tamai Tetsuro , Tatsuta Kuniaki 
Published: August 2006

Abstract
The first total synthesis of herbimycin A (1), the benzoquinonoid ansamycin antibiotic, is described. (2E,4S,5R,6S,8S)-5,6-Dimethoxy-9-(4-methoxybenzyl)oxy-2,4,8-trimethyl-2-nonenal (40), corresponding to the C7–C15 portion of the ansa-chain of 1, was prepared from methyl 3,4-anhydro-2-deoxy-2-C-methyl-6-O-(triphenylmethyl)-α-d-altropyranoside (16), which had been previously prepared from methyl α-d-mannopyranoside according to our developed procedure, by using a regioselective epoxide opening [bis(1,2-dimethylpropyl)borane–NaBH4] and a stereoselective hydroboration (BH3·SMe2) as the key steps. This aldehyde 40 was subjected to the Brown’s diastereo- and enantioselective allylation conditions [[(Z)-3-methoxyallyl]diisopinocampheylborane] to afford the desired syn 3-methoxy-1,5-dodecadien-4-ol derivative. Subsequent three-step conversion of this alcohol furnished the synthesis of the C5–C15 ansa-chain aldehyde, (2S,4S,5R,6S,7E,9S,10S)-9-[(t-butyldimethylsilyl)oxy]-4,5,10-trimethoxy-2,6,8-trimethyl-7,11-dodecadienal (7). Union of 7 and the lithiated aromatic chromophore, prepared from N-(triphenylmethyl)-3-bromo-2,5-dimethoxyaniline and butyllithium, provided the coupling product, which was transformed to herbimycin A (1) through elongation of the C1–C4 carbon unit and macrolactamization. This fully enantiospecific synthesis elucidates the absolute stereochemistry of 1.
Functionalization of 1H-Pyrrolo[2,3-b]pyridine
Authors: Minakata Satoshi , Itoh Shinobu , Komatsu Mitsuo , Ohshiro Yoshiki 
Published: August 2006

Abstract
Functionalization of 1H-pyrrolo[2,3-b]pyridine (7-azaindole) was studied to provide new compounds directing toward agrochemicals and/or functional materials. Amino groups such as NH2, NH(CH2)2NH2, and NH(CH2)2NH(CH2)2NH2 were introduced onto 6-position of 7-azaindole to form multidentate agents. 6-Amino and 6-iodo derivatives were easily converted to podant-type compounds, N,N′-bis(1H-pyrrolo[2,3-b]pyridin-6-yl)-1,3-benzenedicarboxamide and bis(1H-pyrrolo[2,3-b]pyridin-6-yl)acetylene, respectively. Polyacetylene having 1H-pyrrolo[2,3-b]pyridyl group as a pendant was obtained by polymerization of 6-ethynyl-7-azaindole synthesized by ethynylation of 6-bromo derivative. As functionalization at 3-position of 7-azaindole, syntheses of 3,3′-selenobis[1H-pyrrolo[2,3-b]pyridine] and the corresponding 3,3′-thio compound, as well as 3-carboxyethenyl- and 3-vinyl-7-azaindoles were performed. Some of these products exhibited high fungicidal activity.
Solidification of Iodide Ion by Reaction with Bi2O3
Authors: Kodama Hiroshi 
Published: August 2006

Abstract
α-Bi2O3 is a candidate material for the immobilization of radioactive iodine. The present paper discusses a method for removing radioactive iodide ion by fixing it into α-Bi5IO7 by a direct reaction with α-Bi2O3; it also reports on experimental conditions under which aqueous iodide reacts with α-Bi2O3 to form a single phase of α-Bi5IO7. α-Bi2O3 was reacted with aqueous iodide in LiI, NaI, KI, and NH4I solutions. Although a previous paper reported that the concentration of aqueous iodide ion was the most important factor to form a single phase of α-Bi5IO7, the present result shows that it is not an important factor. The α-Bi5IO7 single phase can be obtained regardless of the concentration of iodide ion when the ratio of the gram molecular number of the bismuth oxide and the gram ion number of the radioactive iodide ion is adjusted in the range 5 : 2 to 1 : 2 in a LiI solution, 4 : 1 to 1 : 2 in a NaI solution, and 4 : 1 to 1 : 4 in a KI solution. A reaction in a NH4I solution does not produce a single phase of Bi5IO7 at any ratio.
Synthesis and Properties of T-Cage-Type Se-Bridged Polynuclear Co(III) and Rh(III) Complexes with 2-Aminoethaneselenolate (aese). Crystal Structure of [{Co(aese)3}4Zn4O](ClO4)6
Authors: Okamoto Ken-ichi , Watanabe Yuko , Konno Takumi , Hidaka Jinsai 
Published: August 2006

Abstract
The novel T-cage-type Se-bridged polynuclear complexes with 2-aminoethaneselenolate (aese), [{Co(aese)3}4Zn3Cl]5+, [{Co(aese)3}4Zn4O]6+, and [{Rh(aese)3}4Zn4O]6+, have been synthesized. Of these complexes, the spontaneous resolution was recognized for [{Co(aese)3}4Zn4O]Cl6 and [{Rh(aese)3}4Zn4O](NO3)6 with a “complete” [Zn4O]6+ core. The crystal structure of -[{Co(aese)3}4Zn4O](ClO4)6·4H2O was determined by the X-ray diffraction method. The crystal is cubic, space group P213, a = 19.646(2) Å, U = 7582.2(7) Å3, Z = 4, and R = 0.0725. The four octahedral fac(Se)-[Co(aese)3] subunits are bound to the tetrahedral [Zn4O]6+ core in a tetrahedral arrangement, giving an approximate T symmetrical (T-cage-type) structure. The three Se atoms in each fac(Se)-[Co(aese)3] subunit are bound to the three different Zn atoms. For the isomer, the chiral configurations are regulated to Δ for all four fac(Se)-[Co(aese)3] subunits, and S for all 12 bridging Se atoms. The electronic absorption and CD spectral behavior of the complexes are discussed in comparison with those of the related mononuclear and linear-type trinuclear complexes, and the corresponding T-cage-type S-bridged polynuclear complexes.
Preparation and Characterization of Co(III)-Dimethyldithiocarbamato Complexes Containing 1,2-Bis(dimethoxyphosphino)ethane. Molecular Structures of [Co{(CH3)2NC(S)S}{R2P(CH2)2PR2}2] (BF4)2 (R = CH3O and CH3)
Authors: Kita Masakazu , Okuno Masaaki , Kashiwabara Kazuo , Fujita Junnosuke 
Published: August 2006

Abstract
The [Co(dtc)3−n(dmope)n]n+ (n = 1, 2) complexes were prepared, where dtc and dmope denote a dimethyldithiocarbamate ion and 1,2-bis(dimethoxyphosphino)ethane, respectively. The absorption and magnetic circular dichroism (MCD) spectra, and reduction and oxidation potentials were compared with those of the corresponding 1,2-bis(dimethylphosphino)ethane (dmpe) and related complexes. The molecular structures of [Co(dtc)(dmope)2](BF4)2 (1) and [Co(dtc)(dmpe)2] (BF4)2 (2) were determined by the X-ray diffraction method. Crystal data are; for 1, monoclinic, Cc, a = 18.154(5), b = 12.533(2), c = 14.447(3) Å, β = 101.69(2)°, V = 3219(1) Å3, Dx = 1.61, Dm = 1.60(3) g cm−3, and Z = 4, R = 0.044 for 3259 reflections; for 2, monoclinic, P21/a, a = 18.967(3), b = 10.333(1), c = 14.459(2) Å, β = 90.10(2)°, V = 2833.8(7) Å3, Dx = 1.53, Dm = 1.54(4) g cm−3, Z = 4, R = 0.052 for 5662 reflections. The average Co–P bond distance trans to S is 2.186(2) Å for 1 and 2.240(1) Å for 2, and that trans to P is 2.226(2) Å for 1 and 2.278(1) Å for 2. The Co–P distances in 1 are shorter by ca. 0.05 Å than those in 2, while the average Co–S bond distances are similar, 2.288(1) Å for 1 and 2.282(3) Å for 2.
Hydrophobic Vitamin B12. XI. Preparation, Characterization, and Enantioselective Alkylation of Hydrophobic Vitamin B12 Bearing a Binaphthyl Moiety
Authors: Murakami Yukito , Hisaeda Yoshio , Kohno Hiroshi , Ohno Teruhisa , Nishioka Takuya 
Published: August 2006

Abstract
Hydrophobic vitamin B12 derivatives bearing a chiral binaphthyl moiety, hexamethyl 71-decarboxy-71-[(R)-2′-methoxy-1,1′-binaphthyl-2-carboxymethyl]cobyrinate perchlorate [B12–BINAP(R)] and hexamethyl 71-decarboxy-71-[(S)-2′-methoxy-1,1′-binaphtyl-2-carboxymethyl]cobyrinate perchlorate [B12–BINAP(S)], were prepared from cyanocobalamin. These complexes were characterized by means of electronic and circular dichroism spectroscopy as well as by cyclic voltammetry in comparison with those data for a hydrophobic vitamin B12 without a binaphthyl moiety. The enantioselective alkylation of hydrophobic vitamin B12 derivatives at the β-axial site was examined in methanol with various 3-bromo-2-methylpropionic esters by means of 1H NMR spectroscopy. All the hydrophobic vitamin B12 derivatives used here, the one bearing methoxycarbonyl groups as peripheral substituents without a binaphthyl moiety, B12–BINAP(R), and B12-BINAP(S), were found to bind (S)-2-methylpropionates more favorably than the corresponding R-enantiomers; the highest S-selectivity was observed with the latter two derivatives, 65% e.e. The cause of such S-enantioselectivity was discussed with attention to stereochemical configurations of the peripheral substituents placed in the corrin ring.
Thermostable Intramolecular Coupling Products from Some p-Xylylenebis(anthrylcarboxylate)s and the Relationship between Their Thermal Stability and Relative Distortion Energy
Authors: Sasaki Hiroshi , Kobayashi Setsuo , Iwasaki Kishiroo , Ohara Shuichi , Osa Tetsuo 
Published: August 2006

Abstract
The thermal stability of intramolecular coupling products from three kinds of p-xylylenebis(anthrylcarboxylate)s are evaluated. Upon near-UV irradiation, two anthracene moieties in each derivative react at the 9–9′ and 10–10′ positions. The derivatives then from intramolecular coupling products. These coupling products are identified by means of 1H NMR and a linear combination of the atomic orbital coefficients for the highest occupied molecular orbital and the lowest unoccupied molecular orbital from analogues of each derivative. After keeping for 1000 h at a temperature of 60 °C, the coupling products from 2 species of p-xylylenebis(anthrylcarboxylate)s do not revert to the original p-xylylenebis(anthrylcarboxylate)s and are thermostable. However, these thermostable coupling products are reversed to the p-xylylenebis(anthrylcarboxylate)s by UV (260 nm) irradiation. The thermal stability of these coupling products can be explained on the basis of the magnitude of the relative distortion energy.
Spectrophotometric Determination of Thiocyanate by Its Oxidation with Iodate
Authors: Koh Tomozo , Yonemura Yasunobu , Kanai Hiroaki 
Published: August 2006

Abstract
A simple method for the determination of thiocyanate has been proposed, based on the oxidation of thiocyanate to sulfate with iodate in a sulfuric acid medium and on the spectrophotometric measurement of the iodine as triiodide at 350 nm, formed from the excess iodate with iodide added. The complete oxidation of thiocyanate to sulfate using iodate was achieved in a medium containing varying amounts of sulfuric acid at 30 °C. Thiocyanate reacted with iodate with a mole ratio of 1 : 1 under the conditions employed here. The proposed method is approximately 20-fold more sensitive than the conventional method using iron(III) and can be applied to the determination of thiocyanate in the concentration range 5.6 × 10−7−5.2 × 10−5 mol dm−3 (0.31–30.2 μg of SCN− in 10 cm3). The relative standard deviation (n = 1) was 0.44% at the 3 × 10−5 mol dm−3 thiocyanate (17.4 μg of SCN− in 10 cm3) level.
Correlation Analysis of the pKa Values of Mono- and Di-ortho-Substituted Benzoic Acids
Authors: Sotomatsu Tomoko , Shigemura Masao , Murata Yoshiyuki , Fujita Toshio 
Published: August 2006

Abstract
The pKa values of 10 benzoic acids occupied simultaneously at the 2- and 6-positions by various substituent combinations were newly measured in water at 25 °C. The effects of the substituents were analyzed quantitatively with regression analysis and free-energy-related parameters of the Hammett–Taft type. The results were compared with those of the analysis of the pKa of mono-ortho-substituted acids cited in the literature. The resonance effect of substituents in di-ortho-substituted compounds was insignificant, but the electronic effect of the through-space inductive type in terms of the Charton σI and the steric effect in terms of the Taft–Kutter–Hansch Es were not. The overall effects were additive for two substituents. In mono-ortho-substituted acids, a “regular” electronic effect of ortho substituents similar to that of the corresponding para substituents including the resonance effect component was indicated to work in addition to the steric and the through-space inductive effects. The steric and through-space inductive effects of a substituent were almost unchanged regardless of whether the substituent was involved in mono- or di-ortho substitution. A possible rationale integrating the results for mono- and di-ortho-substituted acids was to assume an intermediate formation for the dissociation process in which the carboxyl group is partly ionized and more easily twisted than the nonionized carboxyl group in the initial state.
Electron-Laser Dual Beam Irradiation of 2-Methylbenzophenone
Authors: Ishida Akito , Yamamoto Kazuki , Takamuku Setsuo 
Published: August 2006

Abstract
Pulse radiolysis of 2-methylbenzophenone (MBP) in benzene gave the triplet excited state (3MBP*) which rapidly decayed by intramolecular hydrogen abstraction resulting in the photoenol. Successive laser flash photolysis elucidated the photochemical formation of dihydroanthrone from the photoenol.
Determination of Aluminium in Natural Waters by Ion-Pair Reversed-Phase Partition HPLC
Authors: Kaneko Emiko , Hoshino Hitoshi , Yotsuyanagi Takao , Watabe Ritsuko , Seki Toshihiko 
Published: August 2006

Abstract
An ion-pair reversed-phase partition high-performance liquid chromatography-spectrophotometric detection system with 2,2′-dihydroxyazobenzene has been successfully applied to the determination of μg dm−3 level of aluminium in natural waters. The detection limit is 0.2 μg dm−3 in pure solution, and 1 μg dm−3 for total aluminium in water sample. The relationship between the aluminium concentration and pH value of the ground waters is also discussed.
[14π]Electrocyclization Followed by Preferential [1,9]Hydrogen Migration in the Thermolysis of 1-Formyl-4-[(2,4,6-cycloheptatrienyl)(phenylsulfinyl)methyl]azulene
Authors: Sugihara Yoshikazu , Saito Junji , Murata Ichiro 
Published: August 2006

Abstract
1-Formyl-4-[2,4,6-cycloheptatrienyl)(phenylsulfinyl)methyl] azulene (8b) was thermolyzed at 65 °C for 100 min to give 7,12a-dihydro-2-formyldicyclohept[cd,g]indene (9b), which was isomerized to 1,10-dihydro-2-formyldicyclohept[cd,g]indene (10b), upon heating at the higher temperature.
A Convenient Method for the Preparation of Hydrogensiloxanes
Authors: Yamamoto Yasushi 
Published: August 2006

Abstract
Chlorosilanes containing fluorinated organo-substituents are hydrolyzed in a stirred mixture of 1,1,3,3-tetramethyldisiloxane and hydrochloric acid to give the corresponding hydrogensiloxanes substituted with dimethylsiloxy groups in place of chlorine atoms.
Stereochemical Aspects on the BF3·Et2O Catalyzed Ring Contraction of 5-Substituted 2,3-Epoxycyclohexanones
Authors: Obuchi Kazuyuki , Hayashibe Satoshi , Asaoka Morio , Takei Hisashi 
Published: August 2006

Abstract
In the BF3·Et2O catalyzed rearrangement of 5-substituted 2,3-epoxycyclohexanones, the stereochemistry of the forming quaternary carbon center was directed by the chirality at 5-position.
Preparation of Niobates of Rhodium and Nickel by Chemical Mixing Methods
Authors: Yin Yuan-Gen , Wakasugi Takashi , Shindo Hisakazu , Uchijima Toshio , Kunimori Kimio 
Published: August 2006

Abstract
Niobates of rhodium or nickel by were prepared by double decomposition of aqueous rhodium or nickel salt solution with tetraalkylammonium polyniobate and with alkali orthoniobate or metaniobate, as well as by decomposition of mixed citrates of niobium with Rh or Ni. The niobates thus prepared were shown by X-ray diffraction to be well-crystallized and essentially monophasic. The calcination temperature required to achieve crystallization of all the samples is much lower than ceramic methods.
13C NMR Study of Chloro- and Methylthiophenium Ions
Authors: Yoshino Akihiro , Takahashi Kensuke , Sone Tyo 
Published: August 2006

Abstract
The 13C NMR spectra of fifteen cations formed from chloro- and methylthiophenes were observed in HSO3F solutions at −50 °C. Protonation occurred at one of the α-carbons in all of the cases studied. In these systems, the 13C chemical shifts are classified into four ranges without overlapping. The result is useful for the identification of the carbons in the cationic species. Protonated protons in the cationic species can exchange intramolecularly and intermolecularly, even with those in solvents.
Prismatic and Antiprismatic [42]Ferrocenophanes ([4](1,1′)[4](3,3′)- and [4](1,1′)[4](3,4′)Ferrocenophanes)
Authors: Hisatome Masao , Nakanishi Kunihiko , Yamakawa Koji , Kozawa Kozo , Ucnida Tokiko 
Published: August 2006

Abstract
[4](1,1′)[4](3,4′)Ferrocenophane (2a), also trivially called antiprismatic [42]ferrocenophane, which possesses a C2 symmetric configuration has been synthesized via intramolecular oxidative coupling of the dienolate ion derived from 3,4′-diacetyl[4](1,1′)ferrocenophane. The antiprismatic phane (2a) and the corresponding prismatic [4](1,1′)[4](3,3′)ferrocenophane (1a), which is bridged by a C2ν symmetric mode, has been characterized by X-ray analysis and 1H NMR and electronic spectrometries. The crystal data of the phanes are as follows: 1a, orthorhom-bic, Pbca, a = 18.469(4), b = 19.994(4), c = 7.610(2) Å; Z = 8; 2a, triclinic, , a = 7.547(1), b = 8.540(1), c = 5.886(1) Å, α = 96.60(1), β = 107.10(1), γ = 101.71(1)°, Z = 1. Antiprismatic phane 2a has a completely staggered conformation about the two cyclopentadienyl (Cp) rings, while prismatic 1a has an intermediary conformation of eclipsed and staggered forms. The Cp–Fe–Cp distance of 2a (3.260 Å) is shorter than that of 1a (3.275 Å). The hypsochromic shift of the d–d* absorption band of 2a in the electronic spectrum is more remarkable than that of 1a (ferrocene, 443 nm; 1a, 420 nm; 2a, 403 nm in THF). Those results reveal that an antiprismatic bridging mode with tetramethylene chains brings about a higher strain in the molecule compared with a prismatic one.
The Hydroboration of 3-Chloro-1-iodo-1-propyne with Dialkylboranes, and Its Application to the Syntheses of Some Geminally Dialkylated Propene Derivatives
Authors: Masuda Yuzuru , Hoshi Masayuki , Arase Akira 
Published: August 2006

Abstract
3-Chloro-1-iodo-1-propyne is smoothly hydroborated with dialkylboranes, giving (Z)-(3-chloro-1-iodo-1-propenyl)dialkylboranes exclusively. Subsequent treatment of the hydroboration mixture with sodium methoxide or aqueous sodium hydroxide results in migration of two alkyl groups from the boron atom to the α-alkenyl carbon atom to provide dialkylated allylboranes, which are protonolyzed with methanol or water to produce 1,1-dialkyl-1-propenes. Oxidation of the allylboranes with alkaline hydrogen peroxide prior to protonolysis gives 1,1-dialkyl-2-propen-1-ols. Treatment of (Z)-(3-chloro-1-iodo-1-propenyl)dicyclohexylborane with Grignard reagents, followed by protonolysis with acetic acid, provides 3-alkyl-3-cyclohexyl-1-propenes in which the alkyl group is derived from Grignard reagent.
13β-Hydroxylation of Milbemycins by Selenium Dioxide
Authors: Tsukamoto Yoshihisa , Sato Kazuo , Kinoto Takao , Yanai Toshiaki 
Published: August 2006

Abstract
Introduction of a hydroxyl group to milbemycin nucleus was examined. Starting from 5-oxo-5-deoxymilbemycins, 13β-hydroxy-5-oxo-5-deoxymilbemycins were obtained stereo- and regioselectively by selenium dioxide oxidation in formic acid and subsequent acidic hydrolysis. The stereochemistry of the hydroxyl group was elucidated by 1H NMR study.
Synthesis of Benzochlorin Monomer, Dimer, and Porphyrin-Benzochlorin Heterodimer from 5-Aryl- and 5,15-Diaryl-octaethylporphyrins
Authors: Osuka Atsuhiro , Ikawa Yoshiya , Maruyama Kazuhiro 
Published: August 2006

Abstract
Vinylogous Vilsmeier formylation of nickel(II) 5,15-di-p-tolyl-octaethylporphyrin gave the corresponding meso-(2-formylvinyl)porphyrin, which, on treatment with trifluoroacetic acid, provided the corresponding benzochlorin derivative. In the case of the copper(II) complex, Lewis acid such as BF3·Et2O and SnCl4 catalyzed the cyclization to the benzochlorin without demetallation. Similar vinylogous Vilsmeier formylation of the nickel(II) and copper(II) complexes of 5-p-tolyloctaethylporphyrin resulted in the selective formation of 5-p-tolyl-10-(2-formylvinyl)porphyrin. Subsequent cyclization of these metal complexes took place with marked different regioselectivity; the nickel(II) complex favors the cyclization at near the 5-p-tolyl substituent, while the copper(II) complex favors the cyclization at the opposite site. Application of these synthetic methods to the 4,4′-biphenylylene-bridged diporphyrin led to the synthesis of porphyrin–benzochlorin heterodimer and benzochlorin homodimer. The steady-state fluorescence spectrum of free base form of the heterodimer suggested the intramolecular singlet excitation energy transfer from the porphyrin to the benzochlorin.
Cd2+-Catalyzed Methanolysis of Phenyl Phosphatosulfate. Selectivity of Metal Ion in the Site of Cleavage of P–O and S–O Bond
Authors: Eiki Toshio , Negishi Shin-ichi , Tagaki Waichiro , Izumi Mitsunori , Ichikawa Kazuhiko 
Published: August 2006

Abstract
It was reported previously that metal ions such as Mg2+, Cr3+, Cu2+, Mn2+, and Ca2+ catalyzed selective P–O bond cleavage of P–O–S linkage in the methanolysis of phenyl phosphatosulfate (PPS), and in contrast, metal ions such as Zn2+, Fe3+, Al3+, and Be2+ promoted selective S–O bond cleavage.1) We have now found that Cd2+ catalyzes mixed cleavage of P–O and S–O bond in a ratio of 58 and 42%, respectively, in the methanolysis of PPS. The value of second-order-rate constant (k2) for Cd2+ catalyzed P–O bond cleavage satisfied the correlation between values of k2(P–O) and ionic radii of metal ions, but that for Cd2+ catalyzed S–O bond cleavage was considerably smaller than that expected from the rate correlation. The presence of chloride ion reduced the rate of Cd2+ catalyzed P–O bond cleavage to about one tenth of that in the absence of chloride ion, but inhibited completely the S–O bond cleavage catalyzed by Cd2+ or Zn2+. The kinetic studies suggested that the inhibition by chloride ion occurred with the formation of ternary (PPS·Cd2+·Cl−) and tetramerous (PPS·Zn2+·2Cl−) complexes of substrate, metal ion and chloride ion. On the basis of these results the selectivity of the metal ion in the site of bond cleavage was discussed.