Synthesis of an antimetastatic tetrasaccharide β-D-Gal-(1→4)-β-d-GlcpNAc-(1→6)-α-D-Manp-(1→6)-β-D-Manp-OMe

An antimetastatic tetrasaccharide T₁,β-D-Gal-（1→4）-β-D-GlcpNAc-（1→6）-α-D-Manp-（1→6）-β-D-Manp-OMe,was synthesized with two approaches.The first approach was a conventional method employing thioglycoside and Koenigs-Knorr glycosylation reaction in 24%overall yield.The second one was a novel route through the azidoiodo-glycosylation strategy by using 2-iodo-2-deoxylactosyl azide as the donor in 36%overall yield.     

Advanced procedure for the enzymatic ring opening of unsaturated alicyclic β-lactams

Enantiopure β-amino acids 1a–4a and β-lactams 1b–4b were prepared simultaneously through the lipolase-catalysed enantioselective ring opening of unsaturated racemic β-lactams (±)-1-(±)-4. High enantioselectivities (E>200) were observed when the reactions were performed with 1 equiv of water in iPr₂O at 70 °C. The resolved (1R,2S)-amino acids (yield⩾45%) and (1S,5R)-, (1S,6R)- and (1S,8R)-lactams (yield⩾47%) could be easily separated. The ring opening of lactam enantiomers 1b–4b with 18% HCl afforded the corresponding β-amino acid hydrochlorides 1c·HCl–4c·HCl (ee >95%).     

Asymmetric synthesis of β-fluoroaryl-β-amino acids

The conjugate addition of lithium (R)-N-benzyl-N-(α-methylbenzyl)amide to a range of β-fluoroaryl-α,β-unsaturated esters gave the corresponding β-amino esters with high diastereoselectivity and in good isolated yields. Sequential treatment of the resultant β-fluoroaryl-β-amino esters under optimised hydrogenolysis conditions, followed by ester hydrolysis with 2.0 M aq HCl, provided access to a range of β-fluoroaryl-β-amino acids in good yield.     

Do lipases also catalyse the ring cleavage of inactivated cyclic trans-β-lactams?

Twelve-membered cyclic cis- and trans-β-lactams 1b and 2b and the corresponding cyclic cis- and trans-β-amino acid enantiomers, 1a, 1c and 2a, 2c were prepared through the CAL-B-catalysed enantioselective ring cleavage of racemic cis-13-azabicyclo[10.2.0]tetradecan-14-one, (±)-1, and trans-13-azabicyclo[10.2.0]tetradecan-14-one, (±)-2. High enantioselectivities (E >200) were observed for the ring opening of both the cis- and trans-β-lactams when the Lipolase-catalysed reactions were performed with 0.5 equiv of H₂O in i-Pr₂O at 70 °C. The resolved β-lactams 1b and 2b (yield ⩾47%) and β-amino acids 1a and 2a (yield ⩾32%) could be easily separated.     

Chemical and enzymatic synthesis of glycocluster having seven sialyl lewis X arrays using β-cyclodextrin as a key scaffold material

An efficient and practical method for the large-scale synthesis of an anti-inflammatory glycocluster having seven sialyl Lewis X (SLeX) residues was established on the basis of chemical and enzymatic strategy from β-cyclodextrin (β-CD) as a key starting scaffold material. A key intermediate, β-CD derivative having seven N-acetyl-d-glucosamine (GlcNAc) residues [(GlcNAc)₇CD], was prepared by a coupling reaction with heptakis 6-deoxy-6-iodo-β-cyclodextrin and sodium thiolate containing a GlcNAc residue. Subsequent sugar elongation reactions of (GlcNAc)₇CD proceeded smoothly by means of β-1,4-galactosyltransferase, α-2,3-sialyltransferase, and α-1,3-fucosyltransferase V in the presence of the corresponding sugar nucleotides (UDP-Gal, CMP-Neu5Ac, and GDP-Fuc) and allowed to give a mono-dispersed glycodendrimer (M_w=7924.5, calcd for C₃₀₁H₄₉₀N₂₁O₁₉₆S₇Na₇; MALDI-TOF MS, m/z 7946 [M+Na]⁺) that completely substituted with seven SLeX branches at C-6 positions in excellent overall yield (74%, 3 steps). Hyper-branched glycodendrimer, (SLeX)₇CD, exhibited highly amplified inhibitory effect on the interaction of E-selectin with SLeXn-BSA immobilized on the sensor chip by means of surface plasmon resonance method.     

Enantioselective 1,4-addition of arylboronic acids to α,β-unsaturated carbonyl compounds catalyzed by rhodium(I)-chiral phosphoramidite complexes

A chiral bidentate phosphoramidite (5a) was synthesized from Shibasaki’s linked-(R)-BINOL and P(NMe₂)₃ as a new ligand for rhodium(I)-catalyzed asymmetric 1,4-addition of arylboronic acids to α,β-unsaturated carbonyl compounds. The effects of 5a and Feringa’s monodentate phosphoramidite (4, R¹, R² = Et) on the yields and enantioselectivities were fully investigated. The reaction was significantly accelerated in the presence of a base such as KOH and Et₃N, allowing the reaction to be completed at the lower temperatures than 50 °C. The addition to cyclic enones such as 2-cyclopentenone, 2-cyclohexenone and 2-cycloheptenone at 50 °C in the presence of an [Rh(coe)₂Cl]₂-4 (R¹, R² = Et) complex resulted in enantioselectivities up to 98%, though it was less effective for acyclic enones (0–70% ee). On the other hand, a complex between [Rh(nbd)₂]BF₄ and 5a completed the addition to cyclic enones within 2 h at room temperature in the presence of Et₃N with 86–99% yields and 96–99.8% ee. This catalyst was also effective for acyclic enones, resulting in 62–98% yields and 66–94% ee. The 1,4-additions of arylboronic acids to unsaturated lactones and acyclic esters with rhodium(I)-phosphoramidites complexes were also investigated.     

Synthesis of rigid and C2-symmetric 18-crown-6 type macrocycles bearing diamide–diester groups: enantiomeric recognition for α-(1-naphthyl)ethylammonium perchlorate salts

A series of rigid and chiral C₂-symmetric 18-crown-6 type macrocycles (S,S)-4, (S,S)-5, (S,S)-6 and (R,R)-2 bearing diamide–ester groups were synthesized. The binding properties of these macrocycles were examined for α-(1-naphthyl)ethylammonium perchlorates salts by an ¹H NMR titration method. Taking into account the host employed, important differences were observed in the K_a values of (R)- and (S)-enantiomers of guests for macrocycles (S,S)-4 and (S,S)-6, K_S/K_R = 3.6, and K_S/K_R = 0.1 (K_R/K_S = 10.3) ΔΔG = 3.19 and ΔΔG = ?5.77 kJ mol^?1, respectively. The results indicated excellent enantioselectivity of macrocyclic (S,S)-6 towards the enantiomers of α-(1-naphthyl)ethylammonium perchlorate salts.     

New chemical and chemo-enzymatic routes for the synthesis of (RS)- and (S)-enciprazine

The chemo-enzymatic synthesis of racemic and enantiopure (RS)- and (S)-enciprazine 1, a non-benzodiazepine anxiolytic drug, is described herein. The synthesis started from 1-(2-methoxyphenyl) piperazine 3, which was treated with 2-(chloromethyl) oxirane (RS)-4 using lithium bromide to afford a racemic alcohol, 1-chloro-3-(4-(2-methoxyphenyl) piperazin-1-yl) propan-2-ol (RS)-6 in 85% yield. Intermediate (S)-6 was synthesized from racemic alcohol (RS)-6 using Candida rugosa lipase (CRL) with vinyl acetate as the acyl donor. Various reaction parameters such as temperature, time, substrate, enzyme concentration, and the effect of the reaction medium on the conversion and enantiomeric excess for the transesterification of (RS)-6 by CRL were optimized. It was observed that 10 mM of (RS)-6, 50 mg/mL of CRL in 4.0 mL of toluene with vinyl acetate (5.4 mmol) as acyl donor at 30 °C gave good conversion (C = 49.4%) and enantiomeric excess (ee_P = 98.4% and ee_S = 96%) after 9 h of reaction. Compound (S)-6 is a key intermediate for the synthesis of enantiopure (S)-1. The (RS)- and (S)-enciprazine drug 1 was synthesized by treating (RS)- and (S)-6 with 3,4,5-trimethoxyphenol 5 using MeCN as a solvent and K₂CO₃ as a base.     

Asymmetric fluorination of β-keto esters catalyzed by chiral rare earth perfluorinated organophosphates

Novel chiral rare earth metal complexes bearing perfluorinated binaphthyl phosphate ligand RE[(R)-F₈BNP]₃ (RE = rare earth; F₈BNP = 5,5′,6,6′,7,7′,8,8′-octafluoro-1,1′-binaphthyl-2,2′-diyl phosphate) have been synthesized and used as a catalyst for the asymmetric electrophilic fluorination reaction of β-keto esters. The use of Sc[(R)-F₈BNP]₃ catalyst in combination with 1-fluoropyridinium triflate (NFPY–OTf) as a fluorinating agent was found to give the desired α-fluoro-β-keto esters in high chemical yields and enantiomeric excesses (up to 88% ee) under mild conditions.     

Synthesis of linear and cyclic homo-β-peptides based on a binaphthylic β-amino acid with only axial chirality

The terminally protected, linear, homo-β-peptides Boc-[(R)-β^2,2-HBin]_n-OMe (n = 2–6) as well as the cyclic homo-β-peptides c[(R)-β^2,2-HBin]₃ and c[(S)-β^2,2-HBin]₄, all derived from the 2′,1′:1,2;1″,2″:3,4-dinaphthcyclohepta-1,3-diene-6-aminomethyl-6-carboxylic acid residue β^2,2-HBin possessing only axial chirality, have been synthesized in solution by the EDC/AtOH coupling method for chain elongation, and by cyclization of pentafluorophenyl esters. A conformational analysis suggested the concomitant occurrence of different intramolecularly H-bonded forms for the linear oligomers in solution.     

Assay of caffeoylquinic acids in Baccharis trimera by reversed-phase liquid chromatography

Baccharis trimera commonly named ‘carqueja’, is wide-spread in South America and are used as raw material for herbal medicines. A reversed-phase liquid chromatography (RP-LC) method coupled to diode array detector was developed for the analysis of caffeoylquinic acids (CQAs), the main compounds responsible for its digestive activity. The identity of the quinic acids was established by mass spectrometry and were them: 5-O-[E]-caffeoylquinic acid, 3,4-O-[E]-dicaffeoylquinic acid, 3,5-O-[E]-dicaffeoylquinic acid, 4,5-O-[E]-dicaffeoylquinic acid and a tricaffeoylquinic acid. The RP-LC method for the quantitation of the caffeoylquinic acids was validated according to ICH guidelines, based on the following parameters: linearity, selectivity, robustness, limits of detection and quantification, precision and recovery. Hydroalcoholic extracts were prepared by the maceration of the plant material with ethanol:water 1:1 (v/v) in a 0.1:25 g mL^?1 plant:solvent ratio in a water bath at 40 °C. Validation data indicated that the HPLC method proposed is suitable for the analysis of caffeoylquinic acids in B. trimera raw material. The results of the LOD and LOQ analyses for the 5-CQA were 4.1 μg mL^?1 and 12.5 μg mL^?1, respectively, 1.3 μg mL^?1, 3.9 μg mL^?1 for 4,5-diCQA and 1.7 μg mL^?1, 5.1 μg mL^?1 for triCQA. The levels of total CQAs ranged from 2.1 to 4.0 g% (w/w). The influence of season harvest and site collection was also evaluated and variations were observed in the results and can be related to phonologic phase, different locations, seasons and soil. Long term and photostability of plant material were carried out and was observed a stable behavior during the time of the experiments.     

A family of dodecanuclear Mn11Ln single-molecule magnets

A series of four isostructural dodecanuclear complexes [Mn^III₉Mn^II₂Ln^III(O)₈(OH)(piv)₁₆(NO₃)(CH₃CN)]·xCH₃CN·yC₇H₁₆ (piv = pivalate; x = ½, y = ¾, Ln = Tb (1); x = 2, y = ½, Ln = Dy (2), Ho (3), and Y (4)) has been prepared for which the structural motif described as ‘a lanthanide ion nested in a large manganese shell’ is observed. All compounds show out-of-phase signals in their ac susceptibilities, and their single-molecule magnet behaviour was confirmed by single-crystal micro-SQUID studies of 1-3 which show hysteresis loops of molecular origin at T < 1.0 K. The SMM behaviour observed in compounds 1-3 is more pronounced than that for 4, which contains the diamagnetic Y^III ion. This is principally the result of ferromagnetic coupling between the paramagnetic anisotropic Ln^III ions (Tb^III, Dy^III and Ho^III) and the manganese shell, which enhances the total spin ground state of the complexes.     

Chloro/bromotrimethylsilane-Cu(NO3)2·3H2O: Safe and efficient reagent system for the decarboxylative ipso-nitration and dibromination of cinnamic acids

Further synthetic potential of halotrimethylsilane-nitrate salt mixture is revealed. A mixture of TMSX-Cu(NO₃)₂·3H₂O system is found to be an efficient reagent system for both the decarboxylative nitration (ipso-nitration) when X = Cl, and dibromination of cinnamic acids, with X = Br, under mild conditions. The reactions are safe and simple, affording the corresponding products (E)-β-nitrostyrenes, and anti-2,3-dibromo-3-phenylpropanoic acids in high yields with high selectivity in a relatively short time. Use of hazardous and toxic nitrating systems such as acetyl nitrate and brominating agents such as molecular bromine can be avoided.     

α-Chymotrypsin-catalyzed peptide synthesis in frozen aqueous solution using N-protected amino acid carbamoylmethyl esters as acyl donors

A kinetically controlled peptide synthesis catalyzed by α-chymotrypsin was performed in frozen aqueous solution (ice, −24 °C). The yield of the peptide was significantly improved by the use of the carbamoylmethyl (Cam) ester as the acyl donor instead of the conventional ethyl ester. The peptide yield increased up to ca. 90% when N-benzyloxycarbonyl (CBZ)-Phe-OCam and H-Phe-NH₂ were used as the acyl donor and nucleophile, respectively. Such an improvement of the peptide yield in ice was also observed in the coupling of other CBZ-amino acid Cam esters as acyl donors. Furthermore, this approach was applied to the synthesis of peptides containing d-amino acids. The peptides such as CBZ-d-Phe-Phe-NH₂, CBZ-Phe-d-Phe-NH₂ and CBZ-d-Phe-d-Phe-NH₂ were also obtained in excellent to moderate yields in ice. A high diastereoselectivity towards the l–l peptide was observed when the racemic amino acid Cam ester was used as the acyl donor in ice.     

A ceric ammonium nitrate based oxidative cleavage pathway for the asymmetric aldol adducts of oxadiazinones derived from (1R,2S)-N-p-methoxybenzylnorephedrine

An N₄-p-methoxybenzyloxadiazinone has been prepared from (1R,2S)-norephedrine through a process of reductive amination, N-nitrosation, reduction, and cyclization. The oxadiazinone was acylated and employed in the asymmetric aldol addition reaction with aromatic and aliphatic aldehydes to yield aldol adducts in isolated yields ranging from 54% to 90%. Selected aldol adducts were treated with ceric ammonium nitrate in aqueous acetonitrile to afford the desired β-hydroxycarboxylic acids through a tandem process of oxidative cleavage of the N₄-p-methoxybenzyl group and acidic hydrolysis of the N₃-acyl side chain. The β-hydroxycarboxylic acids were recovered in high diastereomeric purity as determined by 500 MHz ¹H NMR spectroscopy and the absolute configuration was confirmed by polarimetry. The chiral auxiliary unit, the 3,4,5,6-tetrahydro-2H-1,3,4-oxadiazin-2-one (oxadiazinone), was converted into its corresponding 3,6-dihydro-2H-1,3,4-oxadiazin-2-one (oxadiazinone) through an oxidative pathway promoted by the ceric ammonium nitrate.     

Synthesis and asymmetric catalytic application of chiral imidazolium–phosphines derived from (1R,2R)-trans-diaminocyclohexane

Reaction between a chiral imidazole–amine precursor derived from (1R,2R)-trans-diaminocyclohexane and P¹Cl (where P¹ = PPh₂, P(1,3,5-Me₃C₆H₃)₂, P(2,2′-O,O′-(1,1′-biphenyl), P((R)-(2,2′-O,O′-(1,1′-binaphthyl))) and P((S)-(2,2′-O,O′-(1,1′-binaphthyl)))) followed by RX (where R = ⁿPr, ⁱPr, CHPh₂, X = Br; R = ⁱPr, X = I), respectively, gives a selection of chiral imidazolium–phosphine compounds. Deprotonation of the imidazolium salt gives the corresponding NHC–P ligands that can be used in metal-mediated asymmetric catalytic applications. Catalytic reactions show that NHC–P ligands give a significantly greater rate of reaction for a palladium catalysed allylic substitution reaction in comparison to analogous di-NHC or NHC–imine ligands and that NHC–P hybrids are also effective for iridium catalysed transfer hydrogenation.     

Enantioselective sorption of some chiral carboxylic acids by various cyclodextrin-grafted iron oxide magnetic nanoparticles

A new enantioselective sorption approach to chiral carboxylic acid molecules such as (R)-(?)-N-(3,5-dinitrobenzoyl)phenylglycine (R)-(?)DNBPG, (S)-(+)-N-(3,5-dinitrobenzoyl)phenylglycine (S)-(+)DNBPG, (R)-(+)-N-(1-phenylethyl)phthalamic acid (R)-(+)PEPA and (S)-(?)-N-(1-phenylethyl)phthalamic acid (S)-(?)PEPA regarding their complexation with three diversely functionalized β-cyclodextrin grafted iron oxide nanoparticles in the aqueous phase, was developed. The sorption efficiencies of these carboxylic acids were carried out by high-performance liquid chromatography (HPLC) with an Ace 5 C18 column. The effects of temperatures on the sorption were also investigated. The results showed that the ether functionalized derivative of β-cyclodextrin Al-CD-MNPs has a specific affinity for (R)-(?)DNBPG at 30 °C and pH 7.0. The amine functionalized derivative of β-cyclodextrin Am-CD-MNPs has a greater affinity towards not only (S)-(?)DNBPG, but also (R)-(+)PEPA compared with their other isomers, which are the (R)-isomer of DNBPG and the (S)-isomer of PEPA at 30 °C and pH 7.0. In addition, although amide functionalized derivatives of β-cyclodextrin (Amd-CD-MNPs) have an affinity towards both isomers of some chiral carboxylic acids; no selective affinity was observed at 30 °C and pH 7.0.     

Spontaneous resolution of a novel chiral coordination polymer through supramolecular interactions and solvent symmetry breaking

The spontaneous resolution reaction of racemic trans-2,3-dihydro-2,3-dipyridyl-benzo[e]indole 1 with Cd(ClO₄)₂·6H₂O in the presence of 2-butanol under solvothermal reaction conditions favors the formation of crystal 2 [P-Cd(R,R,-1)₂(ClO₄)₂], while a similar reaction in the presence of ethanol only favors the formation of crystal 3 [M-Cd(S,S,-1)₂(ClO₄)₂]. The crystal structural determination shows that both 2 and 3 crystallize in chiral enantiomorphous space groups (P6₁22 and P6₅22) and their structures are 1D infinite chain, and are just enantiomorphous pairs most like. The spontaneous resolution process displays estimated ee values of ca. +0.6 for 2-butanol and ca. −0.4 for ethanol. Enantiomerically pure (S,S)-trans-2,3-dihydro-2,3-dipyridyl-benzo[e]indole (S,S,-1) can be obtained through the decomposition of mechanically separated 3. Additionally (S,S,-1) also crystallizes in a chiral space group (P2₁). The CD (circular dichroism) spectra of both 2 and 3 in the solid state are also approximately enantiomorphous pairs. However, their fluorescent spectra in the solid state display a moderate difference in maximum emission peaks (Δλ = 19 nm). Crystal data for 2: C₄₄H₃₄Cl₂N₆O₈Cd, M = 958.07, hexagonal, P6₁22, a = 10.5488(5), c = 68.256(4) Å, α = γ = 90°, β = 120°, V = 6577.8(6) Å³, Z = 6, D_c = 1.451 mg m⁻³, R₁ = 0.0498, wR₂ = 0.1124, μ = 0.679 mm⁻¹, S = 0.623, Flack χ = −0.02(6). For space group P6₅22, R₁ = 0.0670, wR₂ = 0.1602, S = 0.725 with a Flack value of 1.03(7); Crystal data for 3, C₄₄H₃₄Cl₂N₆O₈Cd, M = 958.07, hexagonal, P6₅22, a = 10.5446(3), c = 68.265(3) Å, V = 6573.3(4) Å³, Z = 6, D_c = 1.452 mg m⁻³, R₁ = 0.0444,wR₂ = 0.1002, μ = 0.679 mm⁻¹, S = 0.558, Flack χ = 0.01(5). For space group P6₁22, R₁ = 0.0501, wR₂ = 0.1178, S = 0.599 with a Flack value of 1.00(5). The low Flack parameter indicates that the absolute configurations of 2 and 3 are stated; Crystal data for (S,S)-1, C₂₂H₁₇N₂, M = 323.39, orthorhombic, P2₁2₁2₁, a = 9.2598(7), b = 9.4617(8), c = 19.1452(16) Å, V = 1677.4(2) Å³, Z = 4, D_c = 1.281 mg m⁻³, R₁ = 0.0417, wR₂ = 0.1191, T = 293 K, μ = 0.077 mm⁻¹, S = 0.862.     

New iodate materials as potential laser matrices. Preparation and characterisation of α-M(IO3)3 (M = Y,Dy) and β-M(IO3)3 (M = Y,Ce, Pr,Nd, Eu,Gd, Tb,Dy, Ho,Er). Structural evolution as a function of the Ln3+ cationic radius

Anhydrous yttrium iodate presents polymorphism; two crystalline phases are obtained under hydrothermal conditions. α-Y(IO₃)₃ crystallises in the monoclinic space-group P2₁/c with a three-dimensional structure, whereas β-Y(IO₃)₃ crystallises in the monoclinic space-group P2₁/n with a two-dimensional structure. The lattice parameters are a = 7.038(1) Å, b = 8.466(1) Å, c = 13.317(1) Å, β = 99.65(1)°, V = 782.3(2) Å³, Z = 4 for α-Y(IO₃)₃ and a = 8.685(1) Å, b = 5.964(1) Å, c = 14.958(1) Å, β = 96.99(2)°, V = 769.0(2) Å³, Z = 4 for β-Y(IO₃)₃. The α-form is isostructural with α-Dy(IO₃)₃ studied in this work and α-Ln(IO₃)₃ (Ln = Ce, Pr, Nd, Sm, Eu, Gd, Tb, Ho, Er, Tm, Yb, and Lu) already studied. The β-form is isostructural with β-Ln(IO₃)₃ (Ln = Ce, Pr, Nd, Eu, Gd, Tb, Dy, Ho and Er) studied in this work. The structural evolutions as a function of the Ln³⁺ cationic radius are studied. α-Y(IO₃)₃ and β-Y(IO₃)₃ present good thermal stability since they decompose at 600 °C. They are transparent up to 11.5 μm and they have good optical damage thresholds on powder.     

Dialkyl- and diaryl-platinum(II) complexes with secondary phosphines: Preparation,structure and thermal reaction giving the metallopolymer

Alkyl and arylplatinum complexes with 1,5-cyclooctadiene ligand, [PtR₂(cod)] (R = Me, Ph, C₆H₄-p-CF₃, C₆F₅), react with secondary phosphines, PHR′₂ (R′ = i-Bu, t-Bu, Ph), to afford the mononuclear platinum complexes, cis-[PtR₂(PHR′₂)₂] (1a: R = Me, R′ = i-Bu; 1b: R = Me, R′ = t-Bu; 1c: R = Me, R′ = Ph; 2a: R = Ph, R′ = i-Bu; 2b: R = Ph, R′ = t-Bu; 2c: R = R′ = Ph; 3a: R = C₆H₄-p-CF₃, R′ = i-Bu; 3b: R = C₆H₄-p-CF₃, R′ = t-Bu; 3c: R = C₆H₄-p-CF₃, R′ = Ph; 4a: R = C₆F₅, R′ = i-Bu; 4c: R = C₆F₅, R′ = Ph) in 81–98% yields. Molecular structures of the complexes except for 1a, 1c and 2a were determined by X-ray crystallography. Complex 1b has a square-planar structure with Pt–C(methyl) bonds of 2.083(8) and 2.109(8) Å, while the Pt–C(aryl) bonds of 2b–c, 3a–c, 4a and 4c (2.055(1)–2.073(8) Å) are shorter than them. Thermal decomposition of 1b, 2a–c, and 3a–c releases methane, biphenyl or 4,4′-bis(trifluoromethyl)biphenyl as the organic products, which are characterized by NMR spectroscopy. The solid product of the thermal reactions of 2b and 2c were characterized as the metallopolymers formulated as [Pt(PR′₂)₂]_n (5b: R′ = ^tBu; 5c: R′ = Ph), based on the solid-state NMR and elemental analyses.